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By J. H. Keeler

QUESTIONS raised during earlier investigations of the preferred orientation in titanium1 and zirco-nium sheet led to the examination of the rolling and annealing textures of beryllium and hafnium sheet. Since the c/a ratios are 1.568 and 1.584, less than that of ideal close packing, 1.633, it would be expected that the preferred orientations would be similar to those exhibited by zirconium and titanium. This was found to be true. However, in several regards the orientations observed for beryllium differed from those reported by Smigels-kas and Barrett4 and so are given here. The okientations for hafnium are presented since only the cold-rolling texture has been reported in the unclassified literature. The pole figures were determined by transmission using an X-ray spectrogoniometer with copper Ka radiation and the automatic pole-figure recorder designed by Geisler described previously.6 The intensity units in the pole figures in this case are only arbitrary since calibration against a random sample of the same material was not considered necessary for the original purpose of the examination. The beryllium sheet, cold-rolled from 0.036 in. to 0.006 in., a reduction of about 84 pct, exhibited a split texture with the [1010] direction in the rolling direction as shown in Fig. 1. The same specimen annealed in vacuo for 1 hr at 1000°C showed no change in orientation. These textures

Jan 1, 1959

By G. W. Elger, H. E. Bell, J. E. Tress, J. B. Wright

This paper describes laboratory techniques and subsequent results of US Bureau of Mines (USBM) research to produce chlorination-grade feed- stock from an abundant, low-grade, domestic, rock ilmenite ore. The research is part of the Bureau effort to devise technology that may help decrease US dependence on imported raw materials. A rock ilmenite containing about 46 wt % TiO2 was smelted in an electric arc furnace with coke, wood-chips, and Na2CO3 to separate most of the iron as pig iron and to form a low-iron, titanium-enriched slug. The slug was ground, pelletized, oxidized, and then sulfated with mixtures of SO2 and air in a continuous 4.5- to 9.1-kg/h (10- to 20-lb per hour) apparatus at 1023° to 122J0 K (1380° to 1740° F). The sulfated slug, containing 60% to 65% TiOb, was reground and leached in water at ambient temperature to decrease the combined levels of the troublesome calcium, magnesium, and manganese impurities from 7.0 to 1.7 wt 70. The final product was upgraded to about 8.4 wt % TiO2. This material is potentially suitable for chlorination in a fluidized bed reactor. The most favorable results were achieved with leached slug sulfated at a feed rate of 4.5 kg/h (10 lb per hour) and at temperatures of 1073° to 1123° K (1470° to 1560' F).

Jan 1, 1986

The total crude production from the Dutch East Indies, and the British Protectorates of Sarawak and Brunei for 1932 is given in the following table: Production, which had shown a rapid increase from 1921 to 1929, has since been reduced. Exploitation drilling in the majority of the larger fields was suspended and existing production kept within predetermined limits by beaning. Most of the smaller fields were shut down entirely. The depth of producing levels varies widely in the different fields. Shallow fields with drilling depths to 500 meters (1650 ft.) are still numerous as well as those with depths between 500 and 1000 m. (3300 ft.). A few of the newer fields reach greater drilling depths up to 1600 m. (5250 ft.). The deepest exploration well drilled to date (Djambi field, South Sumatra) reached a, depth of 2332 m. (7650 ft.) before abandonment in March, 1930. The specific gravities of the various crude oils produced range between 0.65 (86.2° A.P.I.) and 0.95 (17.5° A.P.I.). The lighter crudes have a high gasoline content and fuel oils are derived from the heavier crudes, which usually are rich in paraffin. Producing companies are: De Bataafsche Petroleum Maatschappij (Royal Dutch-Shell combine in Dutch territory); The Anglo-Saxon Petroleum Co. Ltd. (Royal Dutch-Shell combine in British territory); De Nederlandsch-Indische Aardolie Maatschappij (De Bataafsche Petroleum Maatschappij-Dutch East Indian Government combine); De Nederlandsche Koloniale Petroleum Maatschappij (Standard Oil Co. of

Jan 1, 1933

By David Sinclair, Philip B. Bucky

THE dimensions and shapes of mine structures may at present be determined by (1) field experience, (2) structural calculations, and (3) barodynamic tests.§ None of these, however, provide information as to the stresses, their direction and distribution in a mine structure. For the design of pillars, the placing of openings relative to working places such as gangways, haulage levels, etc., this information is desirable. Photoelastic methods provide this and, while relatively new, their application in all engineering fields is assuming increasing importance. This paper, therefore, will present the method with a few applications to mining, and with sufficient reference for further study by the reader. PART I THE PHOTOELASTIC METHOD The photoelastic method of stress measurement determines the stress distribution in a two-dimensional model by optical means. It makes use of the fact that when a piece of isotropic transparent material, such as glass, celluloid, or Bakelite, is stressed and viewed in polarized** light a picture is seen which indicates by its color bands of light, or fringes, the magnitude of the stresses, their direction and their distribution. GENERAL EXPLANATION The stress at any point 0 in a structure (Fig. 1), may be resolved into two components, P and Q, each a pure tension or compression, at right angles to each other, called principal stresses.1 To fully identify the stress, the values of P and Q and their directions or angle [0] must be known.

Jan 1, 1940

By J. C. Branner

DuriKg the past two or three years I have seen statements regarding the first discovery of fullers' earth in this country that seem to require correction or modification. One appears again in the Mineral Resources of the United States for 1909, part II., p. 738, where it is said that 'fullers' earth was firat discovered in the United States at Quincy, Fla., in 1893." In this connection the following bit of unpublished history concerning fullers' earth in the State of Arkansas is worthy of attention. In April, 1891, when I was State Geologist of Arkansas, a Swede named John Olsen, formerly a copper-miner in Michigan, but then living south of Little Rock, brought me a sample of what he thought mas fullers' earth. He reported that it was from near the town of Alexander, the locality being 1 S. 13 W., section 8, SW. quarter of the SE. quarter. My chemist, Dr. R. N. Brackett, analyzed the material, and reported: Per Cent. Silica,.....SiO2 .... 63.19 Alumina,.... A12O3 .... 18.76 Iron,.....Fe2O3 .... 7.05 Lime,.,...CaO .... 0.78 Magnesia,.... MgO .... 1.68 Potash,.... K2O ,... 0.21 Soda,.....Na2O .... 1.50 Loss on ignition,........7.57 100.74 Water at 110° to 115° C. = 7.84. Another sample from about the same locality, also brought by John Olsen, on analysis by Dr. Brackett gave :

Jan 1, 1913

NORMAN B. PILLING (author's reply to discussion *).-The discussion by Mr, Bassett raised one or two points that deserve further discussion. The printed figure for the lead content of the copper used was 0.015 per cent. and not 0.15 per cent., upon which his comment was based. A copper having the latter figure would, of course, be quite unusual. Mr. Bassett takes exception to the writer's statement regarding the distribution of cuprous oxide in wrought copper and states that "the FIG. 1.--ROLLED AND ANNEALED SHEET. ETCHED WITH AMMONIA AND HYDROGEN PEROXIDE. X 75. eutectic of copper with cuprous oxide is usually found between the crystals of pure copper, whether in the cast or the wrought form." While it is very well known that during the solidification of cast copper the cuprous oxide is segregated completely as an envelope of cuprous oxide-copper eutectic around the crystals of copper free from oxide, it is the writer's opinion that, as a result of repeated rolling, this eutectic structure is quite destroyed and the small particles of cuprous oxide become widely scattered, and in the recrystallization following, during annealing, the rearrangement of the grain boundaries takes place with much indifference to the actual distribution of these particles. In the accompanying micrograph, taken from a rolled and annealed sheet, the random distribution of the small cuprous-oxide particles with reference to the location of the grain boundaries may be seen.

Jan 3, 1919

By A. J. Opinsky

THE purpose of this note is to indicate the locations and sizes of various interstitial holes in the orthorhombic uranium lattice based on a hard-sphere model. First, plane configurations of three and four atoms will be examined, and then the true interstices surrounded by four atoms in space and by five atoms in space will be obtained. The data and notation contained in a report by Tucker' will be used. Plane Configurations Fig. 1 presents the orthorhombic uranium lattice made of spheres touching at the closest interatomic distance. The three light-colored spheres in the ab plane are illustrative of the first type of configuration to be examined. If one edge of the unit cell is taken as the origin, the three atoms can be represented by the vectors [Oi + Oj + Ok], [ai + Oj + Ok] and [(a/2)i + (b/2)j + Ok] where i, j, and k are respectively parallel to a, b, and c. In the future, this notation will be shortened to [000], [a00] and [a/2 b/2 0], respectively. A vector R = [r s t] de-scribes the position of the hole surrounded by the atoms. Since the center of the hole must be equidistant from the three atoms R2 = r2 + s2 + t2 = (r-a)2 + s2 + t2 = (r-a/2)2 + (s-b/2)2 + t2. R = [a/2 (b/4) - (a2/4b) 0] is the solution of these

Jan 1, 1955

By Juan Sodi, John F. Elliott

The standard free energy of ReS2 has been measured in the range of 1050° to 1250°K using H2/H2S mixtures and a slight variation of the method described by Hager and Elliott.1 The result is: The experimental method and apparatus were modified slightly for this study. Measurements on Cu2S were made to verify the application of the method to the work on ReS2. THE EXPERIMENTS AND RESULTS Briefly, the experimental method consisted of exposing a chip of copper or rhenium at a known temperature for 8 hr to a slowly flowing gas stream at the same temperature in which Ph2S and PH2 were known. The chip was withdrawn quickly from the hot furnace, and subsequently it was inspected for the presence of a sulfided surface. In the experiments described here, there was no ambiguity in any case as to the presence or the absence of the sulfide. At a given temperature, gas compositions for sulfidization were explored systematically until two compositions were found whose values of ?G°, Eqs. [I] and [2], were within approximately 100 cal of each other, one of which was sulfi-dizing and the other was not. These are termed the "straddle" compositions and it is assumed that the equilibrium composition lies between them. The chief modification to the apparatus, which is shown schematically in Fig. 1 of Ref. 1, was to support the metal specimen on a small alumina boat which could be moved along the reaction tube, 6 mm ID, by platinum wires. An appropriate seal at each end of the reaction tube permitted the sample to be moved from the cold end of the tube into the hot zone in 2 to 3 sec, and the sample could be withdrawn equally rapidly. Thus, it was possible essentially to quench the specimen from the reaction temperature with the reaction gas or helium flowing and without danger of breaking the reaction tube. The usual practice at the end of the experiment was to switch the gas system to the helium tank, flood the reaction chamber with helium, and pull the sample out of the hot zone. The purpose of the modification was to permit study of the sulfidization of copper without the complication of the back-reaction between the gas and the specimen as the latter cooled during slow withdrawal of it from the hot zone; this was a problem in the earlier work.&apos; A further improvement located the tip of the temperature-indieating thermocouple and the specimen precisely at the hottest part of the furnace. A carefully calibrated thermocouple, with its tip at the position of the specimen and with other conditions duplicating those of an actual experiment, showed that in the temperature range of 900° to 1122°C the temperature of the specimen differed from that of the tip of the indicating thermocouple by less than 0.5°C. The two positions were 0.5 cm apart. The reaction gas was prepared from ultrahigh-purity hydrogen (<l ppm O2, <0.5 ppm H2O) and CP grade hydrogen sulfide (99.5 pct H2S). High-purity helium (99.995 pct He) was used. All of these gases were purchased from the Matheson Co. All flow meters were recalibrated by the soap-bubble method with hydrogen, H2S, helium, and several gas compositions used during the study. These calibrations gave a linear relationship with a slope of 1.0 for the plot of log flow rate vs log pressure drop across the flow meter, in accordance with the Hagen-Poiseuille equation. The analysis of the gas was determined in the same manner as was reported previously. Good checks were obtained between the composition of the gas established by the flow-meter settings and by chemical analysis of the gas taken after the mixing bulb and ahead of the furnace. The pressures of H2S, H2, S2, and HS in the equilibrium gas at temperature were calculated from the following data :3 The pressures of the species S and S8 were negligible for the conditions of the experiments.3 There was no sign of vaporization of ReS2 either by weight loss or deposits in the reaction tube. Thus it is not possible to account for the apparent volatility of the compound reported by Juza and Biltz.2 The inlet gas composition and the calculated equilibrium ratio of PH2 S/PH2 for the "straddle" points of each experiment are shown in Table I. The specimens of metal for the experiment were small clippings of annealed copper (99.9+ pct) sheet 0.005 in. thick that was obtained from Baker and Adamson and of "high-purity" rhenium (99.9+ pct) sheet 0.005 in. thick that was purchased from Chase Brass and Copper Co. A specimen was removed from the apparatus; inspected for the presence of the sulfide, and then stored in a sealed vial. A fresh clipping was used in each measurement. The condition of the surface of each specimen after the experiment is noted in Table I.

Jan 1, 1969

By T. A. Rickard

Our Transactions contain two notable papers descriptive of the stamp-milling practice of the Black Hills and of Grass Valley, namely, the elaborate and complete treatise of Prof. H. 0. Hofman, on " Gold-Milling in the Black Hills,"" and the paper describing the North Star mill, by E. R. Abadie, its superintendent. Having visited and examined the stampmills of both localities, I venture to offer here such comment as more recent information or a different point of view has suggested.†

Jan 1, 1896

[Abrahamson, Guy C., (5&apos;43) Lt., 0-880861, Hammer Field Fresno Calif. Adamec, LAW, (8&apos;42) c/o Braden Copper Co., Rancagua, Chile. Adams, Karl S., (9&apos;43) Univ. of New Hampshire, Durham, N. H. Agnilar, Roperto Q., (9&apos;43) Texas College of Mines, El Paso Texas. Ainge, B&apos;onald Farra, (943) Otago University, Dunedin, New Zealand. Akaran, Cevdet A,, (9&apos;44) Pennsylvania State College, State College, Pa. Albala, Americo, (5&apos;44) School of Mineral Industries, The Pennsylvania State College, State College, PA.]

Jan 1, 1946

Held at San Francisco, Cal., Thursday to Sunday, Sept. 16 to 19, 1915 COMMITTEES Arrangements CHARLES W. MERRILL, Chairman EDWARD H. BENJAMIIN H. C. HOOVER FRED `V. BRADLEY W. C. RALSTON ABBOT A. HANKS G. H. CLEVENGER Excursion and Accommodations ABBOT A. HANKS, Chairman E. T. BLAKE R. H. BEDFORD C. G. DENNIS FREDERICK BRADSHAW C. E. GRUNSKY, JR. EDMUND JUESSEN ARTHUR B. FOOTE F. A. KEITH GEORGE 0. BRADLEY CHARLES JANIN E. N. ENGELHARDT R. S. HASELTINE N. CLEAVELAND

Jan 12, 1915

By Barry S. Siegal

Spectral reflectance data in the wavelength region of 0.45 to 2.4 µm have been obtained for various rock types and different forms of natural vegetation by means of JPL&apos;s portable field reflectance spectrometer. Computer analysis of these data has demonstrated the importance of obtaining remotely sensed spectral data beyond the wave- length region sensed by Landsat. Computer processing techniques have been developed and used for the analysis of these data and their application to a variety of geologic problems.

Jan 1, 1977

By Orvar Nyquist, Klaus W. K. Lange, John Chipman

Liquid Fe-C-Si alloys containing 0 to 12 pet Si and up to 4 pet C were equilibrated with carburizing gases at 1550°C. Two to 5 alloys simultaneously were held in close proximity for 5 to 7 hr to establish uniform carbon activity in the group. Analysis of the data gives the activity coefficient of carbon as a function of the mole fractions of carbon and silicon, Fig. 7. Values of the interaction coefficients at infinite dilution are

Jan 1, 1962

By R. J. Block, G. H. Kehl

IN order to investigate the possibility of a spontaneous low-temperature transformation, resistivity measurements were made on a sample of eutectoid beryllium- copper. A cast specimen of 5.965 pct Be, 94.035 pct Cu was homogenized at 650°C for 22 hr, furnace cooled to 550°C, and held for 2 hr to allow the 0 - a ß-a+? reaction to proceed. In an attempt to refine the ß grain size, the specimen was then reheated to 620°C, held

Jan 1, 1960

By S. Nenno, T. Saburi, Y. Mizutani, M. Yomarnoto, K. Komatsu

In the equilibrium phase diagram of the Ni-Mo sys-tem1,2 available at present, intermetallic compounds (or ordered phases)ß(Ni4Mo) and ?(Ni3Mo) are known to exist to the nickel rich side. In our recent investigations on Ni-Mo alloys, however, it has been found that the quenched alloys from the high temperature region containing more molybdenum than the Ni4Mo do not decompose directly into 0 and when annealed isothermally below the peritectoid temperature, i.e., 865°C. This note is to report the existence of Pt2Mo type superlattice (possibly ordered Ni2Mo) as a metastable phase in the early stage of decomposition. Alloys containing 20.1, 22.7, and 24.4 at. pct Mo were prepared by vacuum-melting electrolytic nickel of 99.9 pct purity and molybdenum powder of 99.9 pct purity in an alumina crucible. From the resulting ingots, sheets 0.3 mm thick were obtained by forging, hot-, and cold-rolling. The sheet specimens were water-quenched from ! region and subsequently annealed for various periods of time at temperatures below the peritectoid temperature. On these specimens were made optical-microscopic and transmis-sion-electron-microscopic observations. Fig. 1- Optical micrograph of the 22.7 at. pct Mo specimen annealed for 100 hr at 700°C after quenching. (ß + ?) region, B, nucleated along a grain boundaries are invading the preexisting (ß + Ni2Mo) region, A. Details of A are observable only by electron microscopy. Etchant: 60 pct HNO3-40 pct CH3COOH.

Jan 1, 1970

By H. C. Chao, Y. E. Smith, L. H. Van Vlack

ThE phase relationships for the MnO-MnS system have been investigated only in the eutectic region. wentrupl reported a eutectic at 1280°C (2345°F) with approximately 50 wt pct of each component, as based on the earlier work of Andrew, Maddocks, and Fowler.2 More recently silverman3 corrected these figures to 2275° ±10°F (1246°C) with 63 wt pct MnS and 37 pct MnO. Neither Wentrup nor Silverman investigated the solid-solution limits in this system. However, Wentrup did suggest with his phase diagram sketch that the maximum solubility of MnS in MnO is 10 wt pct, and the solubility of MnO in MnS is nearer 20 wt pct, Fig. 1. These figures have been utilized in subsequent publications without further verification.4 There had been evidence found in this laboratory that the above solid-solution figures were high. An investigation was therefore conducted using the following procedure. Samples containing MnO and MnS were contained in platinum foil, heated just above the eutectic temperature in a purified nitrogen at- mosphere, and quenched into distilled water. The MnO had been prepared by calcining reagent grade MnCO3 in nitrogen at 1400°C. Only MnO was detected in subsequent X-ray diffraction analyses. The MnS had been prepared by sulfur deoxidation of reagent grade MnSO4 according to the reaction: MnSO4 + S2 ? MnS + 2SO2 The details of the sulfide preparation procedure, which utilized atmospheric sulfur pressures at 950°C, are discussed elsewhere.5 The sulfur content of the sulfide was determined to be 36.8 * 0.2 pct, which matches the stoichiometric value of 36.9 pct. No evidence of either MnO or MnSO4 was detected microscopically or by X-ray diffraction. The single-phase combinations of MnO and MnS at the eutectic temperature indicate the limit of solid solution as shown in Fig. 2(a) and (c), and the revised phase diagram is shown in Fig. 2(d). The melting temperature for MnO is that provided by Glasser.6 The eutectic temperature of 1232° ± 5°C and eutectic composition of 64 wt pct MnS are in close agreement with Silverman&apos;s correction of Wentrup&apos;s work. The maximum solubility of MnO in MnS was determined to be 1.7 ± 0.2 wt pct. The maximum solubility of MnS in MnO was determined to be 1.8 ± 0.2 wt pct. These figures represent the lower limit for the presence of liquid at 1260°C and are significantly lower than the earlier estimated solid-solution figures. The authors wish to acknowledge the support of U.S. Steel&apos;s Edgar C. Bain Laboratory for Fundamental Research. The comments and critical suggestions of Drs. A. S. Keh, R. Rickett, and R. B. Snow are appreciated.

Jan 1, 1963

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,&apos; only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,&apos; and that the solid solution is quite limited in the MnO-MnS system.&apos; The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1&apos; and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na&apos; and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°&apos;K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°&apos;K and

Jan 1, 1968

By J. L. LeBlanc, R. L. Lewis

This study presents an analysis of annular backpressure variations associated with controlled gas kicks and their pronounced effect on casing .strings and exposed under lying formations. A mathematical model describing the volumetric behavior of an extraneous gas as it is transported from reservoir to .surface conditions under changing temperatures and pressures has been programmed in a Kingston FORTRAN II language for digital computer analysis. The gases under investigation typify Gulf Coast reservoir gases within a 0.6 to 0.7 .specific gravity range. The program output has been substantiated by actual field cases. of gas kicks encountered in Gulf Coart we1l.s. The development of empirical equations for calculating suitable gamy deviation factors for unique temperatures and pressures was incorporated in the program to provide realistic solution.. An output listing of annular backpressures and corresponding equivalent fluid densities resulting at a predetermined critical depth (casing setting depth) and total depth for selected .stages of circulation is provided in a chronological .sequence. Additional information including reservoir pressure and temperature, kill rnrid density, produced gas or surface volume of the expanded gas intro vion, drill pipe and annular volumes can he obtained from the model. This paper illustrates that a precise knowledge of the volumetric behavior of extraneous gases in annular flow and its effect on equivalent fluid densities at a critical depth is significant and should receive .serious consideration in controlling threatened blowouts and in the design of drilling programs. Surface pressures in excess of formation limitations are a threat to zones of lost circula/ion and are potentially injurious to productive intervals. A knowledge of annular backpressure and equivalent fluid density profiles for probable gas kicks aids in a technological accomplishment of drilling programs and provides a .sale tolerance in the event a threatened blowout is encountered. Introduction Drilling operations are frequently interrupted when the drill bit penetrates permeable gas sands with reservoir CtfuJ manuscript was received in Society of Petroleum Engineers ofice Am. 1 1967. Revised manuscript received JuIy 7. 1968. Paper (SPE 1860) kae presented at SPE 42nd Annual Fall Meeting held in Houston. Tex., Oct 1-4, 1967. @ Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineem, Inc. pressures greater than that exerted by the drilling fluid. The differential pressures resulting permit an extraneous influx of gas into the wellbore. A suspension in drilling progress is necessary to restore fluid equilibrium throughout the system. Whether formation gas kicks originate unintentionally or by design, the prospect of a threatened or actual blowout exists and a method assuring a safe and effective well control procedure must be observed. A significant contribution to well control technology was advanced by Records et a1.l in 1962. Using the concept of transmitting a constant equivalent formation pressure at the point of intrusion, Records et al. introduced a calculation technique providing the annular backpressures encountered in a well control environment as a func tion of the volumetric behavior of a 0.6 specific gravity natural gas. In essence, the procedure outlined an annular backpressure schedule in terms of fluid volume circulated at different stages of a well control operation. A number of other publications2-&apos; proposing various techniques for controlling gas intrusions in a wellbore achieve pressure control essentially through maintenance of a constant bottom-hole pressure by surface choke adjustments. The subsequent pressure effects induced in the annulus unfortunately receive little emphasis. Due to the tedious and repetitive nature of annular backpressure computations, a theoretical solution by digital computer is introduced for predicting annular backpressure and equivalent fluid density profiles associated with controlled gas kicks. We point out the effects of volumetric behavior of extraneous gases in annular flow and related field phenomena on equivalent fluid densities at a critical depth. The investigation indicated that equivalent fluid densities at a critical depth are of significance and should receive consideration in the control of threatened blowouts and in the design of drilling programs. Theoretical Considerations The mechanism of vertical gas flow through an annulus is governed by the PVT properties of the fluid, the pressure distribution within the system, the fluid flow rates and the geometry of flow. Due to the numerous variables involved in this type of problem, certain assumptions were imposed in deriving the mathematical model and in establishing the solutions. Two gases, characterized by specific gravities of 0.6 and 0.7, were selected to typify Gulf Coast reservoir fluids. The gas intrustion entered the wellbore as an immiscible &apos;References given at end of paper. JOURNAL OF PETROLEUM TECHNOLOGY

Jan 1, 1969

By J. R. Elenbaas, J. A. Vary, D. L. Katz

The development of gas fields, oil fields and aquifers for storing natural gas is treated from two main vieu.-points: (I) the volumetric storage capacity for gas in a given situation and (2) the prediction of the number of wells required for the delivery of gas. Other experiences in the design and operation of storagc fields are incluclerl INTRODUC TION Storage of natural gas in underground reservoirs near the terminus of long distance pipelines has been the prime factor in opening the space heating market to the natural gas industry. Storagc has permitted a major. increase in both the load and the load factor of pipe-lines; some are now operating at steady load throughout the year. Thus, underground storage has been responsible for the rapid increase in demand for natural gas in recent years. Three types of reservoirs have been used for gas storage: natural gas reservoirs, oil reservoirs, and waterbearing sands or aquifers. This paper presents the factors to be considered when developing gas storage reservoirs of these three categories. There are two prime considerations tor any storage reservoir: (1) the volume of gas which a given reservoir will store advantageously and (2) the number 01 wells needed to provide the required peak deliverability. These two problems will be considered for the three types of reservoirs just noted STORAGE IN PARTIALLY DEPLETED GAS FIELDS Early storage operations consisted of replenishing the natural gas in a depleted gas field situated adjacent to the market. Today, newly discovered fields near the market may be considered for storage, and this discussion applies equally to both types of reservoirs. For reservoirs originally containing gas or oil, the question of the impermeability of the cap rock nor-mally does not arise. However, such fields are likely to have many wells drilled either to or through the reservoir under consideration. Positive assurance must be obtained that such wells are or can be made mechanically tight. Corroded casings may need to be lined or permanently plugged. Abandoned wells should bc reopened and properly cemented. The volumetric capacity for gas storage depends upon space available in the porous rock as well as pressure and temperature of the gas in the reservoir. The production-pressure decline data on partially depleted gas reservoirs without water drive permit calculation of the reservoir space for gas. Isopachous maps of sand volume and porosity data for the reservoir rock provide an alternate method of calculating the pore volume for water-drive reservoirs. The pressure range selected for the storage cycle depends upon ()) the safe upper limit of pressure. 2) the flow capacity of wells and (3) compression requirements when injecting gas into the reservoir or delivering to market. Normally, gas and oil fields have pressures at discovery in the range of 0.43 to 0.52 psi/ft of depth. Pressures of around 1.0 to 1.2 psi/ft of depth appear to lift the overburden1-3 and invite uncontrolled movement of fluids in the porous rock. Some top pressure is normally selected for a storage reservoir ranging from below discovery pressure for deeper reservoirs to 0.65 psi/ft of depth for shallower reservoirs. Pressures to 0.66 psi/ft have been experienced without difficulty. The lower pressure limit is set by water intrusion accompanying low pressures, reduced flow capacity for wells at lower pressures and compression requirements. Depletion-type gas reservoirs often encounter water problems in the later stages of gas production. Such water intrusion may be due to movement from the surrounding aquifer. Accordingly, displacement of this water back into the aquifer by gas pressure and subsequent surges of water corresponding to the gas storage pressure cycle must be considered. Storage fields often produce in four months a volume of gas equal to its initial content. Rapid decreases in reservoir pressure occur, such as 20 psi/day. Accordingly, closed-in pressure observation wells which reflect the pressure in the bulk of the reservoir are required for following the operation of the reservoir. It has been found that a plot of observation wellhead pressures against gas content, Fig. 1, is very useful in observing operation of the field, checking the inventory and predicting future behavior. The plot is based on a given quantity of base or cushion gas in place. The injection and withdrawal curves may spread depending upon the homogeneity of the reservoir rock. permeability of the rock, well spacing and flow rates.