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By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1'2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O's. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO's are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.' At 900°C noticeable decomposition takes

Jan 1, 1964

By A. S. Eve

IN the spring of 1930, the question was raised as to the possibility of estimating the depth to which the pyrrhotite-nickel deposit at the Falconbridge mine extended in the earth. This body is 7500 ft. long, it dips at 80° to the north, and it is fairly straight with slight sinuosities. Dr. F. W. Lee suggested that it might be possible to solve the problem by measuring the vertical magnetic intensity, with a good magnetometer, both near the surface of the earth and also at a level a 'few feet higher in the air. The writer regarded this suggestion with some scepticism, but it was decided to put the scheme to a prac¬ tical test. In July, 1930, Dr. Lee, Dr. Keys and I ' the writer, with Mr. Joyce and Mr. Belloc as assist¬ ants, made a firm, light wooden platform (Fig. 1) E measuring 4 by 4 ft. on the top, which was 10 ft. above ground. This platform could be moved easily a few yards by four men, and carried across I country in a wagon or by motor truck. Some iron nails were used in its construction, but we were not able to detect their influence on the - Askania magnetometer. Nevertheless, in future work, the use of iron should be completely avoided. Readings were taken along a traverse at right L angles to the orebody, at several stations, both on FIG. 1.-VERTICAL the ground and on the platform. The excess read- ASKANIA MAGNETOM¬ ETER ings, over the dike, as compared with those about 10 ETER ON A FT. HIGH. PLATFORM 800 ft. away, are shown in Table 1. The largest reading, 6.8, is open to suspicion and should be rejected. The depth of the top of the orebody is known by electrical survey, and by actual drilling, to be about 112 to 123 ft., and the covering is sandy glacial drift. Similar readings were taken over a long straight magnetic diabase dike. These also are shown in Table 1. The magnetic vertical intensity is consistently less at the higher level, which is l0 ft. above the lower level.

Jan 1, 1931

By James K. Stanley

WHEN a plastically deformed metal is heated to a certain temperature, it undergoes a complete change in microstructure, the consequence of which is a marked alteration of mechanical properties such as hardness, strength and ductility. This change in microstructure occurs by recrystallization and is a process involving the formation and growth of strain-free nuclei in the deformed matrix. These nuclei continue to form with time and grow until a new grain structure replaces the cold-worked structure. The formation of the nuclei in the deformed sheet of 1 per cent silicon ferrite is illustrated in Fig. 1. If a recrystallization is conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time leads to an isothermal recrystallization curve, first established in 1942.1 Such recrystallization curves are shown in Fig. 4. These curves show that the recrystallization of a cold-worked metal is best considered as a rate process rather than a time independent process such as is suggested by the improperly named and misleading recrystallization diagrams involving deformation, temperature, and grain size. 2-5 Any study of the rate of recrystallization resolves itself into a study of the component rates of nucleation and growth. The previous paper' provided an account of the determination of the rates of nucleation; N, the number of nuclei formed per unit time per unit of unrecrystallized area, and growth, G, the radial growth in unit time, in the recrystallization of silicon ferrite (1 per cent Si). A method was developed to furnish experimental data for evaluating the effect of the recrystallization variables on N and G. The mathematical analysis for the derivation of the isothermal recrystallization curve was developed for a two-dimensional case (in thin sheets where the diameter of the recrystallized grain is greater than the sheet thickness). The present paper is a continuation of the study of recrystallization of 1 per cent silicon ferrite begun in 1942.1 In this work the effect of the factors deformation, temperature, grain size, composition, and recovery is studied with respect to the rates of nucleation and growth. At the same time it is shown how the cooperation of N and G affects the isothermal recrystallization curve. The study of these variables on N and G has a definite bearing on the mechanism of recrystallization and should lay a foundation for a rational theory on the subject. PROCEDURE The procedure used in these experiments was essentially the same as that described previously but in certain details some changes were made in the interests of speed. With few exceptions, the procedure is the same for the study of all the variables. Where the procedure is different from standard manipulations attention is called to this fact.

Jan 1, 1945

By Nicholas J. Grant, Italo S. Servi

Extensive data of minimum creep rates and rupture times for high purity and commercial aluminum confirm the existence of a transition range from the low temperature-type to the high temperature-type behavior. The data are analyzed in line with the suggested theories of deformation of metals. CONSIDERABLY more work has been done on the rupture and creep behavior of commercial alloys than on the less complex, high purity metals. As a result, certain fundamental behaviors are overlooked. One of the lesser known variables affecting the high temperature behavior of metals is the impurity content (or alloy content). Impurities are known to affect strongly the recrystallization temperature, electrical resistivity, and other properties of metals, but the effect on creep and other high temperature mechanical properties has been determined for very few materials. In view of these facts aluminum appears to be a fairly ideal metal, since it is available in a wide range of purity contents from 99.995+ down through the 2s (99.0 + Al) and 3s (1.2 Mn) grades in small steps. It is highly resistant to oxidation and other surface instabilities, leaving recrystallization and grain growth as virtually the only instabilities. Control of grain size is also well standardized. Limited data on the creep of aluminum have been obtained by Dushman et a1.l for high purity aluminum; by Sherby2 on 2s aluminum of variable grain size; and by Dorn and Tietz³ on cold-worked 3s aluminum. Experimental Procedure The apparatus consisted of a constant stress, creep testing unit similar to the type described by Hop-kin.' The specimens were held at temperature for 30 min before loading. The loading time was less than 2 min. Factors affecting the accuracy of the data were: 1-—the temperature gradient and control, ± 3°F; 2-the stress determinations, ± 1.5 pct; and 3—elongation measurements (1 in. gage), ? 0.001 in. Three grades of aluminum were tested: 1— high purity (99.995 pct Al), 2—2s (99.3 pct Al), and 3—3s (98.2 pct Al). The spectrographic analyses of these materials are reported in Table I. The specimens were annealed then electropolished in a perchloric-acetic mixture before testing. Data on heat treatments and grain size obtained appear in Table 11. The entire creep curve was determined for almost all of the tests. A few tests were interrupted after the beginning of the third stage of creep, and in these cases the rupture time was estimated. Experimental Results Constant stress creep-rupture testing gives a much longer, more accurately measurable second stage of creep than constant load testing. This behavior is in agreement with the results obtained by Andrade for lead (see Fig. 1). If the test is run to completion, the third stage of creep appears as soon as stress intensification occurs. In the case of specimens which fail in a ductile manner, the stress intensification begins when the sample starts "necking". This differs from the "high temperature brittle" specimens in which the stress intensification is caused by intercrystalline cracking. These specimens

Jan 1, 1952

By D. W. Rudd, D. W. Vose, S. Johnson

The permeability of Mo-0.5 pel Ti to hydrogen was investigated over a limited range of temperature and pressuire (709° to 1100°C, 1.i and 2.0 atm). The resulting permeability, p, is found to obey the The experimental data justifies the permeation mechanism as a diffusion contl-olled pnssage of Ilvdrogen atoms through the metal barrier. 1 HE permeability of metals to hydrogen has been investigated by a number of workers and their published results have been tabulated by Barrer' up to 1951. Since most of the work on the permeability has been accomplished prior to this date, the compilation is fairly complete. Mathematical discussion of the permeability process has been reported by Barrer, smithells, and more recently by zener. From these efforts several facts are observed. First, the permeability of metals to diatomic gases involves the passage through the metal of individual atoms of the permeating gas. This is evidenced by the fact that the rate of permeation is directly proportional to the square root of the gas pressure. Second, the gas permeates the lattice of the metal and not along grain boundaries. It was shown by Smithells and Ransley that the rate of permeation through single-crystal iron was the same after the iron had been recrystallized into several smaller crystals. Third, it has been observed that the rate of permeation is inversely proportional to the thickness of the metal membrane. Johnson and Larose5 verified these phenomena by measurirlg the permeation of oxygen through silver foils of various thicknesses. Similar findings were noted by Lombard6 for the system H-Ni and by Lewkonja and Baukloh7 for H-Fe. Finally, it has been determined that for a gas to permeate a metal, activated adsorption of the gas on the metal must take place. Rare gases are not adsorbed by metals, and attempts to measure permeabilities of these gases have proved futile. ~~der' found negative results on the permeability of iron to argon. Also, Baukloh and Kayser found nickel impervious to helium, neon, argon, and krypton. From what was stated above concerning the dependence of the rate on the reciprocal thickness of the metal barrier, it is seen that although adsorption is a very important process, at least in determining whether permeation will or will not ensue, it is not the rate determining process for the common metals. A case in which adsorption is of sufficient inlportance to cause abnormal behavior has been noted in the case of Inconel-hydrogen and various stainless steels.'' APPARATUS The apparatus used in this study is shown in Fig. 1. The membrane is a thin disc (A), but is an integral part of an entire membrane assembly. The entire unit is one piece, being machined from a solid ingot of metal stock. When finished, the membrane assembly is about 5 in. long. Two membrane assemblies were made; the dimensions of the membranes are given in Table I. The wall thickness is large compared to the thickness of the membrane, being on the average in the ratio of 13 to 1. There exists in this design the possibility that some gas may diffuse around the corner section of the membrane where it joins the walls of the membrane assembly, If such an effect is present, it is of a small order of magnitude, as evidenced by the agreement of the values of permeability between the two membranes under the same temperature and pressure. A thermocouple well (B) is drilled to the vicinity of the membrane. The entire membrane assembly is then encased in an Inconel jacket and mounted in a resistance furnace. The interior of the jacket is connected to an auxiliary vacuum pump and is always kept evacuated so that the membrane assembly will suffer no oxidation at the temperatures at which measurements are taken. The advantages of this configuration are: 1) there are no welds about the membrane itself, so that the chance of welding material diffusing into the membrane at elevated temperatures is remote. 2) It is possible to maintain the membrane at a constant temperature. Since the resulting permeation rate is very dependent upon temperature, it is advisable to be as free as possible from all temperature gradients. 3) It is possible to obtain reproducible results using different specimens. The only disadvantage to this configuration is the welds (at C) in the hot zone. The welding of molybdenum to the degree of per-

Jan 1, 1962

By B. Trafton, H. L. Hartman

An earlier paper1 introduced a rapid solution for mine ventilation network problems, employing the digital computer. In this paper, refinements and additions to the computer program which expand its scope of application and a solution to a ventilation network having a coal-mine configuration are presented. The revised program-written in FORTRAN for the IBM 7074 computer in Penn State's Computation Center-is applicable to any mine ventilation network employing natural splitting and having its fan located externally. It accomplishes the following: 1) Distributes an assumed total quantity of air flow among all airways of the network, performing iterations until an acceptable level of error is attained and the flow in each airway is known. 2) Computes the pressure drop (head loss) in all airways and the overall network and mine head losses. 3) Determines the operating point for the mine and a given fan, adjusting all air flows and head losses to the actual values. The basis of analysis used is the Hardy Cross method of successive approximation for solution of any fluid network, explained in detail in the earlier article. In brief, corrections to assumed air flows are computed for all the loops of a network; following distribution to the airways of each loop, the process is repeated until acceptable accuracy is attained. When a hand or desk-calculator solution is used, there is advantage to close approximation of the actual flows in the original assumption of air-flow distribution in the network. Since publication of the previous paper, in which assumption of initial quantities was also necessary in the computer solution, the program has been modified to make the first distribution itself, assigning the total quantity to one specified path in a split and then proceeding to correct the flows. The number of iterations required for a high-accuracy solution is little affected, at least in networks of few loops, 10 to 15 being sufficient to reduce the error to 1 pct or less. The principal limitation of the original program was that it contained no provision for handling a fan. Further, it did not determine the overall head loss in the network and was not designed for multiple parallel openings, such as occur in coal mines. The revised program was written to overcome these disadvantages and also to print out the adjusted flows for all airways, corrected for the system operating point. At the present time, the program can handle only an external fan. The procedure employed in solving a ventilation network is now as follows: 1) Input data consisting of airway characteristics and loop designation along with assumed direction of flow, for each branch of the network and any trunk airways, are fed into the computer. 2) Employing the resistance relationship, where R is resistance, K is friction factor, P is perimeter, L is length, A is area, and n is number of airways (where multiple intakes and returns are employed); values are computed for all airways. 3) An arbitrary, continuous route of flow through the circuit—from beginning to end—is selected and the path identified by airway numbers and read in. 4) Based on a total assumed quantity of flow Q (usually 100,000 cfm.) the computer employs the procedure described in the previous article in distributing quantities of flow among all the airways until a satisfactory level of accuracy has been attained (in the current program, the machine is turned off when the cumulative corrective error in cfm, is reduced to five times the number of airways). 5) Airway head losses H are calculated by the relation H = R Q2 and cumulated along the original designated flow route to find the overall head loss for the network. Trunk airways are then included to obtain the mine head.

Jan 1, 1964

By Noah Fields Drake

This paper is devoted chiefly to the coal-fields of the western part of the province of Chili and the eastern part of the province of Shansi; but the outline of this belt will give some idea of the extension of the coal-fields over northeastern China. This part of China is topographically divided into: (1) the mountainous peninsula of eastern Shantung; (2) the coastal plains, extending W. and SW. from the gulf of Pechili; and (3) the mountains and table-lands N. and W. of the coastal plains. The plains extend N. and W. from the gulf to within from 10 to 25 miles of the Great Wall, while their SW. extension covers western Shantung and reaches W. along the Yellow river almost to the southern boundary of Shansi. A line joining the mapped coal-fields, shown in Fig. 1, almost gives the western boundary of the plains; since these areas lie on the border of the plains—except the Tsê Chou field, which is on the table-land, 20 to 25 miles from that border. The coal-fields which have been mapped and investigated by the author are shown in Fig. 1. The one at and around Tongshan is known as the K'ai-p'ing coal-field; the one W. of Peking has been called the Wang-p'ing coal-basin; the one SW. of Pao-ting and N. of Chêng-ting may be called the Lingshan coal-field; and the one at and around Tsê Chou is known as the Tsê Chou coal-field. I. The K'ai-p'ing Coal-Field. As is shown in Fig. 2, most of this field lies in the coastal plains, and is therefore covered by alluvium and loess, which have buried the older rock-beds, and the more gentle and older topographic outlines, to such an extent that most of the re-

Jan 1, 1902

By Thomas D. West

The fact that iron expands when heated, until fusion takes place, and that molten iron is consequently less dense than solid iron of the same grade, is now universally admitted. It was proved by the extensive experiments of Mr. Thomas Wrightson, reported in the Jownal of the Iron and Steel Institute (1890, No. 1, p. 72, and 1891, No. 1, pp. 75, log), and, in a manner, is illustrated in heavy founding by the shrinkage 'of the molten metal, which must be " fed " in order to obtain solid castings. This decrease in volume requiring " feeding" while the metal is still liquid I call " shrinkage," applying the term " contraction" to the decrease in volume which takes place after solidification, while the iron is cooling to atmospheric temperature. The light-work founder, not having the opportunity to make heavy castings, in which shrinkage can be observed, is apt to confound the two; but they are in fact distinct, and are separated by an act of expanion, which takes place at the moment of solidification. The fact of this expansion was first practically demonstrated by Mr. John R. Whitney, of Philadelphia, Pa., whose experiments are recorded in the National Car and Locomotive Builder of May, 1889. Experiments recently made by the writer indicate that there is a constant relation between this expansion and the preceding shrinkage and forcibly demonstrate the necessity of " feeding " a casting to make its interior solid. This is a matter with which all makers and users of castings have experienced difficulty. The founder being heretofore unable to define correctly the principles involving the urgent necessity of " feeding " has failed to impress the moulder with its importance in making sound castings.

Jan 1, 1897

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By Frederick Laist

The ores received at the Washoe Smelter come almost entirely from the mines in Butte and contain the following minerals : Chalcocite, Cu2S; covellite, CuS; chalcopyrite, CuFeS2, (trace); bornite, Cu3FeS3; enargite, Cu3AsS4; malachite, Cu2CO4 + H2O (trace); pyrite, FeS2; sphalerite, ZnS; rhodo-chrosite, MnCO3, (less than 1 per cent.); rhodonite, MnSiO3, (less than I per cent.). The country-rock of Butte is of the granite family and is a quartz-monzonite containing a little less silica than typical granite. It is made up of the following rock-minerals in approximately the proportions indicated: Minerals. Composition. Per Cent. Quartz SiO2 20 Andesine 1/2 NaAlSi3O8; 4 CaAI2Si2O8 42 Orthoclase KA1Si308 23 Hornblende 1/2 Ca(MgFe)3Si4O12; & (MgFe)2(AlFe)4Si2O12 6 Biotite (HK)2(MgFe)2A12Si3O12 9 Titanite CaTiSiO5 0.1 Apatite (CaF)Ca4(PO4)3 0.05 Magnetite (FeO)(Fe2O3 0.15 Pyrite FeS2 0.02 99.32 The main country-rock (quartz-monzonite) is cut by dikes of aplite, a granite having the following composition: Quartz, 30; andesine, 20; orthoclase, 45; ferro-rnagnesian minerals, 3; pyrite, 0.1; total, 98.1 per cent. Closely associated with the copper-deposits are dikes and bodies of " Modoe" porphyry, technically known as quartz-

Jan 1, 1913

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.'s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By Karl Sundberg

ElectRical investigations carried out in regions containing sedimentary rocks showed that sediments generally are good electrical conductors, a fact which at the present time is used for structural investigations by electrical methods. It is of fundamental importance, not only for these investigations but also for electrical prospecting in general, to know the electrical properties of various soils and rocks. It will be useful, therefore, to discuss this question with the hope that the general points of view discussed in this paper will perhaps be completed by further observations and determinations of material from various localities. This paper is based principally on the study of literature, and the purpose is primarily a discussion of the main factors that determine the electrical conductivity of soils and rocks. It will follow, however, that the factors discussed here also frequently decide how far a certain orebody can be regarded as a good electrical conductor compared with the surrounding rocks. All rocks are more or less porous, and the pores are filled with liquids and gases. Their electrical conductivity, therefore, depends on the following factors: 1. The electrical conductivity of minerals composing the rock. 2. Electrical conductivity of the liquid filling the pores. 3. Proportion of the volume of liquid filling pores of the rocks to the solid rock material. 4. Shape of the pores. 5. Arrangement of the particles of gas and liquids. 6. Temperature. Dry minerals, with the exception of certain ore minerals, are complete nonconductors from the point of view of applied geophysics; in the present investigation we deal with rocks which have no conducting minerals, and factor 1, therefore, is not important. The same is true of soils. The liquids contained in soils and rocks in most cases are waters, sometimes oil. As oil is a nonconductor of electricity, the impregnating waters will determine the electrical conductivity of soils and rocks.

Jan 1, 1932

By R. E. Anderson, R. S. Busk

The mechanical properties of many nonferrous alloys can be modified by heat-treatment. This is almost always effected by controlling the amount of alloy in solid solution and the amount and distribution of second-phase material. The latter often is accomplished through precipitation or age-hardening treatments. The procedure is to solution-heat-treat the metal to provide a supersaturated solid solution and then cause precipitation of the dissolved material at some temperature below the solvus for the alloy. The generally used magnesium sand-casting alloys arc based on the ternary alloy system Mg-Al-Zn. Solid diffusion reactions in the system are slow enough so that a substantially completely supersaturated solulion is maintained even though the metal is relatively slowly cooled from heat-treating temperatures. Consequently, it is general practice to air-cool magnesium-alloy castings from the heat-treatment temperature prior to aging at an elevated temperature. Since it is necessary with many other alloys to cool quite rapidly before aging if optimum benefit from the aging is to be obtained, this study was undertaken to determine the effects of quenching on magnesium alloys. The] alloys used are shown in Table I, being selected as typical of the presently used magnesium alloys. Cooling Rates Since quenching is a means of rapidly extracting heat, there are two factors of interest in its study: (I) the rates of cooling that can be obtained and (2) the effect of various rates on the as-cooled as well as subsequently aged metal. The cooling rates were measured by drilling a hole 1/16- in diameter longitudi~lally in the center of a cylinder % in. in diameter and 3 in. long. The drilling was stopped to place the end of the hole at the center of the long axis of the cylinder. An iron-constantan thermocouple was inserted in this hole and wedged in place. The temperature drop during rapid quenching was recorded by a special1y built General Electric potentiometer recorder capab1e of measuring ' 500°F. temperature drop in 1/10 sec. For the slower cooling rates in air or oil, the temperature drop was measured by a Leeds and Northrup potentiometer recorder with the chart speed increased to One inch per minute' The cylinder was heated to the desired temperature, quenched as desired, and the temperature-time curve recorded. The cooling rates in still air, in oil at 350°F., in water at 180°F. and in a cold, high-pressure water spray were determined in this manner. The results of this study are presented in Fig. I. There is a great difference between water quenching and either air or oil quenching. There is little difference between the hot water quench and the cold water spray. Cooling rates were also

Jan 1, 1945

By Robert A. Rapp, Jan E. Verfurth

From the measurement of internal-oxidation band widths in Ag-In and Cu-A1 alloys, products for the solubility No and the diffusivity Do of oxygen in silver and apparent NODo products in copper have been obtained over a range of temperature. The NODO products for silver are in agreement with the product of the individually determined No and Do values of Eichenauer and Müller. Although interstitial diffusion of oxygen in silver is expected, the temperature-independent factor Do of the diffusion coefficient does not agree well with the theory of Wert and Zener. For Cu-A1 alloys internal oxidation does not follow the expression derived for ideal kinetics, since the apparent NODo product calculated from internal-oxidation measurements is a function of the alloy content in the specimen. Thus, unequivocal values for No or DO or even the product NODO in copper are not available from the literature. RELIABLE values for the saturation solubility NO and diffusivity DO of oxygen in fcc metals are lacking and difficult to determine, partially because internal-friction measurements are not applicable. Permeability experiments and Sieverts7-type adsorption -desorption methods3 have met with difficulty; however, Eichenauer and Müller4 have recently reported on the solubility and diffusivity of oxygen in silver as determined by the latter technique . Rhines, Johnson, and Anderson,5 and independently Meijering and Druyvesteyn,' introduced the possibility of deriving values for the product NODO in a metal from measurements of the widths of internal-oxidation zones (subscales) formed during the internal oxidation of alloys. In addition to these authors, several other investigators7-9 have made such measurements in various silver and copper alloys at various temperatures, mostly using me- chanically polished specimen surfaces. The purpose of this investigation was to determine over a range of temperature the calculated products NODO in silver and copper from systematic measurements of the widths of internally oxidized zones in Ag-In and Cu-A1 alloys, using specimens with electro-etched surfaces. Consider the internal oxidation of a dilute solid-solution alloy in which the base metal is not oxidized. If diffusion of oxygen is the rate-controlling step, then the depth 5 of the internal-oxidation zone is given by where y is a dimensionless parameter and t the oxidation time. Based on the solution of the diffusion equation, wagnerl0 has shown that under certain conditions several mathematical simplifications may be used in the evaluation of y, so that Eq. [I] may be expressed for the case that y « 1, and y(Do/DB) 1, where N(so)the is the equilibrium solubility (mole fraction) of oxygen in the solvent metal for the given oxidizing atmosphere, is the mole fraction of the solute metal in the bulk alloy, 4 is the diffusivity of the solute in the base metal, and v is the ratio of oxygen atoms to solute atoms in the precipitated oxide BO,. Rearranging Eq. [2] Maak' has derived an expression analogous to Eq. [3] for the case that an external-oxide scale, in addition to an internal-oxidation zone, is formed. For this combined external and internal oxidation for the case that 5/2 where 5 is the distance of the internal-oxidation front from the original external s.urface, and X is the distance of the external oxide/metal interface from the original external interface. The function F is defined by the expression

Jan 1, 1964

By E. O. Bennett

When oil is takcn from a subsurface structure it is generally accompanied by gas. The gas thus produced represents the 1ighter hydrocarbons present in the original petroleurn accurnulation, which arc, insoluble at the reduced pressures created around a well when it is producing. In some cases the gas accompanying the oil may come from a gas-bearing stratum not in immediate contact with the oil. The amount of gas from the formation accompanying each barrel of oil is called the natural gas factor. Energy Causing Well to Flow The force causing the flow of fluid into a well when it is drilled into an oil-bearing structure is the pressure differential between the well bore and the formation. A pressure differential between the formation and the well may be set up in three different ways, as follows: (1) pressure due to gas in solution or in contact with the oil, (2) hydrostatic pressure due to water in contact with the oil (it may be either bottom or edge water); (3) pressure difference due to forcc of gravity. The greatest source of energy for producing oil from most oil fields, and the one over which the greatest control can be exerted, is the poten-tial energy in the gas under pressure in the formation. In any pool there is but a definite amount of gas available. Part of this gas may be in solution and a part in contact with oil. The amount of gas in solution in each bard of oil depends on the pressure and temperature in the formation and the characteristics of the oil. Whether the gas is in solution or in contact with the oil it is necessary to use the energy it, contains as efficiently as possible in order to obtain the greatest ultimate recovery from the pool. Bush1 states: Gas being the most efficient aid in moving the oil, it is important to prevent more of it from escaping than is necessary to remove the maximum amount of oil from the sands. The conservation of this energy is far more important to the producer of oil than his returns from sales of gas to distributing companies. The flowing life of the well is the most profitable period, and keeping the gas-oil ratio low, or keeping the

Jan 1, 1928

By Harry Warren

THE Geology Department of the. University of British Columbia has undertaken the task of examining the ores from as many as possible of the gold mines of British Columbia. The object of this work is two-fold. First, it is known that detailed mineralographic studies are useful in attacking ore-dressing problems, and these studies are intended to be helpful to mill operators. Second, it is hoped that mineralogical and mineralographical studies will prove useful adjuncts to those of lithology and structure in throwing more light on problems related to the origin of the deposits. The paper shows that gold, for all practical purposes, is not present in an ore mineral in solid solution nor as a eutectic with any mineral; if the latter were true the gold particles would be distributed equally throughout that mineral. The gold occurs either as native gold or as a gold-silver telluride and is not distributed regularly through any mineral or minerals: The relationship between the gold or gold-bearing telluride and the associated minerals affords a means of classification that is not only simple but also appears to be directly related to the geological nature of the deposit, which may be summarized as follows: 1. Disseminated Gold Type. ;-Precious minerals in extremely small grains, which are distributed without regard to grain size, fractures or grain boundaries: (1) Hedley variety-gold in native form; (2) Surf Point variety-gold predominantly as telluride. 2. Veining Gold Type.-Precious minerals in grains of various sizes, which occur mainly along fractures and grain boundaries: (1) Cariboo gold quartz-gold in native form. (2) Waneta variety-gold as telluride.

Jan 1, 1937

By J. Eric Belford

The Kidd Creek orebody is a massive base metal sulphide deposit with surface dimensions of 168 m by 670 m. The steeply dipping ore- body has been evaluated to a depth of 1 524 m. To date, the mining of the orebody has been divided into three stages. The first stage of mining was an open pit operation which supplied ore from 1966 until 1977 when a depth of 219 m was reached at the widest or north end of the orebody. The second stage of mining, called No.1 Mine, was the development of an underground mine to replace the pit and recover the ore from the floor of the pit to a depth of 792 m. Development of the underground mine started in 1969. Full production of 273 000 tonnes per month was attained in 1977. The third stage of mining called No.2 Mine, was initiated to accommodate a production expansion and included the development of a second underground mining operation to recover the ore from the bottom of No.1 Mine, i.e. the 2600 level; to a depth as yet undetermined but most likely the 4600 foot level. Development of the No.2 Mine began in 1974. Full production of 91 000 tonnes per month will be achieved in 1982. The choice of the 2800 level as the partition between the two underground mines was based on the following factors: The 2600 level is the lowest level which can conveniently be mined through the No.1 Mine crusher on the 2800 level. Development and trial stoping methods for mining at depth could be evaluated in the 2600 to 2800 block utilizing the existing hoisting facilities of No.1 Mine. Early development of the ore in the 2600 to 2800 block would provide additional mill feed sooner than could be achieved by developing from No.2 Shaft. The underground mining plan then is to mine from the pit floor down to the 2600 foot level and at the same time mine from the 2800 level down to at least the 4600 foot level. PLANNING The Kidd Creek operations are designed to follow a logical mining sequence. The grade of ore supplied to the concentrator is the result of following the mining plan. The philosophy of mining has been to mine downward in horizontal slices. In the case of No.1 Mine the slices are 122 m thick while in No.2 Mine the slices will be 183 m thick. The point of this approach is to mine the pillars immediately after creating them rather than allowing them to stand, deteriorate and generate uncontrollable situations. Two types of ore are handled separately to optimize recoverable values in concentrates. The 'A' type ore is a copper zinc ore with some silver and little lead. The 'C' type ore is a zinc silver ore with some lead and copper

Jan 1, 1981

By N. A. Warner

Dense cylindrical specimens of artificial hematite were reduced in hydrogen over a range 0-f total pressures between 0.1 and 1.0 atm and temperatures between 650" and 950°C. Hydrogen reduction at a total pressure of 1.0 atm in the presence of a chemically inert diluent and reduction in hydrogen/water mixtures were also studied Znter.face movement during reduction was followed using metallographic techniques. Substantiu1 partial-pressure gradients are shown to exist in both the gas film and the reduced iron layer. The results are consistent with a mixed-control mechanism involving an interaction of gaseous-difusion effects with a first-order reversible chemical reaction at the iron/wüstite interface. Over the hydrogen-pressure range of 0.1 to 1.0 atm, the rate is not directly proportional to the hydrogen pressure in the bulk gas stream. Nitrogen dilution of the reducing gas masks the true effect of hydrogen partial pressure by influencing the effective molecular dif-fusivity and gives an apparent first-order relationship. The transport of hydrogen and water vapor across the iron layer is consistent with molecular gaseous diffusion rather than a Knudsen diffusion mechanism. ALTHOUGH the literature on the reduction of iron oxides is very extensive, it is only comparatively recently that a definite quantitative model for the reduction of hematite has been proposed. This development has been largely due to the work of McKewan. An extensive literature review of previous work has recently been compiled by Themelis and Gauvin. Exclusive control by gaseous diffusion in the reduction of hematite has been recently advocated by Kawasaki and coworkers.' Although the results of the latter workers are of considerable practical significance, the extreme porosity (approximately 30 pct) of their specimens precludes their application to a kinetic evaluation of the reduction of dense polycrystalline hematite. The salient features of the kinetic model used by McKewan for the gaseous reduction of dense hematite at temperatures in excess of 560°C (when FeO is stable) are: 1) The reduction is a topochemical reaction taking place through 'the series FeO/FesO4/FeO/ Fe; 2) The gas-solid type of reaction takes place only at the FeO/Fe interface and the internal reduction: FeO proceeds by solid state diffusion; 3) The iron layer formed is quite porous and offers negligible impedance to gaseous diffusion; 4) The rate-controlling step in the reduction is a chemical process occurring at the Fe/FeO interface. In view of the relatively fast reaction rates involved when hematite is reduced in a stream of hydrogen, it seemed possible that the simplifying assumptions of negligible diffusional resistance in both the bulk gas phase and the reduced iron layer could introduce serious errors in the interpretation of experimental reduction data. The present work was initiated to elucidate the effect of gaseous diffusion on the reduction rate and to determine its possible influence in the formulation of the reaction mechanism at the metal/oxide interface. EXPERIMENTAL Procedure and Apparatus. Dense cylindrical compacts of artificial hematite were prepared by sintering pressed compacts of reagent-grade ferric oxide, containing 99.6 pct FezO, in air at 1200°C for 80 hr. The resulting compacts had a final porosity of less than 2 pct and a height and diameter of approximately 1 cm. Variations in sintering atmosphere from air to pure oxygen, in sintering time from 20 to 80 hr, and temperature from 1150" to 1250°C had no effect on the subsequent reduction behavior. The reduction of the samples took place in a vertical tube furnace in which was placed a 1-in. transparent silica tube. The 24-in. heated length

Jan 1, 1964

By N. Marusov, D. K. Lowe, J. C. Karp

This paper considers, from an engineering viewpoint, several factors involved in creating, designing and locating horizontal barriers for controlling water coning. This is an effort to consolidate new concepts with previous information so that a reasonable selection of barrier materials, dimensions and vertical position can be made. Coning theories previously developed are briefly reviewed and an effort i,s made to reduce the results of coning-theory calculations to a point where routine calculations can be made with a desk calculator. It is expected that these simplified calculations will give usable predictions of the amounts of improvement attainable with barriers of various dimensions. Apparatus and procedures used for testing the suitability of commercial cements are described and test results are presented. INTRODUCTION Just about as soon as the phenomenon of water coning was recognized as an oilfield problem, there were suggestions that the production of water coning could be controlled or completely suppressed by means of horizontal barriers. It was also suggested that natural barriers such as shale streaks were helpful in restricting bottom-water production. The implication was that wells not having the benefit of continuous shale streaks to suppress bottom waters should, in some way, be supplied with an artificial barrier. With regard to the selection of barrier materials, there are many references which give the merits of liquid barriers.',' These liquids include surface-active agents," recipitates' and emu1sions. There is no real need to review the merits of these materials again. This paper deals with the use of solid barriers which could be made from various cements. The two major restrictions placed on these barrier cements are that (1) they must be commercially available in large quantities, and (2) they must be applicable by means of standard tools and equipment with techniques that have been fully developed and are in general use at the present time. A schematic drawing of a horizontal barrier in a reservoir is shown in Fig. 1. Two maximum stable water cones are illustrated-—-one for the wellbore diameter and the other for a barrier. A maximum stable cone is one that has attained its maximum volume at the critical production rate and is on the threshold of producing water. The volume displaced by each water cone and the rise in water table are indications of the amount of water-free oil produced. Corrections for porosity, connate water and residual oil, of course, must be applied. The water-oil interface which defines a maximum stable cone is called a free surface. It is a surface over which the pressure is constant. This free surface has the shape of a limiting streamline at and below which there is no movement or transport. The shape of the water cone describes the pressure drop in the reservoir. The effect of a completely impermeable barrier on the cone shape is essentially the same as extending the wellbore out to the barrier radius. The placement of a horizontal barrier requires that a horizontal fracture be created using a single-point entry technique. Two methods may be employed for filling this fracture. One method consists of propping the fracture before filling with cement. The other consists of fracturing with fracture fluid, then immediately following with cement