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By M. S. Rashid, C. J. Altstetter

Allotropic transformations in cerium have been studied by dilatometric, resistometric, X-ray diffraction, and metallographic techniques. The dilatometric study indicated that, on cooling below O°C, the high-temperature fcc phase, y, transforms partly to the hexagonal phase, ß, and, on further cooling, to the collapsed fcc phase, a. The amount of $ phase present at room temperature is increased by repeated cycling through the a-y transformation. It has been shown metallograPhically that the y-ß transformation has many characteristics of a martensitic transformation. In contrast to the y-ß transformation the ?-a transformation does not give the manifestation of a shear transformation. Small cellular ? domains of random shape and size collapse to a in a short time with no apparent coordination with neighboring domains. The considerable confusion in the literature over the existence of more than one high-temperature fcc phase is discussed. Two such phases have been reported in the literature and an attempt is made in this study to clarify the situation. Twelve fcc and two hcp structures have been shown to be easily reproduced or eliminated. It is proposed that the two "additional" allotropes reported in the literature and fourteen of the phases detected here are not allotropes of cerium but are due to contamination. CERIUM exists in several allotropic forms, but there is some disagreement over what the forms are. Furthermore, the conditions favoring the presence of a particular allotrope and the nature of the transformations from one form to another are uncertain. The objectives of this research were 1) to ascertain the allotropic forms of cerium, 2) to establish the conditions under which the allotropes exist, 3) to study the effects of annealing and thermal cycling on the allotropic transformations, and 4) to study the transformation mechanisms. Dilatometric, resistometric, metallographic, and X-ray diffraction techniques were employed. The form of cerium commonly found at room temperature is fcc and is designated ?. A complex hexagonal phase, 8, forms when y is cooled to slightly below room temperature. At still lower temperatures the y fcc structure transforms to an fcc form with a much smaller lattice parameter, termed a cerium. A bcc form, 6, which exists just below the melting point (800°C), will not be considered further in this work. There is a substantial body of experimental evidence (reviewed by Gschneidnerl) which favors the acceptance of these four allotropes, though some investigators have tried unsuccessfully to observe the ß hexagonal form.'-' There is disagreement, however, over the phase-transformation temperatures, due, in part, to broad hysteresis and overlapping of the transformations between the a, ß, and ? forms. The transformations are also sensitive to prior thermal and mechanical treatment. The differing purity of cerium used by different investigators is undoubtedly a factor. Cerium is difficult to separate from other elements and is quite reactive, igniting spontaneously when it is filed in air. The highest purity of cerium to date is reported to contain several hundred parts per million by weight of impurities, and early investigations were carried out on cerium containing several percent of impurities. There have been reports of more than one fcc allotrope at room temperature. Gschneidner, Elliott, and McDonald5 obtained diffraction patterns of an fcc phase with a lattice parameter about 1 pct less than that of the ? phase, instead of the y phase, on slowly cooling cerium filings from 23° to -198°C and warming them back to room temperature. However, when the sample was heated to 447°C and cooled to room temperature it consisted of only the ? phase. They have designated this new fcc phase "a-? intermediate", and say it is quite sensitive to impurities. After prolonged high-temperature treatment of a powder specimen, Weiner and Raynor2 obtained a diffraction pattern of an fcc phase of lattice parameter about 1 pct less than the ? phase. This they called the y' phase. It could not be reconverted to the y phase and is claimed to be different from the a-? intermediate phase.5,6 Dialer and Rothe3 reported two fcc phases* after cycling their powder specimens between room temperature and -192°C. Gschneidner, Elliott, and McDonald5 suggested that one of the fcc structures obtained by Dialer and Rothe was equivalent to their "a-? intermediate" phase. Table I presents some pertinent data on the proposed allotropes. For the ?(fcc)-ß(hexagonal) transformation

Jan 1, 1967

By L. Dudley Stamp

In my last report on Petroleum in Burma and India1, details were given of production and development up to 1932. It was pointed nut, that the only statements available for Burma were those published officially by' the Government of India in the Annual Review of the Mineral Production of India (Records of the Geological Survey of India), which are issued about 10 or 11 months after the close of the year. Operations in Burma are almost entirely in the hands of three companies—the Burmah Oil Co., the British Burmah Petroleum Co. (with its subsidiary, the Rangoon Oil Co.) and the Indo-Burma Petroleum Co.—and these companies preserve a policy of secrecy, so that details are not available of new wells, depth, wells abandoned, or of other figures, except in so far as the Government considers it advisable to publish the information in its possession. GeneRal Developments in 1933-1934 As predicted in 1933, there have been no spectacular developments and no new fields have been discovered. Nor are there any new indications of a likelihood of fresh discoveries. The policy of extremely careful exploitation. has been continued and intensified; production is being maintained at an almost steady level and can be so maintained for many years to come—indeed, it is the policy of the leading company to permit refinery and local market requirements to dictate the production required. Contrary to experience in practically every other part of the world, India has shown a slightly decreased demand for petroleum products—especially kerosene, but also for gasoline. The increased use of electricity would explain the lower demand for kerosene, but the falling off in the demand for gasolinc can only be attributed, according to the Chairman of the Burmah Oil Co., to the depression and to the incidence of heavy taxation. In India (including Burma) as a whole, production was 305,018,751 Imperial gallons in 1931 (8,714,822 U. S. barrels); 308,606,031 Imp. gal. in 1932; 306,009,022 in 1933 and is estimated at 308,000,000 in 1934.

Jan 1, 1935

By B. L. Landrum, J. Simmons, J. M. Pinson, P. B. Crawford

Patentiometric model data have been obtained to estimate the effect of vertical fractures on the areas swept after breakthrough in water flooding and miscible displacement programs such as gas cycling where the mobility is near one, The data are presented for the case of the fire-spot pattern in which the cemer well is fractured various lengths and orientations, the data indicate that for 10-acre spacing, fractures extetidirrg over 1300 ft in either directior1 from the fractured well may re.srrlt in reductions in sweep efficiencics from 72 to approximately 34 per cent. However. the area swept after break through may be quite largr and only 10 or 12 per cent 1ess than would be obtained if the reservoir were trot fractured. For the specific case when the volume of fluid injected is equivalent to 100 per cent of the pattern vol-unie, the swent area may vary from 80 to 88 per cent, depending on the lenght of the fracture. The former value is that which occurs when the break through or sweep efficiency was orrly 34 per cent and the latter figrrre of 88 per cent is that which is obtained if the reservoir were unfrac-ttm'd. It is pointed out that although the sweep efficiency may he very low in vertically fractured five-spot patterrz.s, the area swept at low water-oil ratios may be only 5 to 10 per cent less than those achieved if the reservoir were unfractured. INTRODUCTION Since the initiation of commercial reservoir fracturing techniques it has been desirable to determine the effect of fractures on the areas swept after breakthrough. Most water flooding or gas cycling projects are continued for substantial periods after the brcakthrough of the injected fluid. Although the sweep efficiency serves as one criterion for rating various flooding patterns. the area swept after breakthrough for various water-oil ratios or percentage wet gas, if cycling. is of perhaps more importance than the sweep efficiency alone. Sweep efficiency data on the vertically fractured five-spot have been presented3. Previous work on the line-drive pattern has shown the effect of vertical fractures on the area swept after breakthrough for the case in which the distance between injection and producing wells divided by the distance between adjacent input wells was equivalent to 1.5 (see lief. 2). The data indicated that for the line-drive pattern it may be desirable to flood or cycle substantially perpendicular to the fractures in order to achieve the greatest recovery for the smallest volume of fluid injected. For this study the center well of a five-spot is assumed as the fractured well. All fractures were assumed to originate at this well and extend into the reservoir for various distances and orientations. All the fractures are straight and are of large permeability compared to the matrix proper. These data are presented to aid the engineer in estimating fractured five-spot pattern performance. ANALOGY The potentiometric model was used in making this study. The model used was 20 20 in. by approximately 1-in. deep. For certain portions of the study one corner of this model was considered to be an injection well and the opposite corner a production well. To simulate vertical fractures a copper sheet was soldered to the wire well and made to conform to the desired length and orientation. In other studies the same model was used except that the four corners of the model might be considered as the corner wells of a five-spot pattern and a fifth well was placed in the center of the model. The well placed in the center of the model was fractured. The total fracture length is L and the well spacing. d. The complimentary fracture angles will be obvious from Figs. 3 and 4. The data obtained on the potentio-metric model assumes the pay to be uniform and homogeneous, the mobility ratio is one, steady-state conditions exist and gravity effects arc neglected. The permeability of the fractures is very great compared to that of the matrix proper. The po-tentiometric model has been used widely both in water flooding and gas cycling projects, and may be used for miscible displacement; how-ever. it is believed that the poten-tiometric model data are more properly applicable to gas cycling than water flooding because the model as-

By ALEXANDER L Hay, Alexander L.

THE Sydney coal field, the largest and most valuable in Nova Scotia, is on the northeastern coast of the Island of Cape Breton, extending from Mira Bay on the south to Cape Dauphin on the north, a distance of 30 miles, and has a general dip northeast under the sea. The field embraces the mining villages of Morien, Birch- grove and Reserve and the towns of Dominion, Glace Bay, Waterford and Sydney Mines. The city of Sydney is about midway between the northern and southern extremities of the field and on the western fringe of the productive coal measures. Sydney harbor crosses the coal field, cutting off direct rail connection between Sydney Mines and the greater part of the field to the southeast.

Jan 1, 1928

By H. Biloni, R. Morando

The surface structure and substructure of Al-Cu alloys solidified as conventional ingots and under particular conditions such as those used by Bower and Flemings are studied. The influence of lampblack coating on the mold walls is especially considered and the results compared with those obtained in copper and graphite molds where no coatings exist. When high heat extraction conditions exist the observations show that mechanism of copious nucleation is responsible for most of the chill zone. When the heat extraction through the mold walls is low, a coarse grain structure with dendritic morphology arises, with a size that depends on the degree of convection present, analogous to that analyzed by Bower and Flemings. In both cases the effect of the convection on the macroscopic and microscopic appearance is discussed. The ingot macrostructure consists of one or more of three zones: "chill zone", "columnar zone", and central "equiaxed zone". The mechanism of the columnar-equiaxed transition has been subject of considerable interest and at present at least three theories exist about the formation of the equiaxed region: 1) the constitutional supercooling theory1 maintains that the equiaxed crystals nucleate after the columnar zone has formed, as a result of the constitutional supercooling of the remaining liquid; 2) chalmers2 pointed out, however, that there were several objections to this proposal, and that consideration should be given to the possibility that all the crystals, equiaxed as well as columnar, originated during the initial chilling of the liquid layer in contact with the mold; 3) Jackson et aL3 and O'Hara and ~iller~ suggested that a remelting mechanism of the dendrite arms is responsible for the formation of the equiaxed region. After the work of Cole and Bolling and other authors6 it became evident that convection (natural, reduced, or forced) plays a very important role in the transition from columnar to equiaxed and on the size of the resultant equiaxed structure. Until recently the accepted explanation of the chill zone was that it occurs as a result of copious nucleation in the liquid layer in contact with the mold walls.798 The columnar region is a subsequent result of the growth of favorably oriented grains and, as a result of a selection mechanism studied by Walton and Chalmers,9 elongated grains with marked texture are formed. Recently, however, Bower and Flemings" using an ingenious laboratory experiment introduced the idea that the "copious nucleation" mechanism is not responsible for the formation of the chill zone and that the presence of convection, introducing some form of "crystal multiplication", plays a decisive role in the formation of the chill zone. Unfortunately, it is important to consider that for their conclusions Bower and Flemings extrapolated the results obtained in their special experiments to the case of conventional ingots, and that these authors only analyzed the macrostructures of the specimens. Let us consider the work by Biloni and chalmers" concerning predendritic solidification. These authors were able to show that a study of the segregation substructure of A1-Cu gives information about the nucleation and growth of crystals formed in contact with a cold surface. A spherical predendritic region characterizes the first part of every grain nucleated in contact with the surface as a result of the chill effect. The aim of this paper is to elucidate through the observation of the segregation substructure the conditions under which (in the Bower and Flemings type of experiments and in conventional ingots) either the nucleation or the multiplication mechanism gives rise to the structure in contact with the mold walls. I) EXPERIMENTAL TECHNIQUES The experiments were performed on two alloys: Al-1 wt pct Cu and A1-5 wt pct Cu. The purity of the aluminum was 99.99 pct and the copper 99.999 pct. The results obtained with both alloys were similar. In the Bower and Flemings type of experiments the apparatus employed to obtain rapid solidification against a surface was similar to that used by those authors. The liquid was drawn by partial vacuum into the thin section mold cavity. Plate casts were 5 cm wide and usually 7.5 cm high. The thicknesses of the cast were 0.1 and 0.3 cm. Two different materials were used for the mold, copper and nuclear-grade graphite. The internal mold surfaces were polished and left uncoated for some experiments. In other experiments, the copper or graphite surface was coated with a thin film of lampblack material. In some of these particular experiments one of the mold walls was left with an uncoated region (usually in the form of a cross). The conventional ingots were cast in graphite or copper molds. In different experiments the mold walls were sometimes uncoated or coated with lampblack material. The results obtained in conventional and Bower and Flemings copper molds were compared with those obtained with copper molds coated with a very thin film of graphite; the results obtained were essentially similar. The size of the conventional ingots was 5 cm diam and 7 cm high in all cases. The cast surfaces produced by the Bower and Flemings type of experiments and conventional methods were observed macroscopically and microscopically without any metallographic preparation. As Biloni and Chalmers showed," the observation of the chill surface can give considerable information about the structure and segregation substructure.

Jan 1, 1969

By S. F. Shaw

IN 1913, the Tiro General mine, at Charcas, S.L.P., Mexico, which had been making from 125 to 150 gal. of water per min., was allowed to become flooded, after all the pumps had been removed, and in 1918 the problem of unwatering it came up for solution. There are two vertical shafts, the Tiro General, 1390 ft., and the San Fernando, 1225 ft. in depth, with five connecting levels between them. The San Fernando shaft had been partly retimbered, while the Tiro General had been newly timbered from the collar to, 1090 ft. in depth. It had been possible to place guides in only one compartment of the Tiro General, from the collar to the seventh or 850-ft. level, to which it was necessary to lower the water before station pumps could be installed. Soundings indicated that compartments in the Tiro General were open to 1082 and 428 ft., and in the San Fernando shaft to 471, 488, and 586 ft. The water had risen to a point 140 ft. below the collar of the Tiro General shaft. PUMPING EQUIPMENT The steam plant at the Tiro General shaft includes one 300-hp., one 150-hp. and one 100-hp. Erie City water-tube boiler, and two 160-hp. Heine water-tube boilers. All but one of these boilers were supposed to be in good shape, but it was soon discovered that six years of idleness in a climate that is foggy for several months of the year had left them in poor condition. The compressed-air plant comprises one Nordberg cross-compound compressor with piston displacement of approximately 2500 cu. ft. of free air compressed to 96 lb. per sq. in.; and another Nordberg cross-compound with piston displacement of 1235 cu. ft. of free air, to the same pressure.

Jan 2, 1920

By C. M. Moncrief, B C. Craft

A bentonite-clay drilling mud when treated with tetrasodium pyroarsenate underwent substantially the same reduction in viscosity and water loss as when treated with the complex phosphates. The complex arsenate showed a slightly higher reversion after heating; the other arsenates showed poor viscosity-reducing properties. Introduction During the past 10 years the chemical control of drilling mud has become of major importance in affecting the successful drilling and working over of wells. The desired properties of drilling mud have been well established, and in obtaining these characteristics there has developed a large market for viscosity-reducing chemicals. Viscosity reduction produced by humic acid, tannic acid, sodium silicate, sodium tannate, Calgon, and the complex phosphates has been described by Loomis, Ford, and Fidiam.l The effects Of treatment with complex phosphates and ammonium PolyPhosPhates on the rheological properties of muds were investigated by Fancher2 and the alkali vanadates have been described by Williams.3 Laboratory Investigations It is the purpose of this paper to point out the effects of arsenates in controlling the viscosity and gelling characteristics of a drilling mud. Viscosities and gel strengths were measured at room temperatures with a Stormer viscosimeter calibrated in centipoises and operated at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester at a pressure of I00 lb. per sq. in. for 30 min. The hydrogen-ion concentration was measured with a glass electrode. The bentonite-clay suspensions were prepared in the laboratory and allowed to age several days before testing. Members of the Arsenic Group in the periodic Table include arsenic, antimony and bismuth, but this investigation was limited to arsenic. Phosphorus also occurs in Group V of the Periodic system and phosphorus and arsenic form many closely related compounds such as pH3 and AsH3, P2O5 and As2O5, H3PO4 and H3AS04 Samples of tetrasodium pyroarsenate were prepared by fusing c.p. disodium arsenate (Na2HA5O4.7H2O). According to Friend,' this re-forms the ortho-arsenate on dissolution in water. Sodium trihydrodiorthoarsenate was prepared as described by Mellor,5 from arsenic pen-toxide as follows: As2O5 + 3H20 -> 2H3AsO4 2H3AS04 + 3NaOH Na3H3(AsO4)2 .3H20 Sodium dihydrogen orthoarsenateWaHz-As04) was obtained by fusing together equivalent quantities of arsenious Oxide and sodium nitrate, dissolving the residue in water and allowing it to crystallize.

Jan 1, 1946

By C. M. Moncrief

A bentonite-clay drilling mud when treated with tetrasodium pyroarsenate underwent substantially the same reduction in viscosity and water loss as when treated with the complex phosphates. The complex arsenate showed a slightly higher reversion after heating; the other arsenates showed poor viscosity-reducing properties. Introduction During the past 10 years the chemical control of drilling mud has become of major importance in affecting the successful drilling and working over of wells. The desired properties of drilling mud have been well established, and in obtaining these characteristics there has developed a large market for viscosity-reducing chemicals. Viscosity reduction produced by humic acid, tannic acid, sodium silicate, sodium tannate, Calgon, and the complex phosphates has been described by Loomis, Ford, and Fidiam.l The effects Of treatment with complex phosphates and ammonium PolyPhosPhates on the rheological properties of muds were investigated by Fancher2 and the alkali vanadates have been described by Williams.3 Laboratory Investigations It is the purpose of this paper to point out the effects of arsenates in controlling the viscosity and gelling characteristics of a drilling mud. Viscosities and gel strengths were measured at room temperatures with a Stormer viscosimeter calibrated in centipoises and operated at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester at a pressure of I00 lb. per sq. in. for 30 min. The hydrogen-ion concentration was measured with a glass electrode. The bentonite-clay suspensions were prepared in the laboratory and allowed to age several days before testing. Members of the Arsenic Group in the periodic Table include arsenic, antimony and bismuth, but this investigation was limited to arsenic. Phosphorus also occurs in Group V of the Periodic system and phosphorus and arsenic form many closely related compounds such as pH3 and AsH3, P2O5 and As2O5, H3PO4 and H3AS04 Samples of tetrasodium pyroarsenate were prepared by fusing c.p. disodium arsenate (Na2HA5O4.7H2O). According to Friend,' this re-forms the ortho-arsenate on dissolution in water. Sodium trihydrodiorthoarsenate was prepared as described by Mellor,5 from arsenic pen-toxide as follows: As2O5 + 3H20 -> 2H3AsO4 2H3AS04 + 3NaOH Na3H3(AsO4)2 .3H20 Sodium dihydrogen orthoarsenateWaHz-As04) was obtained by fusing together equivalent quantities of arsenious Oxide and sodium nitrate, dissolving the residue in water and allowing it to crystallize.

Jan 1, 1946

By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf's remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By Frank T. Wheby

The cost of tunneling is highly sensitive to the rock characteristics through which the tunnel is to be driven. These characteristics affect in a major way the rates at which tunnels and shafts can be driven and the degree to which the openings must be supported to maintain them in a permanent stable condition. Tunnel and shaft design and cost criteria have been computerized, permitting estimates of tunnel-shaft systems to be made directly from inputs of rock mechanics characteristics and other data. Curves of quantities of steel, rock bolts, and other rock support items as related to tunnel size and rock quality designation are presented. An illustrative example of the use of the program in calculating the cost of a hypothetical tunnel system is included.

Jan 1, 1971

By Hans Lundberq

IINDUSTRY'S attention is now focused on the production of munitions thereby creating a demand for certain minerals which in prewar days were produced only in limited quantities. Now production of these minerals must he increased from the known deposits and new deposits must be found. Can geophysics help? "War minerals" such as tin, vanadium, tungsten, antimony, manganese, chromium, and cinnabar have no physical characteristics sufficiently different front the country rook to permit their direct location by ordinary geophysical methods. As already demonstrated in work on gold and oil, useful information may be obtained indirectly, however, outlining structural features or geological conditions favorable for the deposition of such ores or the accumulation of oil. Recently, more direct and truly qualitative methods have been brought into a useful and practical stage, and by the combined application of old and new methods a technique has been developed which, it is hoped, will be of importance in the search for these vital minerals.

Jan 1, 1941

By L. L. Melton, W. T. Malone

Fluid mechanics research conducted with non-Newtonian fluid systems now permits prediction of the behavior of these fluid systems in both laminar and turbulent modes of flow through circular pipes. Present work concerns non-Newtonian fluid systems currently used in the hydraulic fracturing process. During fracturing treatments, an unsteady-state condition may frequently be encountered arising from. the reaction rate of a chemical additive. This condition must be evaluated in order to predict the actual behavior of a particular fluid during field application. Design and operation of the apparatus used to determine fluid-flow behavior permit obtaining data under such non-equilibrium conditions. This paper shows methods used to obtain rheology measurements, develop hydraulic relationships and evaluate chemical reactions producing unsteady-state conditions. Engineering application of this research is illustrated by employing measured rheological values and developed hydraulic retationships to produce frictional pressure loss (psi/100 ft) us flow rate (bbl/min) charts of common tubing and casing sizes for an example fracturing fluid. How these charts and chemical reaction rate information are then combined to predict actual turbulent hydraulic behavior during unsteady-state field conditions is also discussed INTRODUCTION Many fluids used in hydraulic fracturing contain chemical additives which impart non-Newtonian fluid properties that may drastically alter their hydraulic behavior. Equally drastic alteration in wellhead pressure, injection rate and hydraulic horsepower requirement may result from these fluid properties. Prior research conducted to relate non-Newtonian fluid properties with hydraulic behavior has not as yet produced a universal relationship, particularly for the turbulent flow region. which of the many Possible non-Newtonian fluid properties is responsible has not been conclusively established. A systematic description, suggested by Metzner, of the many possible non-Newtonian fluid properties exhibited by real-fluid behavior, and a current discussion of theoretical and applied aspects of non-Newtonian fluid technoloy can be found in Handbook of Fluid Dynamics. f Little or no research has previously been attempted with fluids exhibiting time - dependent properties. Addition of chemicals during a fracturing treatment is often accomplished by continuously mixing and displacing the fluid. This produces a time-dependent effect or unsteady-state condition while the fluid is progressing through surface and wellbore conductors. This condition is due to solution or chemical reaction of the additive. Considerable departure from conventional methods of obtaining and interpreting data was found necessary to consider these conditions. Therefore methods were developed to obtain hydraulic behavior information under these complex, unsteady-state conditions. Relationships presented in this paper to predict hydraulic behavior of non-Newtonian fluids in circular pipes were obtained by constructing and operating a small pipeline apparatus in the manner of a pilot-plant study. These relationships are suggested as scaleup equations and are not proposed as fundamental rheological parameters. While perhaps deficient from a fundamental research viewpoint, a pilot-plant study does permit the determination and convenient evaluation of variables pertinent to a process. A pilot-plant study can result in a valid engineering application procedure even when fundamental relationships are still undefined. An excellent series of articles by Bowen has appeared in the chemical engineering literature.2-8 These give a thorough review of proposed hydraulic relationships and their limitations for non-Newtonian fluid behavior in circular pipes. A graphical method is presented to scale up data for a fluid exhibiting an anomalous hydrau1ic behavior in the turbulent flow region. Considerable assistance has been obtained from these articles to interpret the anomalous behavior noted during this investigation. These articles also provided assurance that a pilot plant is a practical approach to evaluate the hydraulic behavior of non-Newtonian fracturing fluids. _____________

Jan 1, 1965

By Lawrence H. Van Vlack, Otta K. Riegger

Periclase-type oxides were examined microscopically after being exposed to siliceous liquids. The rate of grain growth was found to be inversely proportional to the grain diameter. Grain growth proceeds more rapidly at higher temperatures, but is retarded by increasing liquid contents. aMag-nesiowiistites with higher MgO contents grow less rapidly than those with higher FeO contents. The growth rate is reduced by the presence of a second solid phase. The silica-containing liquid penetrates as a film between the individual magnesiowus tite grains. This is independent of time, temperature, amount of liquid, or the MgO/ Fe0 ratio. When present, olivine and spinel-type phases can provide a solid-to-solid &apos;&apos;bridge" between magnesioustite grains. THIS paper presents the results of a study of the microstructures of periclase type oxides in the presence of a silicate liquid. The purpose was to learn more about the effect of service factors such as 1) time, 2) temperature, and 3) liquid content upon A) grain growth, and B) liquid location among the solid grains. This study was prompted by the fact that periclase refractories are known to have very little solid-to-solid contact when the phases which are present are limited to periclase and liquid. Such a micro-structure gains industrial significance because it permits fracture during service when stresses are applied at high temperatures. The details of ceramic microstructures have not received extensive attention. This is in contrast to the extensive attention given to a) the phase relationships pertaining to refractory compositions, and b) the details of the microstructures of comparable metallic materials. A brief review will be made of the pertinent phase relationships and microstructural considerations in general, as well as of refractory compositions. a) Phase Relationships. This investigation was limited to those compositions in which (Mg, Fe)O was the solid phase. MgO and FeO form a complete series of solid solutions. Pure MgO has the name of periclase. The related FeO structure is called wustite. Both have the NaC1-type structure: however, wustite possesses a cation deficiency so that the true composition is Fe<10 even in the presence of metallic iron. The phase relationships involving solid (Mg, Fe)O and a silicate liquid are shown in Fig. 1. In this case. the liquid is saturated with (Mg, Fe)o. There-fore its SiOz content is below that encountered in orthosilicate liquids. As a consequence the liquid phase specie:; are primarily the following ions: and 0-&apos; plus occasional Fe+ ions. Two features are of importance: a) the liquid contains relatively small species and b) the liquid contains large quantities of the same species as the solid. viz., Fig. 2 shows the system, FeO-SiOz, which will be used in some of the discussions that follow. This diagram is the right side, vertical section of Fig. 1. Here, as pre\iously, the composition at the FeO end of the diagram is nonstoichiometric, varying from Feo.950 when the liquid oxide is in contact with the solid iron, to about Fe 0, when the solid oxide is in equilibrium with an atmosphere of equal proportions of CO and C02 at the solidus temperature. The Fe/O ratio will be maintained in wustite in the presence of SiO,. However, the FeM/Fe++ ratio in the liquid will be lower because of the effect OIF the SiO, on the activity of the FeO. With the addition of MgO to wustite, the over-all composition (IvZg, Fe)@, has a value of x lying between 0.9 and 1.0 when the COz/CO ratio is 1.0&apos;. b) Microstructures. In general, published attention to refractory microstructures has been directed toward the phase analyses that accompany compositional variations. This is illustrated by Harvey6 in his work on silica brick and by wells7 in his work on periclase brick. In each case, a series of altered zones is encountered which provides a sequence of phase associations. If due consideration is given to reaction kinetics, such an examination reveals phases that are compatible with equilibrium studies. Admittedly, however, it is often necessary to determine more complicated polycomponent systems to account for all the phases present.8 Relatively little attention has been given to microstructural geometry in ceramic materials. Certainly less attention has been given to this aspect of ceramic microstructures than to the size, shape, and distribution of the constituent phases in metals. Burke has pointed out that the grain size of oxides follows the same growth rules as for metals, viz.,

Jan 1, 1962

By Sam N. Dewitt, Albert S. Trube

This paper presents a discussion of the pressure maintenance operations which were begun in the New Hope Field. Franklin County. Texas. in 1944. The project has required the injection of extraneous waters at depths from 7.300 to 8.000 ft with intake well-head pressures up to 4.000 psi in three different reservoirs — the Bacon. Hill. and Pittsburg. Records of oil and water production. water injection and the GOR have been kept for each reservoir and reservoir pressures were taken at regular intervals. These data indicate that the Bacon Reservoir had no apparent water encroachment up to the time of water injection. However. the Pittsburg and Hill reservoirs had some natural water influx hut not sufficient to prevent pressures from declining below the bubble point. The Bacon and Hill reservoirs responded almost immediately to water injection. while the Pittsburg which is the least permeable. has shown good pressure response only since .August, 1948. The principle objective of the project has been to increase ultimate recovery. Success of the project to date also has resulted in reduced lifting costs. Esti- mates based on the initial water breakthrough patterns indicate that the primary objective of substantial additional recovery will he accomplished, and there is a possibility that the original estimates elf oil recovery with pres-sure maintenance will he exceeded. INTRODUCTION This pressure maintenance project was one of the earliest primary pressure maintenance programs to he attempted on a multiple zone field. There are three producing reservoirs into which water is being injected for the purpose of maintaining pressure and increasing the ultimate recovery- from each. This paper is limited in scope to al1 account of the development of the project. the pressure production relationship prior to the injection of water and the effect of water injection on the producing reservoirs. Also discussed are the nature of the injection system and the indicated results on initial water break-through in the Bacon Reservoir. FIELD CONDITIONS The New Hope Field, which is located about 12 miles northeast of Winusboro, Franklin County, Texas, is an elongated symmetrical anticline containing four known oil reservoirs. The reservoirs are of the Trinity group of the Comanchean or Lower Cretaceous period and are found in Table I. The oil productive portion of each reservoir is not present in all of the producing wells because their areas and positions vary with respect to one another. Fig. 1 shows the relative position of the four reservoirs and illusIrate? how some wells could penetrate all four, while others are restricted to three. two. or perhaps one. depending on structural location. The first three reservoirs contain undersaturated oil. The deepest. the Elledge, has a primary gas cap. Although this reservoir covers a considerable area of the field. it has a very thin section and a low order of permeability. Elledge producing wells have generally been characterized by an early increase in GOR, making it necessary to recomplete them in other reservoirs. (At present. one well is completed in the Elledge. which is still producing.) Because of the difficulties en-countered in producing oil from this reservoir. and the small quantity of oil actually present. future attempts at producing it will probably be on a salvage basis during the later life of the program. For this reason, the remainder of this report will be confined to a discussion of the Bacon, Hill and pius-burg reservoirs.

Jan 1, 1950

By J. F. Ednie

SCRAP metals to the value of more than a billion and a half dollars were recovered in the United States in 1939 for further use in industry. Few people have any true conception of the magnitude of the secondary-metal industry as related to that engaged in the production of the primary, or virgin, metals; of its importance, particularly when a shortage of primary metals exists, as at present; or of the advance that has been made in standardizing and improving the quality of its products. Of the iron and steel produced in the United States in 1939 (the data used in this article are largely taken from Bureau of Mines reports for that year) just over 50 per cent came from scrap and slightly less than 50 per cent from ore. Of the principal nonferrous metals-aluminum, anti-mony, copper, lead, nickel, tin, and zinc-63 per cent came from domestic ores and 37 per cent from scrap. Fig. 1 presents graphically the relative tonnage and value of primary and secondary production of ferrous and nonferrous metals. In this chart only purchased secondary metals are considered, the figures being exclusive of "home" or "plant" scrap which amounts to rather large figures in the iron and steel industry. Incidentally, the chart shows that from the tonnage standpoint the iron and steel industry is some twenty times larger than the nonferrous industry, though with regard to the value of the product the ratio drops to about two to one.

Jan 1, 1941

By W. J. Rude

LARGEST of the known commercial deposits of pebble phosphate are those found in Polk County, Florida. The phosphate bed, commonly known as the matrix, will consistently average 6 to 9 ft. in depth, and is found under 3 to 60 ft. of over-burden. The phosphate pebbles, white and black in color, varying greatly in grade, are found imbedded in a matrix of sand and clay; and range in size from the fines to pebbles 1 1/2 in. in diameter, although the average coarse size is approximately 1/2 in. in diam¬eter. On some of the washers all material under 14 mesh is lost. High-grade phosphate (75 per cent plus of bone phosphate of lime, CasP2Oa) is generally soft, the pebbles breaking up during the mining operation and in pumping; low-grade phosphate, 67 to 69 B.P.L., is black in color with hard pebbles with no loss encountered in pumping.

Jan 1, 1941

By A. E. Belton

The individual projections for large mines in the Pittsburgh coal seam in northern West Virginia are discussed with emphasis on roof control and ventilation requirements. All four mines use continuous miners with panel belts and rail for main line haulage. Both development and retreat-type mining are covered. There are a variety of mining projections being used currently in northern West Virginia. To discuss each would be impossible, so an arbitrary cross section has been selected in an attempt to indicate a fair degree of representation. Four mines, hereinafter referred to as Mines A, B, C and Dl will be discussed separately. The greater part of northern West Virginia coal production is mined from the Pittsburgh seam. This is the seam worked by all the mines discussed here. Although the coal bed outcrops at the eastern and southernmost points, these mines are all working in a depth ranging from 400 to 1400 ft below the surface. Some steep gracles have been encountered but are only considered local in nature; the overall average dip of the seam is 1 1/2 % northwest. In each of the operations the particular mining scheme used has proved advantageous, since they have been designed to satisfy particular equipment and/or physical condition requirements. So regardless whether such projections utilize a partial or full recovery principle, the productivity performances appear better than average. MINE A Full retreat is the basic mining approach for mine A, although current mining is primarily in the entry-driving stages to expand territory in preparation for pillar work. Only one section unit now on retreat. The average clean coal production at this mine is 7000 tons per day. Initially, a ripper-type miner was used for development at this mine. But with a rather weak roof overlying the coal bed and the greater horizontal span left at the top by a ripper machine, roof control became a critical problem. Even though roof bolts were used concurrently in the mining cycle for initial support, the majority of the roof in these entries

Jan 1, 1962

By Bjorn N. P. Paulsson

A number of granitic rock specimens have been studied from the Stripa mine site in connection with a large-scale geomechanics research program. The purpose of the program was to evaluate and develop field and laboratory techniques for rock mass characterization and to determine design parameters for storage of nuclear waste. In this paper a minicomputer-based technique for studying dynamic rock properties in the laboratory is described, together with results from the tests. The specimens were tested under different uniaxial and saturation conditions. Specimens from a field-heated rock mass were also tested to determine if temperatures typical of those encountered with nuclear waste would introduce additional fracturing. Both Vp and Vs increased with stress for both saturated and dry specimens. Both Vp and Vs were higher for saturated specimens at all stress levels compared with the dry. The velocities increased linearly or near linearly with saturation. The test results on the previously heated samples indicate that attenuation is more sensitive to thermally-induced microfracturing than velocities. Analysis of the attenuation values with stress show that rock heated to 200°C is damaged, and that the damage is in form of low-aspect ratio fractures.

Jan 1, 1984

By Halbert Powers Gillette

In every chemical reaction heat is either developed or absorbed, and this plus or minus heat of formation is as definite in quantity as the weights of the reacting elements. In this paper I shall show that each chemical element and each chemical radical has its own definite heat-valency,—a fact which, so far as I know, has hitherto escaped the attention of investigators, but, I feel sure, will be admitted after the demonstration here given, and may lead to some practical conclusions of value. When Berthelotys " law of maximum work " was found to have so many inexplicable exceptions, the pendulum of a scientific theory swung away from a recognition of the truth underlying that proposition; and this reaction went so far that not only has thermal chemistry been relatively neglected by recent investigators, but it is not uncommon now to find textbooks on physical chemistry which practically ignore all that Thomsen, Berthelot and others have done. To this temporary tendency of thought I attribute the failure to recognize the principles herein announced and explained. Not long ago, while studying tables of the formation-heat of various salts, I noticed that in this respect all potassium salts in solution differ from the corresponding sodium salts by 9.3 cal.1 I found also that similar differences exist between other salts, not only when the basic radical is varied, while the acid radical remains constant, but also when the acid radical is the variable. Thus chlorine salts in solution differ from bromine salts in this respect by 10.9 cal. Upon further study, I found that Thomsen had noted similar constant differences, but, so far as I can ascertain, he appears to have attached no great significance thereto.

Jan 1, 1904

By John B. Miles

THE present period of depression in the iron industry, with the resultant close approximation of the cost of production to the selling-price of pig-iron, should make the discussion of this subject at this time not only interesting but, profitable. It is possible that it may result, in the collection of data, which when added to those set forth in this paper will clearly indicate the influence of the rate. of driving a blast-furnace upon its fuel-economy. The question is not whether an excessive rate of driving (meaning a rate definitely in excess of the average rate in the United States) results in, an increase in the fuel-consumption, but rather whether a rate considerably less than the average does not result in a marked decrease in the fuel-consumption. The commercial and metallurgical sides of. this problem must be kept separate. With a large margin between the cost of production and the selling-price of pig-iron, and a plant already in operation, it is frequently profitable to sacrifice a couple of hundred pounds of fuel per ton of pig-iron in order to secure the greater gross profits resulting from a larger tonnage. When this margin decreases with a plant in operation, or when the determination of the size of a new furnace intended for a certain production . confronts the management, a clear understanding of the effect of the rate of driving upon fuel-economy becomes necessary. If it be granted that slow driving leads to low fuel-consumption, it should he borne in mind in the design of a new plant for the production of a certain tonnage that the adoption of an economical rate of driving increases only the size of the furnace proper, whereas, due to the decrease in quantity of blast required on account of the decrease in fuel burned, the stoves, the blowing-engines, the boilers and the piping may be de-

Sep 1, 1908