Search Documents

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By H. J. Beach

This paper describes the properties and uses of cementitious mixtures containing 10 to 20 per cent bentonite and 2 per cent or more sodium chloride. Salt additions improve bentonite cement by increasing early strength and stabilizing viscosity without changing thickening time. The volume yield of cement is increased 20 per cent or more without lowered early strength. The unique properties of salt in this type of system make savings of more than 10 per cent possible where light-weight, low-strength cementitious material is adequate to fill behind pipe. The density range of these mixtures is 12 to 13 1b/gal and the filtration rates are medium-low, aiding the placement of long columns in primary cementing. Where available, sea water is an ideal salt source in preparing these slurries. INTRODUCTION Accelerators increase the rate of cement hydration. In speeding reaction with water, they can affect cement performance by reducing thickening time and increasing early strength after set. Accelerators that cause both effects can be considered "total", and those which produce only one effect can be called "partial". Materials that act conversely to accelerators are retarders. and they also can be total or partial. Partial retarders. make high-temperature cementing possible by prolonging thickening time while impairing early strength only slightly. Most known accelerators are total. A useful partial accelerator would increase strength without altering thickening time. This report concerns material combinations in which a normally total accelerator exerts unique partial properties. Utilizing these limited effects improves bentonite cement. SEPARATE EFFECTS OF SODIUM CHLORIDE AND BENTONITE ON CEMENT Sodium chloride and calcium chloride are commonly used in cement, and at low concentrations their effects are similar. Ludwig1 studied sodium chloride in API Class A and Class E cements.' Figs. 1 and 2 sum- marize his data taken at 140°F on slurry pumpability and early strength. Normal water-to-cement ratios are 0.46 and 0.40, respectively, for Class A and Class E cements. At saturation the salt content is 12 to 14 per cent of the weight of cement solids. The illustrations, therefore, cover the range of salt solubility in the mixing water. The data show that sodium chloride is a total accelerator of the Class E cement studied over the range of solubility. It is total in Class A cement to 6 per cent. Above this concentration salt becomes a retarder— partial from 6 to 10 per cent and total above. These results are general for different brands of Class A cement, although the shift from acceleration to retardation may occur at different salt concentrations for different temperatures. The results are specific for the Class E brand studied. In discussing his data, the investigator emphasized that different Class E cements might respond erratically to salt, depending on the brand chosen. Morgan and Dumbauld3 escribe the properties of bentonite cement in a paper that is a standard reference in using these systems. Bentonite functions in cement as an enabling agent; each bentonite addition equal to 1 per cent of the weight of dry cement makes possible the further addition of 4.5 per cent water.' Thus, 10 per cent bentonite in Class A cement, normally slurried neat with 46 per cent water, enables the slurry to contain another 45 per cent before settling. Water is one of the lightest and cheapest cement extenders; it reduces density and cost. Bentonite cements produce uniform slurries having low susceptibility to solids separation. After set, they offer low resistance to perforation.

By S. Leber

Pole figures and pole distributions were used for the quantitative detevinination of the preferred orientations in swaged tungsten rods and the effect of subsequent wire drawing on the texture. In the swaged rod, the preferred orientation could best be described as a pseudo (111-112) [110] cylindrical texture. A secondary component was assigned the indices (110) [001]. Further reduction by swaging retained these cylindrical textures. Wire drawing caused lattice rotations about the wire axis, converting the cylindrical texture into a normal fiber texture. The conversion was initiated and proceeded lnost rapidly in the center of the wire. The (110) /001] component was converted into a (110) fiber texture by wire drawing. The effective rotations were about axes contained in the lransverse plane. The preferred orientation associated with tungsten wire usually has been assumed to consist of a (110) fiber texture. This implies rotational randomness around the wire axis. Leber1 has shown that rotation about the wire axis may be restricted resulting in a preferred orientation designated as a cylindrical texture. Specific crystal planes tended to remain aligned parallel to the wire surface. This texture seemed to be the result of the swaging operation used in the intermediate stages of fabrication. Bhandary and cullity2 detected similar textures in swaged iron wires. Peck and Thomas3 suggested that the preferential alignment of crystal planes parallel to the wire surface was the result of tangential flow, characteristic of swaging. Wire drawing, following swaging, twisted the crystals about axes parallel to the wire axis, converting the cylindrical texture into a normal fiber texture.4 In this investigation, quantitative techniques were used to more accurately characterize the cylindrical texture and to study its conversion into a normal fiber texture. PROCEDURE The material investigated was lamp-quality tungsten. Three ingots were rod-rolled and swaged to 112 mils diameter, and were then drawn to 10-mil wire. Samples were obtained after each drawing pass. (110) and (200) pole figures were obtained from samples prepared as shown in Fig. 1. To form the sample shown in Fig. l(a), l-in. lengths of wire were glued side by side to form a l-in. square. The composite was ground and electropolished to form a diametral reference surface. For certain specific tests, samples were prepared as shown in Fig. l(b). This composite was made from 10-mil-thick strips prepared by grinding on parallel longitudinal planes. The polished reference surface in this case was, in essence, the wire surface. The two forms of samples [~igs. l(a) and l(b)] were related by a 90-deg rotation around the wire axis. Because of ease in preparation, most data was obtained from the diametral samples. The X-ray data were obtained using a Siemen's pole-figure goniometer. These data were not corrected for absorption or defocusing effects, since only the angular locations of the intensity maxima were of interest. Regions of the pole figure more than 80 deg from the center were not investigated. Partial monochromatization was achieved by the use of unfiltered copper radiation and a krypton-filled proportional counter. No evidence of spurious white radiation effects5 could be detected. Therefore, more elaborate X-ray techniques were not required. Intensity levels were chosen to show all pertinent details of the orientation distributions. The reference plane for the pole figures was the diametral section. The orthogonal reference directions, shown in Fig. 1, were the wire axis, the radial axis per-

Jan 1, 1965

By J. P. Heller

The purpose of this discussion is to comment briefly on one of the points raised in the paper. The topic is that referred to in the Conclusion 2, in which the authors note a "disproportionate increase in mixing rate" as they proceed from a displacement performed at viscosity ratio 0.998 to one at 1.002. The recovery curve of this displacement, Fig.2A, shows a quite noticeable difference between the two runs in which displaced and displacing liquids were interchanged. This difference is ascribed by the authors to the change in viscosity ratio between the two experiments. This interpretation of the experimental results must certainly be based on rather precise measurements of the fluid viscosities or, at least, of the ratio of their viscosities. The ordinary Ostwald viscometer, employed in the usual way, is only just able to distinguish between liquids whose viscosities differ by two or three parts per thousand. The experimental refinements which then must have been necessary to measure with any precision a viscosity ratio of 1.002 would be worthy of mention. Indeed, one would have expected the authors to devote at least a paragraph to the display of this technique. For the same reason - to emphasize that the details of such unusually critical experimental work should be reported and discussed in the literature — I would have liked to see some comment by the authors on the requirements for temperature control during both the viscosity measurements and the displacement experiments. The temperature coefficient of viscosity of Soltrol C at room temperature has been measured in this laboratory at about - 1.9%/1°C. How much did the coefficients for the fluid mixtures used in the experiment differ from this and from each other Even if the two fluids were identical in this respect, it would appear that a temperature difference of .l°C between them in the flow system would produce a viscosity con- trast equal to that imposed by their composition. Reference to the experimental solutions of these problems would render Conclusion 2 more credible. Published theoretical work on the stability problem contains no indication of such extreme sensitivity to the viscosity ratio in the immediate neighborhood of unity. On the contrary, perturbation calculations such as those made by Chuoke1 and Perrine2 lead to initial finger growth rates proportional to the first power of the viscosity difference. The later instability growth calculated by Scheidegger,3 using the assumption of zero pressure gradient perpendicular to the average flow, is also simply proportional to the viscosity difference. The conflict regarding the sensitivity of the dependence of instability growth or mixing rate on the viscosity contrast needs explicit recognition in the literature. In particular, it would seem that the experimental work reported here should be supported by a more detailed description of the viscosity controls. Further discussion of possible alternative interpretations of the data would also be in order. For instance, is it possible that the unconsolidstted bead pack used changed its characteristics between the runs (due, perhaps, to the handling and inverting involved in the injection of the front) Or, are the data points of Fig. 2A averages from several runs performed in a series in which the two liquids alternated as displaced and displacing fluids? To summarize, it seems to me that the relationship asserted by Conclusion 2 in the paper needs the support of more detailed experimental evidence. REFERENCES 1. Chouke, R. L., van Mews, P. and van der Poel, C.: "The Instability of Slow Immiscible Viscous Liquid-Liquid Displacements in Porous Media", Trans., AIME (1959) Vol. 216, 188.

By S. R. B. Cooke, W. Philippoff, Donald E. Cadwell

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953

By D. N. Seidman

In the course of a study of the electronic and thermodynamic properties of Pb-Se alloys it was found necessary to have an accurate knowledge of the phase diagram. However, the literature is in disagreement as to whether or not a monotectic reaction occurs in the lead rich portion of the phase diagram. Pelabonl reported only a two-phase region consisting of lead-rich liquid and solid PbSe extending from almost pure lead to the compound PbSe, and gave the melting point of PbSe as 1065°C. The data of Friedrich and Leroux2 are in general agreement with this type of diagram, with the melting point of the compound being 1088°C. However, Nozato and Igaki by inverse rate thermal analysis observed a monotectic reaction isotherm exlacing at 860°C with a monotectic composition of 20.5 at. pct Se. The miscibility gap in the liquid state extends from 7.5 to 20.5 at. pct Se. Hansen and Anderko4 accepted Nozato and Igaki&apos;s phase diagram in the region of the lead-rich monotectic. To reinvestigate this portion of the phase diagram, both thermal analysis and metallographic examination of various compositions were performed. The thermal analysis apparatus was constructed according to the specifications of the National Bureau of Standards. A t/t-l pct Rh thermocouple was calibrated against the melting point of copper (NBS), zinc (NBS), and antimony (A. D. Mackay), the emf being measured with a Rubicon Type B potentiometer sensitive to lpv. The absolute accuracy of the thermal analysis obtainable with this system is ± 0.5oC. Starting materials were semiconductor grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999 pct pure with only trace impurities detected upon spectroscopic examination. One hundred galloys were sealed in quartz crucibles with a central thermocouple well under a vacuum of less than 1 p. This procedure prevented any composition change due to vaporization during the run. Cooling curves were obtained on the alloys listed in Table I. Data was taken by the direct method at cooling rates ranging between 1/2 to 2°C per min. The alloys were heated well above the liquidus and shaken vigorously to insure homogeneity. No evidence of an arrest indicative of the monotectic reaction was observed, and the two-phase region reported by Pelabonl and Friedrich and Leroux? was confirmed in general, although our data give higher liquidus temperatures than Friedrich and Leroux. The melting point of stoichiomet-ric PbSe determined for two different samples was 1080.7 0.5oC. The results of this investigation are compared with Nozato and Igaki&apos;s data in Fig. 1. To Complement the thermal analysis data, an 86 at. pct Pb specimen was examined microscopically. This composition was in the center of the miscibility gap reported by Nozato and Igaki.3 The alloy was heated to 1000°C, held for 1/2 hr, and water quenched. The specimen was polished using standard metallographic techniques for lead. The alloy was etched with an acetic-nitric acid etchant for 10 min at 45°C. Microscopic examination did not indicate the existence of two separate layers or solidified droplets imbedded in a matrix, as would be expected if a miscibility gap were present. The mi-crostructure shown in Fig. 2 consists of uniformly dispersed, dendritic PbSe in a lead-rich matrix.

Jan 1, 1962

By J. W. Goss, M. J. Coolbaugh

A survey of literature published in the U.S. on grouting indicates that most such work has been done to stop water flow in mines and for stabilizing foundations of various man-made structures. Apparently San Manuel is one of the first mines in this country to use grout extensively underground for the strengthening and stabilizing of ground about drifts, shafts, and stations.

Jan 3, 1961

By Carl A. Holley

Agglomeration is very closely identified with the mining industry. Ores must be crushed finer and finer to separate minerals from gauge and the fine ore concentrates must be agglomerated so they can be handled for further processing. This paper reviews each type of agglomeration device and summarizes the areas of usage for each type of agglomerator.

Jan 1, 1980

By G. C. Kuczynski

Two particles in mutual contact form a system which is not in thermo-dynamical equilibrium, because its total surface free energy is not a minimum. If such a system is left for a certain period of time, the bonding of the two particles will take place in order to decrease the total surface area, even though the temperature is lower than the melting point. This phenomenon of bonding of two or more particles with the application of heat only and at temperatures below melting point of any component of the system will be called sintering, although the powder metallurgists use this term in a broader sense, including the presence of molten phase and pressure. It is the objective of this paper to study this process and the mechanisms involved in it. This problem is of utmost importance to powder metallurgy and powder ceramics, and its technological aspects have been studied for a good many years. However, the powder metallurgical operations are too complex and include too many superimposing mechanisms, and too many variables for a direct study. It was therefore advisable for the purposes of this study to reduce the variables to a minimum. In this work the radius of the interface formed during bonding in a simple system composed of a spherical particle and a large block of the same metal was studied as a function of time and temperature. It is believed that the mechanism involved in this simple process is fundamental to any sintering operations. Previous Work J. Frenkell was the first to make a serious attempt to develop a theory of sintering. He assumed that the process consists of a slow deformation of crystalline particles under the influence of surface tension which reduces to a viscous flow where the coefficient of viscosity n is related to the self-diffusion coefficient D by the following equation 1 _ D D6kT [1] where 6 is interatomic distance, k the Boltzman constant, and T the absolute temperature. This type of viscous flow of a crystalline substance is essentially different from the ordinary plastic flow. The latter is a specific propcrty of crystals and cannot take place in amorphous bodies. According to Frenkel this viscous type of flow is due to the diffusion of the holes or vacancies arising in the lattice. He was able to derive an equation relating the growth of the interface between two spherical crystalline particles or between a particle and a semi-infinite crystal (Fig 1) to time t at constant temperature. This relationship can be written as follows: x²— 3/2 a/nt [2] where x is the radius of the interface assumed to be circular, a the original radius of the sphere and a surface tension of the material. The other assump- x tions are that x is less than 0.3 and that during the period 1 the original radius, a, of the metallic particle did not change appreciably. A. J. Shaler and J. Wulff2 followed closely the ideas of Frenkel in their theory of sintering of a mass of metallic powder. Neither Frenkel nor Shaler has validated his theoretical speculations with conclusive experimental data. Two measurements reported by

Jan 1, 1950

By Theodore B. Comstock

The paper of Mr. S. F. Emmons on the structural relations of ore-deposits, presented at the Boston meeting in February last, having been, as I am informed, unavoidably delayed in publication, was not distributed in the preliminary edition to members until immediately before the sheets of Volume XVI. of the Transactions, containing it, were sent to press. Consequently, I saw it for the first time too late to offer any comments which might have accompanied it in that volume. This is my justification for present-

Jan 1, 1889

By Joseph P. Lyden

In the Picher field, structure made openings for the circulation of the mineralizing solutions by flexing, shearing, and fracturing the sedimentary beds. This structure is used with the spatial and genetic relationship of the ore minerals, sphalerite and galena, and the gangue minerals, dolomite and jasperoid, in prospecting for ore bodies.

Jan 12, 1950

By Theron Wasson

During 1936 the state of Michigan produced 11,868,573 bbl. This is approximately 4,000,000 bbl. less than produced in 1935. The principle reason for the decrease in production over the previous year was the rapid decline of the Crystal field, which reached its peak in October 1935. The old producing area—Mt. Pleasant, Porter, Yost-Clark— accounted for over 7,000,000 bbl. during 1936. Crystal produced a total of 2,400,000. Outstanding among the old fields were Vernon and

Jan 1, 1937

By H. I. Aaronson

Isothermally formed plates of proeutectoid a, lengthen at approximately the rates predicted by the Zener-Hillert equation, indicating that their lengthening kinetics are controlled by the volume diffusion of chromium in the ß matrix. Solution annealing treatments in the vicinity of the transus introduce a second mode of transformation, in which the lengthening rate is at least 1.8 x 104 faster than predicted by this equation. Little or no volume diffusion appears to accompany the latter transformation. The Presence of oxygen is evidently a Prerequisite for the occurrence of this reaction. X HE effects of thermal history prior to the initiation of transformations which proceed by nucleation and diffusional growth are currently evoking considerable interest. The rate of nucleation (but not the rates of growth) of pearlitel and of bainite,2 and the over-all rates of aging reactions in Al-cu3 and Al-si4 alloys have been shown to be appreciably dependent upon thermal history in the solid-solution region"&apos; or in the two-phase region prior to the onset of pre~ipitation.3,4 In none of these reactions, however, was the transformation mechanism changed by variations in the temperature-time path used to reach the reaction temperature. Preliminary experiments reported by M. K. McQuillan5,8 and a systematic investigation by Farrar and Margolin7 have disclosed that the transformation behavior of hypoeutectoid Ti-Cr alloys is considerably more sensitive to thermal history. Qualitative evidence strongly suggests that not only the rate of nucleation but also the rate of growth and even the mechanism of the ß — a reaction can undergo remarkable changes when a solution annealing treatment in the vicinity of the ß/a +ß, or transus temperature, is interposed between a high-temperature solution anneal (conventionallq at 1000°C) and the isothermal reaction treatment. The present investigation was undertaken in an attempt to ascertain the nature and origin of these effects. Study of the changes in the kinetics and morphology of the ß - a, reaction produced by varialtions in thermal history was the primary means employed for this purpose. EXPERIMENTAL PROCEDURE The compositions of the alloys used in this in~esti~ation are given in Table I. These alloys were homogenized for 5 days at 1050° C in evacuated (2 x 10 -5 mm of Hg), zirconium-gettered fused quartz capsules. The capsules themselves were enclosed in a porcelain chamber evacuated with a mechanical pump during the homogenization anneals. Upon completion of homogenization, the alloys were cooled to room temperature and then reheated to 550°C for 3 1/2 days in order to transform the alloys to a finely divided mixture of a and TiCr2, and thus provide an approximately constant initial mi-crostructure. Individual specimens were sealed in evacuated and internally gettered Vycor capsules and heat treated as previously described.8,9 EXPERIMENTAL RESULTS Ti-10.64 Pet Cr. This investigation was largely performed on the 0.64 pet Cr alloy. The "base"

Jan 1, 1962

By Edward A. Loria

Vanadium is one of the materials being considered for use in fast-breeder nuclear reactors. It is a good heat conductor and nearly transparent to radiation, properties regarded as ideal for nuclear fuel containers. The problem has been the metal lacks ductility needed for forming. In our program at Reno Laboratory the effects of the U.S. Bureau of Mines (previous affiliation) the effects of oxygen, nitrogen, and carbon have been reported21,22 nd most recently the effects of boron and boron with carbon.23 The continuing study by the Ames Laboratory of the effects of hydrogen, the most subtle and fugitive element in its relationship to structure and properties, is commendable. The solubility of oxygen, nitrogen, and hydrogen in vanadium (and other bcc metals as well) is related to material purity. With the available limit on metal purity and the interaction (clustering) of hydrogen with the other interstitial and substitutional elements present in their base metal, would the authors comment on the tolerance of hydrogen in relation to oxy- gen that will avoid intergranular fracture and above what content or how seriously harmful in oxygen at various carbon levels? Understanding the true effects of hydrogen (and other interstitial impurities) in vanadium depends on knowledge of the amount present under various conditions and its distribution between various possible positions. Significant amounts of hydrogen may be in "thermo-dynamic" solution, but not as individual atoms in interstitial positions. It may be in grain boundaries, in subgrain boundaries, in vacancies, or in dislocations. Some of the hydrogen may be paired or in complexes with impurities in substitutional solid solution in vanadium. This makes the analysis of the effect of hydrogen vastly more difficult. It should not be expected that hydrogen in grain boundaries will affect slip in the same manner as hydrogen in interstitial positions, nor will the complexes react to heat treatment the same way as hydrogen in dislocations. It is gratifying that the authors have quoted results from two of our inestiations,&apos; but neglected one2&apos; which applied the Petch theory to electrorefined vanadium of high purity and analyzed the effects of oxygen, nitrogen, and carbon on the ai and ky values obtained by the extrapolation and grain size methods. Details can be found in the paper. Briefly, we obtained a ui value of 10,300 psi (t = 5150 psi) at 273°K. The metal also exhibited profuse twinning with high ductility at 123" and 77°K. Nitrogen was more effective than oxygen in increasing ui, the increase being about twice as much for the same impurity level. Carbon additions resulted in only minimal changes in Ui. The corresponding ky increased as oxygen and nitrogen increased, with nitrogen being more effective. Carbon additions resulted in little change. Although the difference in yield strength of vanadium was explained on the basis of the Cottrell-Bilby model of the tearing away of dislocations from the impurity atoms,

Jan 1, 1970

By Rex W. Woods

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

Jan 1, 1956

By J. R. Kyte, V. O. Naumann, C. C. Mattax

Imbibition and waterflooding tests at reservoir conditions show that conventional tests at room conditions sometimes lead to recovery estimates that are too low. Core samples which are of intermediate wettability at normal test conditions may be strongly water-wet at reservoir conditions. This was found to be true for samples from two of three reservoirs investigated. For the other reservoir, less difference was observed between the wettability of samples at normal test conditions and at reservoir conditions. Samples which became more water-wet at reservoir temperature and pressure also water flooded more efficiently at reservoir conditions. These results show that core analysis tests on intermediate wettability samples should be performed at reservoir conditions to obtain representative data. INTRODUCTION Throughout the oil industry, core analysis tests normally are performed using refined oils and at room temperature and pressure. This procedure has always been subject to question because the possibility is generally recognized that the reservoir environment may influence displacement behavior. Burkhardt, et al,&apos; have performed waterflood tests at reservoir conditions on East Texas cores. They found little difference between results obtained at reservoir conditions and results of conventional flooding tests at room conditions. As they pointed out, however, this situation might not be general since they obtained data on only one rock and crude-oil system. This paper presents data which demonstrate that it is sometimes necessary to perform core analysis tests in a simulated reservoir environment to properly represent the reservoir wettability and displacement characteristics. The work is specifically concerned with reservoirs which were thought to be of intermediate wettability on the basis of conventional test results at room conditions, i.e., core samples imbibed only small amounts of either oil or water and exhibited no decided preferential wettability characteristics. Tests were performed on cores from three such reservoirs to determine their behavior in the reservoir environment. lmbibition and waterflood tests were used to demonstrate the effect of reservoir environment on reservoir rock wettability and displacement characteristics. Results of tests performed at reservoir conditions were compared with results from conventional tests. Imbibition tests were performed on samples from all three reservoirs. Waterflood tests were performed on samples from only one reservoir. Fluid properties for the three reservoirs studied are shown in Table 1. Tests at reservoir conditions were performed using bottom-hole crude oil at reservoir temperature and pressure. The aqueous phase used in these tests was a synthetic brine approximating the reservoir brine composition. Conventional tests were performed at room conditions with refined oils and synthetic reservoir brine. The oil-to-water viscosity ratios were adjusted to the reservoir values. The cores used in all the tests were taken from the reservoirs using either brine alone or a bentonite-car-boxymethylcellulose mud without additives as coring fluids. Previous tests show that these fluids have no significant effect on the wettability of reservoir rock samples.1 The cores were preserved in brine at the wellsite to prevent wettability changes during shipment and storage. Wellsite imbibition tests have been performed on fresh samples from several reservoirs (including Reservoir A) and compared with later laboratory imbibition tests on samples preserved in brine. The comparison showed that the wettability of the preserved cores was the same as that of fresh, surfaced cores at the wellsite.2 IMBIBITION TESTS Conventional imbibition tests were performed on preserved cores using the apparatus and procedures described by Bobek, et al.2 A sketch of the apparatus for imbibition tests at reservoir conditions is shown in Fig. 1. The preserved samples were first centrifuged to expel excess water and then placed in a stainless-steel container which served

By W. Rostoker, H. Nichols

It has been demonstrated in previous work1&apos;2 that wetting of aluminum alloys by liquid mercury can cause fracture to occur with substantial suppression of prior plastic flow. This has been interpreted as the action of a critical liquid species in reducing the cohesive strength of a stressed solid at sites of potential crack nucleation. In this way the critical transverse stress for fracture nucleation is reached at much lower stresses than is normally the case. The stresses for both fracture nucleation and fracture propagation are depressed by the same mechanism. In so doing the plastic-energy component of fracture energy is reduced to a level which is of the same order of magnitude as the surface, interfacial, or cleavage energy. Recent work2 has illustrated the influence of dispersed precipitates, cold work, and combinations of these on brittle fracture associated with plastic strains of the microyield order of magnitude. This has been rationalized in terms of the contribution of internal microstress fields to the stress magnifications at points of obstruction of active slip bands in a stressed metal. The presently reported studies on an Al-4-1/2 pct Mg alloy amplify this subject by introducing thermal-mechanical conditions which can produce strain aging. As amply demonstrated by Phillips, Swain, and borall, the tensile behavior of aluminum alloys containing magnesium reveals a yield-point elongation and successive discontinuous elongations over the whole plastic-strain range. This gives a stepped or serrated character to the stress-strain diagram. The yield-point elongation is not temperature-dependent. On the other hand, the discontinuous extensions in the plastic-strain range are gradually suppressed by lower temperatures of testing. At -78"C, only the yield-point elongation persists. The yield-point elongation itself can be suppressed by rapid quenching to room temperature from an annealing temperature of 500°C. The argument presented by Phillips et 1. and Cottre114 is that the yield-point elongation derives from surmounting at a critical stress the restraint to slip by grain boundaries which have been reinforced by appreciable magnesium-atom segregation. The serrated character of the plastic-strain range is the result of rapid strain aging during the test. This is made possible by the inevitable proximity of magnesium atoms to any dislocation line. In the Al-4-1/2 pct Mg alloy there is one magnesium atom for every twenty-two aluminum atoms and, with a coordination number of 12, a magnesium atom is on the average only about two atomic distances from any given lattice site. Rapid strain aging is therefore a reasonable expectation. A study of mercury embrittlement of the Al-4-1/2 pct Mg alloy (commercial designation 5083) provides an opportunity to relate the interplay of grain size, grain boundary restraint to slip and strain aging in the brittle-fracture process. One lot of commercial sheet material of 0.125-in. thickness was used for all of the tests. The specimen shape and test procedures used were the same as those described in a previous publication.2 A range of grain sizes between 0.0057 and 0.0125 mm was produced by various combinations of plastic prestrain and annealing. The coarsest grain was somewhat elongated in shape. In this case the measurement was taken in the direction transverse to the axis of tension as more meaningful to a brittle-fracture process. In the annealed condition, specimens wetted with mercury failed with zero permanent elongation at stresses slightly below the normal yield point, i.e., stresses at 0.05 to 0.2 pct strain. Since this occurs before yield-point elongation can begin, fracture derives from slip contained within individual grains and restrained from propagating across grain boundaries. No significant difference in wetted fracture stress was observed between specimens which had been water-quenched or furnace-cooled from the annealing temperatures. This signifies that the degree of magnesium segregation at grain boundaries

Jan 1, 1964

By E. S. Machlin, C. W. Chen

RECENTLY Chen and Machlin&apos; proposed a mechanism for intercrystalline cracking in metals during high-temperature stressing. According to this mechanism the formation of voids at grain boundaries is primarily responsible for intercrystalline cracking. A model has been provided to demonstrate the initiation of submicroscopic cracks and voids at jogs of grain boundaries where grain boundary sliding is inhibited. Submicroscopic cracks can grow as a result of either further grain boundary sliding or localized tensile stress. In the former case, it is believed that grain boundary sliding produces more voids which link together to produce macroscopic cracks and which may lead to the eventual failure of the metal. Concurrently, Nield and Quarrell2 reported their interesting results obtained in a systematic investigation of intercrystalline cracking in two aluminum alloys under various creep conditions. Their observations are generally in agreement with the above mechanism, especially the conclusion that voids are formed as a direct consequence of grain boundary sliding. On the basis of the volume fraction occupied by voids, they could find no confirmation of vacancy condensation as the mechanism for void growth. Furthermore, an important feature of intercrystalline cracking has been likewise pointed out by them that the majority of cracks are not formed at grain corners. Nield and Quarrel1 meanwhile emphasized the importance of grain boundary migration by designating it as one of two main processes operative in the mechanism of crack formation during creep. The designation seems unnecessary because overemphasis of grain boundary migration only complicates the mechanism of void formation. There are two reasons which militate against the inclusion of grain boundary migration in the mechanism of void formation. In the first place, the formation of intercrystalline voids per se does not require grain boundary migration. Secondly, in addition to grain boundary migration, void formation may be minimized by any other process such as plastic deformation which is capable of relieving localized stresses around jogs. Chang and Grant3 have shown that intercrystalline cracking is prevented in aluminum by lattice bending in high stress regions. The influential role played by grain boundary migration in creep has also been realized in our studies. In several cases, voids did not appear at all in grain boundaries whenever grain boundary migration took place prominently during creep. The purpose of this paper is to discuss the effect of grain boundary migration on the formation of intercrystalline voids and other related rupture properties. Experimental evidence indicates that in an unstable grain structure void formation may be markedly modified by structural changes. The abnormally high ductility and the transcrystalline mode of fracture observed in copper at elevated temperatures reveals that effective grain boundary migration minimizes void formation. Grain boundary migration has long been known as a common high-temperature phenomenon in metals with the grain configuration in a nonequilibrium state. Its effect on ductility and mode of fracture has not been recognized until recently.4 Since the introduction of the term "Equicohesive Temperature," the conventional belief has been that below the equicohesive temperature the ductility of metals increases moderately with decreasing temperature until the ductile-to-brittle transition temperature of fracture is reached. In this temperature range, metals fracture in a ductile mode with a "cup-and-cone" fracture surface. Above the equicohesive temperature, ductility remains invariably low and decreases slightly with increasing temperature. The mode of fracture is strictly brittle and intercrystalline. Typical examples have been shown for a brass and copper in Fig. 1 and 9, respectively, in the paper by Greenwood, Miller, and Suiter.5 The observation in the upper temperature range that ductility of metals is low and insensitive to temperature may be explained in terms of void formation at grain boundaries. It is also in accordance with the findings of McLean6 and Fazen, Sherby, and Dorn7

Jan 1, 1961

By J. Skrove, C. R. Boardman

In situ permeability of the rock outside the Hardhat chimney was determined by pressurization of long holes with air. Experimental data indicated a remarkable difference between fracture permeability of the rock near the chimney and that at a considerable distance. Although permeable fault zones were known to exist in the granite stock, the measurements of background permeability were quite low, on the order of tenths to several millidarcies. The observed difference is about two or three orders of magnitude above this background in the region 125 to 215 ft radially from the shot point, or 80 to 165 ft radially from the vertical axis of the chimney. The presence of a collapsed drift immediately beyond this region precluded measurements which could have defined the maximum extent of the zone of high permeabilily. INTRODUCTION Previous exploration has revealed that contained nu-clear explosions create cavities which generally collapse, resulting in rubble-filled chimneys and annular fractured zones. These geometries have been shown to result in complex flow regimes which should increase the production rate from hydrocarbon reservoirs.&apos; Empirical scaling equations have been developed for estimatina chimney radii and heights for a variet; of rock media.&apos; The exten; of the annular fractured zone has been documented and associated permeability changes have been observed qualitatively for several explosions. This study was begun to establish the nature and magnitude of the permeability of the latter region. It is anticipated that results will be useful in estimating permeability changes and consequent production stimulation which might ensue from a contained explosion in a hydrocarbon reservoir. The post-shot environment of the Hardhat event (a 5-kt contained nuclear explosion in granitic rock) was c&apos;hosen for the experimental measurements. The Hardhat device was detonated at a depth of 939 ft, and subsequent exploration revealed a chimney of broken rock with a radius of 65 to 70 ft and a height above shot point of 281 ft.&apos; BeFore the explosion, the Hardhat medium was highly jointed and fractured (Fig. I). Jt was expected that differential rock motion along these and other weaknesses induced during cavity growth and collapse would significantly alter the permeability of the rock mass. EXPERIMENTAL METHOD Initially, three 2-in. diameter holes (Nos. 10, 12 and 19) were drilled about 25 ft outward through the walls of the 500-ft level drift (elevation 4,253 ft, Fig. 2). One was drilled near the chimney and two holes, one vertical and the other horizontal, were drilled near the shaft. Order-of-magnitude differences in permeability obtained by pressurization measurements indicated further: investigation was warranted. A series of 3-in. diameter holes was then drilled with water as a coolant into the walls and roof of the drift (Fig. 2). An 11-in. long packer was set from 1 to 8 Et inside each hole and air was injected at measured Row rates. Hole pressures were monitored at the collar. Permeability was low enough in the holes near the access shaft that pressure could be maintained long enough to obtain good pressure decay rates. In the vicinity of the chimney, however, permeability was so high that this was not possible and air was injected under steady-state conditions. About one year later, these same holes were retested to

Jan 1, 1967

By P. Shahinian, R. L. Stegman, M. R. Achter

Creep strength has been determined as a function of oxygen pressure for nickel at 510" and 600°C. Creep-rupture life drops from its highest value at the ultimate vacuum of 10-7 torr to a high pressure plateau of nearly constant life which, at 600°C, commences at torr. This behavior is described in terms of a model that relates surface gas adsorption and the generation of fresh crack surfaces. In a calculation based a this model the predicted pressure beyond which the creep strength should not decrease further has been found to agree well with the observed value. The introduction of oxygen during creep in vacuum was found to cause a prompt rise of the creep rate. The magnitude of the environmental effect was much less than generally observed in fatigue and this is attributed to the diffarent crack morphologies in creep and fatigue. GASEOUS environments are known to affect creep resistance adversely1-5 but the effects have received less attention than the much larger ones in fatigue. At low temperatures it has been shown for nickel that the creep rates are faster and the rupture lives are shorter in air than in vacuum and that these environmental effects can be correlated with faster crack growth rates in the reactive environment.&apos; In support of a mechanism of gas adsorption at the crack tip to explain the above effects, a calculation based on kinetic gas theory showed that surface coverage by gas was not as rapid as the exposure of fresh metal at the crack tip in the ultimate vacuum but was in air.7 In fatigue a number of investigations have demonstrated that the reduction of life with gas pressure usually follows a step curve with most of the reduction occurring in a transition range at intermediate pressures and little or no change at high and low pressure.8 There have been no studies, however, in which creep strength has been determined as a function of reactive gas pressure to see whether similar effects would be found. This investigation was undertaken to study the kinetics of the environmental effect in the creep of nickel. EXPERIMENTAL PROCEDURES The environmental creep apparatus was constructed to minimize many of the experimental conditions which can cause scatter in data. Dead weight loading is employed and weights are contained within the environmental chamber to eliminate bellows and the necessity for compensation for gas pressure changes. Elongation over the specimen gage length is recorded from a Riehle Model DV Controlled Environment Extensometer which provides readout to 2.5 x 10- in. Temperature is monitored and controlled from a thermocouple at- tached to the specimen gage length to +0.5oC or better. The freon trapped oil diffusion pump vacuum system included an auxiliary liquid nitrogen trap and, with a wide range variable conductance leak valve, pressures from the ultimate vacuum of 10"7 to l03 torr of any desired gas are obtainable. Pressure is measured by means of a hot filament ionization gage below 10"3 torr and a NRC Model 530 Alphatron Vacuum Gauge above 10-3 torr. The oxygen, which was leaked into the environmental chamber, was an Aviator&apos;s Grade of 99.5 pct purity with a dew point of -80°F. Analysis of the nominal 99.8 pct Ni showed the following percentages of major impurities: 0.02 C, 4.01 Mn, 0.005 Si, 0.01 Cu, 0.02 Fe, and 0.034 Mg. Cylindrical specimens were machined with a 0.180

Jan 1, 1970