Search Documents

By G. R. Speich

The distribution of carbon and the type of substructure in iron-carbon martensites containing 0.02 to 0.57pct C has been studied in the as-quenched condition and after tempering at 25" to 700°C by using electrical resistivity, internal friction, hardness, and light and electron microscope techniques. in marten-sites containing less than 0.2 pct C, almost 90 pct of the carbon segregates to dislocations and to lath boundaries during quenching; in martensites containing greater than 0.20 pct C, appreciable amounts of carbon enter normal interstitial positions located far from defects. Tempering martensites with carbon contents below 0.20 pct at temperatures below 150°C results in additional carbon segregation to dislocations and to lath boundaries but no carbide precipitation whereas -carbide precipitation occurs in martensites with carbon contents exceeding 0.2 pct. Above 150°C, a rod-shaped carbide (either Fe3C or Hagg) is precipitated in all cases. At 400°C, spheroidal Fe3C precipitates at lath boundaries and at former aus-tenite grain boundaries. At 400" to 600"C, recovery of the martensite defect structure occurs. At 600" to 700°C, recrystallization of the martensite and Ost-waW ripening of the Fe3C occur. The effects of the carbon segregation that occurs during quenching and the subsequent substructural changes that occur during tempering on martensite tetragonality, hardness, and precipitation behavior are discussed. A mathematical analysis of carbon segregation during quenching is presented. RECENT studies of the strength of low-carbon martensitel-4 emphasize the importance of carbon segregation to the martensite lath boundaries and to the dislocations contained between them during quenching. Unfortunately, very few studies of the tempering of low-carbon martensites have been conducted, so the exact nature of this segregation is poorly understood. In fact, most early tempering studies5,6 were restricted to carbon contents greater than 0.20 pct. Moreover, these studies did not determine the amount of carbon segregated to the martensite substructure during quenching so that the initial state of the martensite was not established. Aborn7 studied the precipitation of carbide in low-carbon martensite during quenching but did not establish whether carbon segregation occurs prior to carbide precipitation, nor did he study the subsequent tempering sequence in detail. In the present work we have used electrical resistance and internal friction measurements, supplemented by electron transmission microscopy to establish the carbon distribution in as-quenched specimens. Specimens thin enough to avoid carbide precipitation (but not carbon segregation) were employed. The redistribution of carbon on subsequent tempering below 250°C was followed by measurements of elec- trical resistance. Additional studies were made on specimens tempered at 250" to 700°C to elucidate the overall tempering behavior of low-carbon martensites, including the formation of cementite and recrystalli-zation of the martensite. EXPERIMENTAL PROCEDURE Eight iron-carbon alloys with 0.026, 0.057, 0.097, 0.18, 0.20, 0.29, 0.39, and 0.57 wt pct C were prepared as 8-lb ingots by vacuum melting. Typical impurities in wt ppm were 40 Si, 20 Mn, 30 S, 10 P, and 10 N. These alloys were hot rolled to 3 in. plate at 1095°C) (2000°F). The hot-rolled plates were surface ground to remove scale and the decarburized layer, then cold rolled to 0.010 in. sheet. Specimens cut from the sheet were austenitized for 30 min at 1000°C (1830°F) in a vacuum tube furnace in which the pressure did not exceed 2 x 10-3 torr. Chemical analysis of specimens after austenitization indicated no decarburization at this pressure. Immediately before quenching, the furnace was filled with prepurified helium. The specimen was then pushed rapidly through an aluminum foil gasket, which sealed the bottom of the furnace, into an iced-brine bath (10 pct NaC1, 2 pct NaOH). The quenching rate at the M, temperature is about 104'c per sec for 0.010 in thick specimens, as calculated from Newton's law of heat flow2 using a heat transfer coefficient of 25 ft-'. This quenching rate is sufficiently high so that all the alloys transformed completely to martensite throughout the entire 0.010 in thickness and no carbide precipitation occurred in the martensite. All specimens were immediately transferred to liquid nitrogen after quenching and stored there until needed. Tempering below 250°C (480°F) was done in silicone oil baths thermostatically controlled to *;"C. Tempering above 250°C was done in circulating air furnaces or lead pots with the specimens contained in evacuated silica capsules. Electrical resistance was determined by measurement of the potential drop across both a standard resistance and the specimen, connected in series. All resistance measurements were made in liquid nitrogen (77K, -196°C) to minimize thermal scattering of electrons and thus maximize the contribution of impurity scattering to the resistance. Specimen dimensions were 5.10 by 0.19 by 0.025 cm. Although the precision in the electrical resistance measurements was +0.1 pct, the electrical resistivities could only be measured with an accuracy of +5 pct because of uncertainty in the specimen dimensions. Internal friction measurements were performed in an inverted pendulum apparatus at vibration frequencies of either 1.9 or 66 Hz. The specimen dimensions were 5.10 by 0.375 by 0.025 cm. Hardness measurements were made with a Leitz-Wetzlar microhardness machine with loads of 100 g. Specimens were examined by light microscopy after etching in 2 pct Nital and by electron transmission microscopy after preparation of thin sections by electrolytic thinning in a chromic-acetic acid solution.

Jan 1, 1970

By P. R. Sahm, T. V. Pruss

Mixtures of fine GaSb and Gds as well as preal-loyed GaSbl,As, powders were hot-pressed at 690°C and 25,000 psi. Dense alloys with compositional gradients of less than 5 pct were obtained from mixtures containing about 20 mol pct GaAs. For x < 0.2, there were increasing compositional gradients, and for x > 0.2 a GaAs-rich second phase appeared in the microstructure. Densification as well as alloying wlechanisms were enhanced by dissociation and, possibly, oxidation reactions of the powders. Densification of coarse prealloyed material, however, primarily depended on plastic flow phenomena and required temperatures just below solidus and pressures of 50,000 psi Thermal and electrical properties were measured. Although in no case was the figure of merit of melt growth materials approached closer than to within 25 pct, the better overall thermoelectric properties were found in coarse-grained, prealloyed materzals which had been compacted to near theoretical density and where grain regrowth had been induced. Similar results are believed to hold in other binary 111-V compound systems if processed under similar conditions. The densification of unalloyed GaSb powders during pressure sintering (= hot pressing) was shown to depend strongly on powder particle size.&apos; Fine powders displayed a "liquid skin effect" that enhanced compaction through the presence of liquid gallium, whereas coarse powders compacted predominantly by plastic flow. The liquid skin effect, in particular, appeared attractive for alloying GaSb with other, higher-melting, III-V compounds, and to densify these in a one-step operation. This is of special interest in the case of III-V compound alloys as the conventional techniques of melt growth or long-time annealing of powders2 is very time-consuming, especially in cases where a large separation of liquidus and solidus can be expected, such as in GaSbl alloys.2 It was felt that experimentation with this system, a particularly unfavorable example, would allow us to extrapolate to several other, more favorable, cases. Uses of Ill-V alloys are most evident in thermoelectric energy conversion devices.&apos; For this reason certain thermal and electrical properties were measured and compared to those of melt-grown material and to hot-pressed prealloyed powders. EXPERIMENTAL PROCEDURE The pressure-sintering apparatus has been previously described.&apos; Using this equipment, both powder mixtures of GaSb with GaAs and prealloyed GaSbl-,As, powders were hot-pressed. The mixtures were pre- pared from cast GaSb and melt-grown GaAs. The prealloyed material was obtained from stoichiometric melts, initially heated to 1200°C in an evacuated quartz ampoule, and then annealed in the solidus-liquidus interval. A typical annealing cycle consisted of a heating to 850°C (1 hr), extended successive annealing at 750°C (65 hr), and slow stepwise cooling (25 hr) to below solidus. The GaSb, GaAs, and GaSbl-,As, materials were ground in a vibrational mill to particle sizes below 500 . A jet mill reduced these further where necessary. Fine powders were analyzed by Coulter counting for their size distribution. Average sizes by volume were calculated from the data. Mixing of the powders, where necessary, was carried out through rapid vibrational motion. The hot-pressing operation consisted of a degassing period of 15 hr, in most cases at 690°C, followed by several hours of compression, normally 25,000 psi at 690°C for powder mixtures and 50,000 psi at 710°C for prealloyed powders. The chemical compositions were confirmed by X-ray fluorescence analysis. To estimate the degree of solid solution achieved, lattice parameters were determined and interpreted according to Vegard&apos;s rule. In addition, optical microscopy helped to correlate the relative amounts of the phases present as well as the degree of porosity to the measured density. To reveal grain boundaries, polished surfaces were etched4 with H 2 O:H 2 O:HCl = 2:l:l. In several cases microscopic concentration gradients were monitored by electron-probe analysis-. RESULTS AND DISCUSSION Alloying and Densification of GaSn-GaAs Powder Mixtures. After preliminary experiments showed that no appreciable alloying took place in mixtures of coarse GaSb (22.5 p) and fine GaAs (2.5 p) powders, hot pressing of mixtures was confined to fine powders only (3.1 and 2.4 p, respectively). Alloying and densification apparently occurred simultaneously with a grain regrowth mechanism which depended on the presence of a liquid phase.&apos; The liquid phase was provided by the dissociation of GasbS particles into liquid gallium and antimony above 555°C. This not only enhanced grain regrowth and densification, as in unalloyed GaSb,&apos; but took on additional importance here for the alloying process. Alloying was speeded up by the resulting liquid-solid interaction as compared to the very slow solid-state diffusion process normally expected at these temperatures.&apos; The results obtained with a series of powder mixtures have been compiled in Table I. It is seen that for mixtures with less than 20 mol pct GaAs, x < 0.2, the compositional ranges increased and for x > 0.2 a GaAs-rich phase and free antimony appeared in the microstructure in sizable amounts.

Jan 1, 1968

By C. W. Binckley, F. R. Burgess, E. R. Haymaker

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well&apos;s actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2&apos;&apos; O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By E. R. Haymaker, C. W. Binckley, F. R. Burgess

A method of establishing stabilized back-pressure curves for gas wells producing from formations of extremely low permeability is presented. Actual well performance under many different operating conditions is shown by the stabilized back-pressure curve. By use of the method. it is possible to conduct back-pressure tests with a critical-flow prover on wells that stabilize slowly, and save approximately 88% of the gas ordinarily vented to obtain satisfactory test data, with a great reduction in time required for testing. INTRODUCTION The reasons for establishing dependable back-pressure curves on gas wells have been pointed out by previous publications. The publication most referred to. of course, is the United States Bureau of Mines Monograph 7, titled "Back-Pressure Data on Natural Gas Wells and Their Application to Production Practices". The technique generally established therein has been accepted and used by many engineers; and, when proper tests are conducted, the results can be used for the analysis and solution of several practical problems concerning field operation and development. Even where formations of low specific permeability are encountered, the determination of a well&apos;s actual performance by the back-pressure test method permits the engineer to analyze many problems in individual well operation and also to predict necessary future field development. Such problems as the determination of the ability of a well to produce into a pipe line at a predetermined line pressure, the design of gas gathering systems and meter settings, and the determination of the time and the number of wells required to be drilled to meet future market obligations, can be solved, in part., by the use of a reliable back-~ressure curve. In addition, the computed well delivery rates determined by data from backpressure tests ordered by state regtilatory bodies, when compared with the true back-Pressure curve, permit the operator to ascertain whether such data represent unstable or relatively stabilized delivery rates for given pressure conditions of the well. The technique of back-pressure testing, as described in this report, was developed by Phillips Petroleum Company engineers from data obtained during a testing program that started in 1944 and has been continued to date. Three hundred and eleven back-pressure tests were conducted on 299 wells located in the southern part of the Hugoton Field. The gas-bearing zone is composed of several dolomitic formations of the Permian Age; the important ones are the Herington, Upper Krider, Lower Krider, and Winfield. The average bottom-hole temperature is approximately 91 °F.. and the initial wellhead shut-in pressures range from 400 to 440 psig. The spacing pattern is 640 acres per well with each well located near the center of the section. The range of back-pressure potentials on wells tested was from 500 to 23,000 Mcfd. All gas wells were acidized, and the quantity of acid used, expressed in 1574 hydrocloric acid, varied from 12,000 to 22,000 gallons per well. The quantity and concentration of each treatment depended on the stage, the formation being treated, and experience gained from previously completed wells. The gas in the Hugoton Feld is a "dry" gas. It has a gasoline content of approximately 0.25 gallons per thousand cubic feet, as determined by charcoal test, and its specific gravity averages about 0.71 as compared to air (air = 1.00 at 60°F.). Of the wells tested, 71 were completed with 7" casing, 3 with 9 5/8" casing, and 1 with 6%" casing set on top of the upper producing formation with the well bore through the gas bearing formations being open hole. Two hundred and twenty-four were completed with 5 1/2&apos;&apos; O.D. casing set through the gas bearing formations and perforated. For the purpose of establishing reliable back-pressure curves in the area, Phillips Petroleum Company personnel has computed data on the basis of 24-hour flows per point. Early in the program, many tests were actually permitted to flow 24 hours to obtain data for each plotting point, at great expense in man power and time. Presently, however, such tests have been replaced by tests of short duration flows which can be made to effect results that correspond to the tests obtained by flows of much longer duration. METHOD When a gas well producing from a reservoir of low permeability is opened for production through a constant size orifice, both the rate of flow and working pressure decline. first at a high rate and later at a lower rate until after several hours the decline becomes difficult to ascertain. In this paper the rae of flow and working pressure are considered to be stabilized when it becomes difficult to observe changes in working pressure during a period of three hours by the use of a deadweight pressure gage. Stalibization of pressure in the literal sense is never obtained in a producing gas well. In formations of low permeability. such as those in the Hugo-ton Field, most wellhead working pressures approach stabilization closely enough to be used satisfactorily in the determination of a back-Pressure potential curve after flow periods of 24 hours. We shall therefore describe the backpressure curve calculated from ohserved rates of flow and working pressure at the end of 24-hour flow periods.

Jan 1, 1949

By R. S. French, W. R. Hibbard

M. Balicki—As one who some years ago spent much time searching for an alloy with high thermoelectric power that would be suitable for heat energy-electric energy converter based on the principle of a thermoelectric pile, I would like to make a few comments touching upon that aspect of this excellent paper. The specifications which one of the authors has formulated so aptly do not appear to me as complete, and I would like to add to them the following two demands: (1) Melting point not less than 500°C and (2) elongation on 2 in. at least 5 pct. Condition 1 would insure good thermodynamic efficiency of the pile by permitting a reasonably high temperature of the hot junction and at the same time making it suitable for such application as salvage of vast amounts of energy which is lost in the form of sensible heat of waste gas leaving industrial and other furnaces. Condition 2 is also a very important one; particularly, because of the fact that all elements and alloys which exhibit attractive thermoelectric properties seem to be as a rule very brittle. The design, erection, and maintenance of a pile incorporating a brittle material in one of the most crucial parts of the converter would be a very difficult and costly affair indeed. To illustrate this point I may mention great difficulties I encountered when trying to make thermocouples of silicon. Casting of 1/4-in. rods in iron or graphite mould yielded only broken pieces which had to be welded into a bar. Such a bar had to be handled very carefully during the determinations. Raising the molten silicon by vacuum into a silica tube and solidifying it there solved the problem of stability as well as that of electrical insulation of a bar. On tests this bar (98.5 pct Si) showed dE/dT = — 275.5 microvolts per degree C vs. copper. Thermocouples made of this grade of silicon and pure nickel developed 0.39 v when temperature of the hot junction was approximately 1000°C. The possibility Dr. Gonser has mentioned of trying to impart to metals good thermoelectric properties by alloying them with silicon, has been considered. The preliminary survey which I have made was, however, disappointing. Perhaps, it will be advisable to record the results obtained (table VI), as this might save repetition of search in fields already covered.

Jan 1, 1951

By J. B. Cheatham, C. E. Murphey

Presently, computer control of Borobolic direction cannot be obtained during drilling, and most straight-holc drilling methods attempt to resist hole deviation rather than control direction. Many of the theories advanced as possible explanations of the cause of hole deviation are Summarized berein. A new correlation of physical partables is introduced to indicate bow factors such iis drill collar stiffness clearance and hit weight influence borehole deviation, .A methord is proposed for predicting the rate of change of hole angle when drilling conditions are changed. INTRODUCTION Control of borehole direction during drilling can be difficult and costly. Unintentional crooked holes are often lrilleti in dipping formations and many times directional drilling is required when the surface location is not directly above the target area —- for example, at offshore and mountainous locations. Prilllng progress can be greatly hindered in either air or liquid drilling when it be comes necessary to use low bit weight to prevent excessive hole angle build-up. If hole inclination becomes too great, drill pipe drag becomes excessive and fishing risks are increased, logging is more difficult and problems of differential sticking, key seating and fatigue failures may be encountered. Dog-legs and key seats are more serious problems than steep inclination angles: therefore, reducing rate of direction change is preferred to attempting to maintain absolutely vertical holes. Consequently, a straight inclineti hole is preferable to a nearly vertical crooked hole containing numerous dog-legs. In this paper, theories of the cause of hole deviation and analyses of drill string behavior under down-hole conclitions are summarized. Methods for computing hole deviation are presented und systems for resisting deviation as well as neans for provic!ing control of holt- direction are iliscusseI. A new correlation of physical variables is introduced tu indicate how factors such as drill collar stiffness, clearance and bit weight influence borehole deviation. A method is oroposeti for predicting the rate of change of hole anFrle when drilling conditions are clianged. IIEVIEU&apos; OF PREVIOUS WORK ON HOIaE DEVIATION Significant progress in the theoretical analysis of hole deviation problems has been made in the past 1 5 years. The pioneering work has been primarily a result of the efforts of Lubinski and Woods.l-5 In 1950, Lubinski 1 considered the buckling of a drill string in a straig:rt vertical hole, a problem also considered by Willers6 in 1941. It wns concluded that very low bit weights must be used to prevent hole deviation resulting from drill collar buckling. The use of conventional stabilizers was proposed2 in 1951 by Mac Donald and Lubinski as a method for permitting greater Sit weights to he carried without drill collar buckling. These authors pointed out that a 2° nearly vertical spiral hole can cause severe key seatinp, and drill pine near, wilereas n 3 straight inclined hole with deviation all in one direction, while not vertical, will not result in serious drillirig or producing problems. Studies were continued with an investigation of straight inclined holes by Lubinski and Woods3 in 1953. In this paper they concluded that perfectlv vertical holes cannot be drilled even in isotropic forriations unless extremely low bit P-eights are used. .l&apos;l~ey postulated that constant drilling conditions produce holes of constant inclination angle and varying conditions cause the hole to drill at a neiv equilibrium angle. This analysis was not concerned with drill string buckling since it was based on an equilibrium solution in which the ~irill string Was presumed to lie along the lower side of the hole abcrve the point of tangency. Weight of the drill collars below the point of tangency tends to force the hole toyard the vertical, whereas the weight on hit tends to force the hole aurav from the vertica l. The concept of an anisotropic formation Lvas introduced as an empirical method for explaining actual drilling data and as a means for extrapolating known deviation data to otiier conditions of hit

Jan 1, 1967

By R. J. Brison, O. F. Tangel

The development of a new method of mineral separation was sponsored by the International Salt Company, which requested Battelle Institute to investigate means for improving the quality and appearance of rock salt from the Company&apos;s Detroit mine. Although developed specifically for removing impurities from rock salt, the general method may be applicable to other separation problems. The principal impurities in rock salt from the Detroit mine are dolomite and anhydrite which represent 2 to 5 pct of the weight of the mined salt. In the size range from 1/4 to M in. (the range of primary interest in this project) the impurities are only partially liberated from the halite in normal production. Further size reduction to improve the liberation of impurities is not practicable in view of the market requirements for the coarse grades of rock salt. Laboratory separations in heavy liquids showed that, to improve the quality and appearance of the rock salt substantially, it would be necessary to remove not only free gangue particles but also a large proportion of the locked-in particles. Because rock salt is an inexpensive commodity, a low-cost process was required. Gravity methods were, of course, considered. The heavy-liquid separations indicated that a split at an effective specific gravity of 2.2 to 2.3 would be required. (The specific gravity of pure halite is 2.16.) Heavy-media separation was investigated but had the disadvantages that it was necessary both to operate with saturated brine and to dry the cleaned salt, and that the cleaned salt was darkened by the magnetite medium. Air tabling was tried but did not give the desired separation. It soon became apparent that established methods would not provide a satisfactory solution and work was undertaken on the development of a new process to solve the problem. PROCESS DEVELOPMENT Preliminary Experiments: At the start of the investigation, an analysis of the problem indicated that the diathermacy of rock salt—that is, its ability to transmit radiant heat—might form the basis for an efficient separation process. Under this theory, the impurities might be selectively heated by radiant heat. The particles could then be fed over a belt coated with a heat-sensitive substance so that the warm impure particles would adhere preferentially to the coating. After the initial experiments, made by heating the rock salt with an infrared lamp and separating the product on small sheets of resin-coated rubber, proved encouraging, a small continuous separation unit was set up. This comprised 1) a simple heating unit consisting of a vibrating feeder covered with aluminum foil and an infrared lamp mounted above the feeder and 2) a separation belt 6 in. wide and 36 in. long. A sketch of the device is shown in Fig. 1. Results with this apparatus confirmed the fact that a good separation was possible. It was apparent, however, that a considerable amount of experimental work would be needed to develop the scheme to a practical and economical process. The Process: Basically, the process consists of two main steps: 1) selective heating by radiation and 2) separation of the heated particles on a heat-sensitive surface. Because neither of these steps had previously been utilized commercially in mineral processing, it was necessary to do basic research on both aspects. Factors studied in the investigation included type of heat source, design of heating unit, design of separation belt, selection of heat-sensitive coating, removal of heated particles from the belt, contact between particles and coating, and maintenance of the heat-sensitive surface. Part of the experimental work was carried out on a small-scale unit consisting of the 36x6 in. belt and auxiliary apparatus, and part on a larger unit. For simplicity, discussion of work on both of these units is grouped together. SELECTIVE HEATING Radiant-Heat Source: The essential requirements for a radiant-heat source were 1) that the radiant heat be in a wave length range which is effectively absorbed by the impurities but not absorbed appreciably by the rock salt and 2) that it be dependable, practical, and economical. Selection of a heat source of suitable wave length range was one of the first considerations. It is well known that pure halite is highly transparent to radiant energy in wave lengths from 0.3 to 13 microns. However, the available data on infrared transmission by dolomite and anhydrite, particularly in the range below two microns, were not complete enough to serve as a reliable basis for selection of a heat source. Although it may have been possible to obtain sufficient data on infrared transmission and absorption to enable one to select the best heat source, a more direct procedure was used. This consisted simply of exposing the crude rock salt to each of several types of radiant-heat source on the small continuous separation device. The heat sources investigated, approximate source temperature used, and calculated wave length of maximum radiation are tabulated in Table I. Of the two types of tungsten-filament lamps investigated, both the short wave length photoflood lamps and the longer wave length infrared lamps were satisfactory from the standpoint of selectivity

Jan 1, 1961

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.&apos; The vCO3 structure, which was determined very recently,&apos; has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

By K. F. Veith, R. L. Marovelli, T. S. Chen

An analytical study is made of thermal stress distribution in a thin circular disc subjected to a peripheral thermal shock at various rates of heat transfer. The problem is of importance in predicting the thermal shock response of a rock body of finite size. The theoretical analysis is based on radial heat flow by conduction in the disc and heat exchange by convection between the disc and the surroundings. The case of constant properties and plane stress is treated. Solutions of the stress distribution are presented for both cooling and heating shocks and an average stress theory is formulated. Preliminary experimental verification was obtained from the results of shock tests on thin rock discs insulated on both flat end faces so that heat exchange took place through the exposed peripheral surface. Physical properties vital to the analysis are Young&apos;s modulus, tensile strength, coefficient of linear thermal expansion, thermal diffusivity and thermal conductivity. Plots of these properties are presented. Historically, thermal energy has been used for primary rock removal throughout the ages. Although it is not widely known, the fire-setting method of thermal rock fragmentation was still in use 100 years ago in systematic underground mining operations in Scandinavia.&apos; There, the availability of cheap labor and abundant wood fuel made the method competitive with the early blasting powders. By 1880, as high explosives replaced powder, use of the method declined and it was finally abandoned about 1885. Only 40 years ago, some experimental fire-setting methods were used for rock removal underground at Pribram and Zinnwald in Central Europe.2 Compressed air-oil burners replaced the earlier wood fuels. About 15 years ago, gaseous oxygen-oil burners were introduced in the United States and gained acceptance for difficult blasthole drilling and some quarry opera- tions. At present, there is renewed interest in the compressed air-oil burner designs. The literature included information on thermal secondary processes for rock weakening or particle liberation3,4,5,6,7,8 on thermal spallation of rock 9,10,11,12,13 and on the thermal fracture of materials other than rock. The 1955 Symposium on Thermal Fracture14 and the later work of Hassel-man, cover recent developments in thermal shock investigations on brittle ceramics. Although the number of published analytical and experimental investigations conducted on ceramic and refractory materials is large, the literature reveals that there is a lack of information on both the theoretical and actual response of rock to thermal shock. Many of the thermal shock studies on ceramic and refractory bodies are based on the case of heat transfer at the solid&apos;s surface by convection in either liquid or air. A similar heat transfer situation was adopted for a theoretical analysis of the thermal stresses in a thin circular disc subjected to a peripheral thermal shock. Experimental thermal shock tests were then conducted on rock specimens to check the analytical results. Specially insulated quartzite, basalt and taconite discs were shocked in either liquid or still air bath at various rates of heat transfer. The work was done in order to resolve the question as to whether theoretically determined tensile stresses are actually realized in a finite rock body undergoing thermal shock. Specifically, if theory predicts that the tensile strength of a rock should be exceeded in a particular type of controlled thermal shock, will fracture occur? This information is needed by Bureau researchers working on thermal and electrical rock fragmentation methods. The object of this paper is to present the main features of the theory and procedure being used in the authors&apos; approach to quantitative prediction of rock response to a thermal shock. THEORETICAL ANALYSIS In the analysis to follow, simple geometry of a thin circular disc is considered. The disc is assumed to be isotropic, homogeneous and perfectly elastic, and to have constant thermal and mechanical properties. The effect of radiation is neglected so that heat is transferred by conduction inside the disc and by convection with its surrounding. In addition, the end

Jan 1, 1967

By John J. Elango

Strain gage load cells, the most widely used type of nonmechanical weight sensor, are capable of taking measurements between 0.45-4.5 million kg (1-1 million lb) with an accuracy of 0.05%. They are available in a wide range of standard capacities, configurations, and accuracies, and special load cells may be custom-manufactured to meet unusual requirements. Typical applications include automated batch processing, process monitoring and control, mixing of powders and liquids, weighing coal or other materials in silos, and in large platform systems that weigh trucks and railcars. Because the strain gage load cell produces an electrical signal proportional to the applied load, it readily interfaces with readouts, keyboards, computer terminals, and alarm systems.

Jan 6, 1979

By Porter W. Shimer

(New York Meeting, February, 1912.) IT does not seem to be generally known that some American pig-irons contain notable amounts of vanadium, and while the present investigation is far from covering the whole range of irons, it is hoped that, at least, it may serve to call attention to the importance of looking for this element. The majority of the pig-irons investigated were made in the Lehigh Valley and neighboring furnaces, using more or less New Jersey magnetite in their mixtures. Many of these ores, and probably all of them, contain a little vanadium as well as titanium; the ore from one of the largest of these mines contains 0.05 per cent. of vanadium and 0.60 per cent. of titanium. Dr. Thomas M. Drown was the first to detect the presence. of vanadium in the incrustations 1 occurring on certain pig-irons, and he also found this element in a number of magnetites, but the methods for its accurate determination had not, at that time, been well worked out. In a general way, it may be said that the Lehigh Valley pig-irons contain from 0.02 to 0.05 per cent. of vanadium and from 0.10 to 0.20 per cent. of titanium. These elements follow the silicon; that is, the furnace-conditions which produce a high-silicon, low-sulphur iron will cause the maximum reduction of vanadium and titanium, and the lower grades of iron, with low silicon and high sulphur, have a lower content of these elements. The following analyses of irons made from the same mixture, but under varying furnace-conditions, show this very well Vanadium. Silicon. Sulphur. Per Cent. Per Cent. Per Cent. NO. 1 X, . . . 0.042 3.46 0.022 No. 2 plain, . . 0.038 2.26 0.041 Mottled, . . . 0.0&apos;29 0.52 0.106 1 Robertson and Firmstone, Note Concerning Certain Incrustations on Pig Iron,Trans., xii., 641 (1883-84).

Aug 1, 1912

By S. O. ANDROS

RECORDS in mining operations naturally fall when improved equipment and methods are developed. And tunneling through the Continental Divide is a mining operation, even though the tunnel was not driven to strike a vein at depth. Although many engineering feats have been successfully accomplished in the development of water supplies in the Western States, the Twin Lakes Tunnel in Colorado presents some unusual features that make it noteworthy. To begin with, it is the first trans-mountain water diversion project in the West. The fact that the Continental Divide intervenes between where the water is and where it is needed was brushed, aside as of minor importance. It was enough to know that on the western side of Independence Pass, the highest in Colorado, with an elevation of 12,095 ft., there was water which was needed on the eastern side, where the Twin Lakes are situated, forming the

Jan 1, 1934

By Max Ball

AN intelligent discussion of the oil situation and its needs, whether from the standpoint of the prospector, the operator, the engineer, or the public administrative officer, must be founded upon a knowledge of the law under which oil lands are obtained. A consideration of new legislation must be prefaced by an understanding of the present law and its results. This paper undertakes to present no new remedy for the ills of the present situation, no new solution of the problems the oil business is facing. It attempts merely to summarize the present law, its provisions, its origin, its development, and its effects. The discussion does not pretend to be exhaustive from a legal standpoint. It aims to avoid legal intricacies Which tend to confuse rather than clarify. It seeks but to present the essentials of the existing situation. The title to government lands known to contain valuable deposits of petroleum may be acquired only under the terms of the placer law as embodied in Section 2329 et seq. of the Revised Statutes. As a preliminary to considering the desirability of this situation it is profitable to examine into its origin. ORIGIN OF THE LAW Congress has left no room for doubt as to the legal applicability of the placer law to oil lands. The Act of Feb. 11, 1897 (29 Stat., 526), provides: "that any person authorized to enter lands under the mining laws of the United States may enter and obtain patent to land containing petroleum or other mineral oils, and chiefly valuable therefor, under the provisions of the laws relating to placer mineral claims."

Jan 6, 1914

By Harry A. Wahl

Precent fracture design procedures are bared on the total fracture area created. A method to distinguish beI,,.ecn total area and [he propped or effective fracture area has not been available. This paper presents a solution to this problem, applicable to horizontal fractures. The difierences between effective fracture area and torn] area are demonstrared in example calculations. This work is hayed on experimentally determined transport efficiencier of solids in sand-liquid slurries. Newtonian and non-Ne~vtoninn systems are considered. INTRODUCTION Fifteen years after commercial introduction, hydraulic fracturing remains the most successful stimulation technique in the oil field. This success is primarily due to ability of induced fractures to penetrate and alter permeabilities deep within formations. Many fields producing today could not have been developed without the hydraulic fracturing process. Because of wide usage, fracture-treatment design has received a great deal of engineering and research effort. This work, resulting in improved equipment and materials, has increased the benefits from fracture treatments as well as the applicability of the process. A major contribution was the development of fluid-loss additives. Necessarily, the number of parameters to be considered in treatment design has steadily increased, resulting in more complicated design techniques. Almost all present design procedures are based on the precepts set forth by Howard and Fast. Relating the fluid volume lost into the formation, the volume required in extending the fracture, and the total slurry volume injected, they developed an expression for the total fracture area created in terms of pertinent treatment parameters. Fluid loss during treatment was expressed as a function of time for three flow mechanisms. Although modifications of fluid loss equations have been made, the total fracture area concept has remained unaltered. A vast amount of field data indicate that induced fractures must be propped and held open to be effective. A notable exception is the Mesa Verde formation in the San Juan basin. However, analysis of these treatments shows that improved well productivities are obtained when propping agents are incorporated in the treating fluid. Although propped fracture area has been recognized as an important design parameter, a method to distinguish between total area and effective fracture area has not been available. The necessary information on slurry-sand transport in fractures has been lacking. Interest in the propped region of induced fractures is not restricted to areal extent alone. The distribution of sand within fractures is important from the standpoint of fracture flow capacities. Flow capacity affects the increase in well productivity after stimulation. The work of Huitt and Darin4 hows that partial monolayers of sand have large flow capacities compared to thick* dense sand packs. It has been postulated that gelled fluids have the ability to transport sand within the fractures at the deired low concentrations. An early contribution in the area of sand placement in fractures was made by Kern et al.&apos; They studied sand movement in a transparent vertical fracture model. It was observed that the sand tended to settle out in the bottom of the model before moving very far. When the fluid velocity exceeded a certain critical value, all of the sand injected began moving through the crack even though it settled to the bottom. This critical velocity was determined under several flow conditions. Some work on sand movement in horizontal fractures has been reported in Russian publications. Sand movement was studied by Izyumova and Shan&apos;gin&apos; using a transparent "pie-shaped" flow model to simulate a horizontal radial flow system. However, the data were limited, especially in a quantitative sense. Dorozhkin, Zheltov and Zheltow studied the behavior of sand-liquid slurries in a horizontal linear flow model. The quantitative data were restricted primarily to the thickness of sand deposits formed at the bottom of the fracture. An earlier paper provided basic data on the flow of sand in horizontal fractures. This study was designed to yield specific quantitative information on rate of advance of sand particles and pressure behavior under various flow conditions. A comprehensive photographic study was undertaken in a 10-ft windowed flow cell to provide the necessary qualitative and quantitative data. Since the number of potential variables far exceeded the capacity of the initial study, emphasis was placed on the effects of sand concentration, oil viscosity and oil flow rate. A detailed description of these experiments and the results are described in Ref. 9. However. the implications of this work on the fracture design calculations were not discussed. An analysis of these data as well as new data is provided in the following sections. EXPERIMENTAL RESULTS The primary objective of the experimental investigation was to provide information on the rate of advance of the solids in sand-liquid sturries. A 10%-ft long transparent

Jan 1, 1966

By A. R. Hendrickson, C. F. Smith

Hydrofluoric-hydrochloric acid mixtures have been successfully used to stimulate sandstone reservoirs for a number of years. Hydrofluoric acid (HF) has a specific reactivity with silica which makes it more effective than HCl for use in sandstone. Kinetics of the reactions of HF have been studied to determine the related effects of reservoir composition, temperature, acid concentration and pressure on the spending rate of HF. Secondary effects from by-product formation are noted and described. Predictions are made concerning the improvement in productivity resulting from HF treatment of skin damage. The kinetic order of HF reaction in sandstone was experimentally determined to be first order, i.e., the reaction rate is proportional to concentration. HF reacts faster on calcite than on clay, which, in turn, is faster than the reaction rate of HF on sand. Static conditions retard the HF reaction rate. As HF is forced into cores, there is a temporary reduction as a function of flow rate and acid concentration. Extensive deposition of calcium fluoride in acidized cores was not observed. Although some CaF, was defected, it was not considered a major source of damage in cores containing moderate amounts of carbonate. Other fluosilicates could be potentially more dangerous than CaF, in reducing permeabiliry. INTRODUCTION Hydrofluoric acid has been widely used in stimulation treatments since 1935, when mud acid was introduced to the petroleum industry. Originally, this hydrochloric-hydrofluoric acid mixture was intended to remove mud filter cake, but it has since been successfully applied to many other oilfield problems. Mud acid treatments have been unusually successful in sandstone reservoirs where hydrochloric acid is unreactive due to a lack of enough calcite in the formation. The relatively small amount of hydrofluoric acid present (2.1 per cent) reacts with sand grains, clays and traces of calcite which are generally present in sandstone reservoirs. Since hydrofluoric acid (HF) is the key to mud acid success, this research effort has been dedicated to gaining a more thorough understanding of the basic chemical and physical principles involved as HF reacts. Hydrofluoric acid&apos;s reactivity with silica makes it unique in application. Other mineral acids such as hydrochloric, sulfuric or nitric are unreactive with most silicious materials which comprise sandstone formations. A typical sandstone reservoir may contain 50 to 85 per cent silicon dioxide, more commonly called sand or quartz. Hydrofluoric acid reacts as follows: 4HF + SiO2 + SiFO + 2H2O The silicon tetrafluoride (SiF,) is a soluble gas, in some ways similar to CO2, and is capable of undergoing further reaction when held in solution by pressure. These reactions will be considered in detail later. Kinetics of the reactions of HF have been studied to determine the effect of reservoir composition, temperature and pressure on the spending of the acid. Secondary effects from by-product formation have been noted and described. The individual reactions of HF on quartz, glass and clay are reported. Mathematical correlations have been drawn, then applied to studies of HF spending in cores obtained from actual producing sandstone formations. The research reported herein is only the beginning of a continuing approach to better understanding and use of HF in petroleum reservoirs. THEORY AND DEFINITIONS Through the years, a concentrated effort has been made to understand the effects of many variables on hydrochloric acid (HCI) spending in limestone. Hendrickson el al., have given mathematical relationships for HC1 reactions which made possible the engineered approach to acidizing. The same variables—temperature, acid concentration, formation composition, pressure and permeability-porosity relationships—which affect HC1 behavior in limestone also govern HF behavior in sandstone. Insoluble by-products of HF reaction have been isolated and identified. Their effect on fluid flow has been measured under varying conditions in an attempt to evaluate the extent of possible damage and means of eliminating it. In general, HF follows the same reaction paths as HCI. It will react with limestone and dolomite with speed and ease. Thin sections of acidized cores show the reaction of HF with limestone or calcite faster than its reaction with either clay or sand. When HF reacts with calcite (CaCO,), theoretically, calcium fluoride (CaF2) is precipitated, and has been blamed as a major cause of reduced permeability. On the other hand, pH and pressure such as that encountered in an underground formation under acid treatment definitely retard CaF2 formation,&apos; so the whole question of CaF, deposition in wells is a subject for study.

Jan 1, 1966

By E. S. Messer

A knowledge of the magnitude of the irreducible inter.;titial water in a porous medium is so important to petroleum engineering that its determination has become routine in core analyses. The method of determination, being a production problem, should encompass the basic requirements of simplicity in technique and calculations, with reproducible results obtainable in a short interval of time. The results of the evaluation tests outlined in this report indicate that the evaporation method for determining the irreducible water is a technique which meets the requirements. The procedure consists, as the name implies. of permitting the saturant in the pore spaces to evaporate until only an irreducible volume remains. The determination of this volume can be made either graphically or by a mathematical comparison of fluid flows; the time required for each determination being dependent on the fluid used. When fluids other than those having reservoir characteristics were used, a volume factor had to be calculated which was based on the relative volume of various liquids adsorbed on grain surfaces and retained in pores. This factor made possible the calculation of an irreducible water volume when more volatile fluids such as toluene and benzene were used as the saturants. Also presented is the theoretical discussion necessary for the calculation of the capillary pressure as determined from the evaporation curve. A comparison is made between the calculated values and those obtained by experimental means. INTRODUCTION In all geological formations there exists, in the pore spaces of the rock structure, water that is held in a state of equilibrium between capillary and hydrostatic forces. "Interstitial water" is the term given to this water and is defined as that water coexisting in the pore space with the oil prior to exploitation. The term &apos;&apos;connate water" has often been used synonymously with this term; however, this can be true only by a specific definition since, geologically, it means the water in place at the time the rock structure was formed. The quantity of the interstitial water is a variable factor in any formation, since it depends on the hydrostatic forces present in any multiple-phase system. These forces may become unbalanced by the introduction of an extraneous force such as the raising or lowering of the "water table" or the migration of oil into a water-filled formation. Any unbalanced force results in a change in the interstitial water. There exists, however, an irreducible interstitial water. for a particular sand, that is the fraction of the pore space occupied by water when the capillary pressure at the particular point in question is at an equilibrium with the hydrostatic head of the oil sand in the reservoir. For this discussion the term "irreducible water saturation" will be used in place of "irreducible interstitial water saturation" for the sake of brevity; however, they are understood to be identical. A great amount of work has been devoted to the theory and methods for studying the irreducible water saturation and its related capillary pressure. As a result of the publications of Leverett;&apos; Hassler, Brunner and Deahl;2 Calhoun and Lewis;3 and others, the role of capillary pressure studies is being accepted by the industry as a tool for studying suhsurface phenomena. Many techniques have been developed and published for determining the capillary pressure and irreducible water. In general, these techniques may be grouped into three classifications. One of the first was the capillary pressure method described by Leverett1 and expanded by Bruce and Welge.4 The experimental results were compared with water saturation of cores obtained using oil-base mud. Thornton and Marshall compared the irreducible water saturation of core samples determined by the capillary pressure method and by salinity and reported good agreement between the two methods. The second classification for determining the irreducible water and capillary pressure may be referred to as the "centrifugal force method." The general technique is similar to the capillary pressure method except that the force driving the reservoir fluid from the sample is of a centrifugal nature. A complete description of this method was presented by J. J. . McCullough and F. W. Albaugh.6 A process, the reverse of the capillary pressure method, was presented by W. R. Purcell.7 Mercury under pressure is driven into the pores of the rock and the saturation of the core determined at each applied pressure. The resulting capillary pressure curve is used to evaluate the irreducible water saturation. The techniques mentioned are singular in their approach to the irreducible water saturation. In all cases. an external force was applied to the core. The forces employed in the evaporation method are the vapor pressure of the liquid causing evaporation, the kinetic diffusion forces. adsorptive forces and. to a lesser degree, the viscous forces resisting flow to the surface. The basic definition of irreducible water is that water held in a state of equilibrium between capillary and hydrostatic forces This water has been described by previous investigators as being held in the microcapillaries too small to support fluid flow. Actually, this fluid volume is made up of the water in the microcapillaries and as a film adhering to the surface of the crystals. All capillaries. therefore, possess some liquid as a film, the thickness of the film being dependent on the properties of the fluid and solid. A discussion of experiments with references pertaining to the measurement of this immobile layer next to the solid surface can be found in the text by J. J. Bikerman.8 Eversole and Lahr calculated the thickness of this layer to be in the order of 10 &apos; to 10&apos; cm for aqueous solutions and glass. Between two quartz surfaces they found the thickness to be 2 x 10 cm. The work of Volkova, on the capillary movement of water and toluene in quartz grains, indicated the thickness of the Immobile layers to be near 10&apos; cm. Since any measurement is an average value, it is easy to understand that an absolute value would depend on the roughness of the surfaces involved and the complexity of the system. A calculated effective pore radius of 2 x 10 cm is obtained at the, irreducible saturation of a porous media in a water-air system when a capillary pressure of 100 psi is applied. Since the separation of the sand grains is of the same approximate magnitude as the immobile layer.

Jan 1, 1951

By E. S. Messer

A knowledge of the magnitude of the irreducible inter.;titial water in a porous medium is so important to petroleum engineering that its determination has become routine in core analyses. The method of determination, being a production problem, should encompass the basic requirements of simplicity in technique and calculations, with reproducible results obtainable in a short interval of time. The results of the evaluation tests outlined in this report indicate that the evaporation method for determining the irreducible water is a technique which meets the requirements. The procedure consists, as the name implies. of permitting the saturant in the pore spaces to evaporate until only an irreducible volume remains. The determination of this volume can be made either graphically or by a mathematical comparison of fluid flows; the time required for each determination being dependent on the fluid used. When fluids other than those having reservoir characteristics were used, a volume factor had to be calculated which was based on the relative volume of various liquids adsorbed on grain surfaces and retained in pores. This factor made possible the calculation of an irreducible water volume when more volatile fluids such as toluene and benzene were used as the saturants. Also presented is the theoretical discussion necessary for the calculation of the capillary pressure as determined from the evaporation curve. A comparison is made between the calculated values and those obtained by experimental means. INTRODUCTION In all geological formations there exists, in the pore spaces of the rock structure, water that is held in a state of equilibrium between capillary and hydrostatic forces. "Interstitial water" is the term given to this water and is defined as that water coexisting in the pore space with the oil prior to exploitation. The term &apos;&apos;connate water" has often been used synonymously with this term; however, this can be true only by a specific definition since, geologically, it means the water in place at the time the rock structure was formed. The quantity of the interstitial water is a variable factor in any formation, since it depends on the hydrostatic forces present in any multiple-phase system. These forces may become unbalanced by the introduction of an extraneous force such as the raising or lowering of the "water table" or the migration of oil into a water-filled formation. Any unbalanced force results in a change in the interstitial water. There exists, however, an irreducible interstitial water. for a particular sand, that is the fraction of the pore space occupied by water when the capillary pressure at the particular point in question is at an equilibrium with the hydrostatic head of the oil sand in the reservoir. For this discussion the term "irreducible water saturation" will be used in place of "irreducible interstitial water saturation" for the sake of brevity; however, they are understood to be identical. A great amount of work has been devoted to the theory and methods for studying the irreducible water saturation and its related capillary pressure. As a result of the publications of Leverett;&apos; Hassler, Brunner and Deahl;2 Calhoun and Lewis;3 and others, the role of capillary pressure studies is being accepted by the industry as a tool for studying suhsurface phenomena. Many techniques have been developed and published for determining the capillary pressure and irreducible water. In general, these techniques may be grouped into three classifications. One of the first was the capillary pressure method described by Leverett1 and expanded by Bruce and Welge.4 The experimental results were compared with water saturation of cores obtained using oil-base mud. Thornton and Marshall compared the irreducible water saturation of core samples determined by the capillary pressure method and by salinity and reported good agreement between the two methods. The second classification for determining the irreducible water and capillary pressure may be referred to as the "centrifugal force method." The general technique is similar to the capillary pressure method except that the force driving the reservoir fluid from the sample is of a centrifugal nature. A complete description of this method was presented by J. J. . McCullough and F. W. Albaugh.6 A process, the reverse of the capillary pressure method, was presented by W. R. Purcell.7 Mercury under pressure is driven into the pores of the rock and the saturation of the core determined at each applied pressure. The resulting capillary pressure curve is used to evaluate the irreducible water saturation. The techniques mentioned are singular in their approach to the irreducible water saturation. In all cases. an external force was applied to the core. The forces employed in the evaporation method are the vapor pressure of the liquid causing evaporation, the kinetic diffusion forces. adsorptive forces and. to a lesser degree, the viscous forces resisting flow to the surface. The basic definition of irreducible water is that water held in a state of equilibrium between capillary and hydrostatic forces This water has been described by previous investigators as being held in the microcapillaries too small to support fluid flow. Actually, this fluid volume is made up of the water in the microcapillaries and as a film adhering to the surface of the crystals. All capillaries. therefore, possess some liquid as a film, the thickness of the film being dependent on the properties of the fluid and solid. A discussion of experiments with references pertaining to the measurement of this immobile layer next to the solid surface can be found in the text by J. J. Bikerman.8 Eversole and Lahr calculated the thickness of this layer to be in the order of 10 &apos; to 10&apos; cm for aqueous solutions and glass. Between two quartz surfaces they found the thickness to be 2 x 10 cm. The work of Volkova, on the capillary movement of water and toluene in quartz grains, indicated the thickness of the Immobile layers to be near 10&apos; cm. Since any measurement is an average value, it is easy to understand that an absolute value would depend on the roughness of the surfaces involved and the complexity of the system. A calculated effective pore radius of 2 x 10 cm is obtained at the, irreducible saturation of a porous media in a water-air system when a capillary pressure of 100 psi is applied. Since the separation of the sand grains is of the same approximate magnitude as the immobile layer.

Jan 1, 1951

By W.M. Peirce

The present work has been done in an endeavor to correlate and complete the data on the constitution of alloys of zinc with other common metals, dealing exclusively, however, with the zinc-rich alloys in which the zinc content is between 90 and 100 per cent. This investigation has included the systems lead-zinc, cadmium-zinc, iron-zinc, copper-zinc, aluminum-zinc, nickel-zinc, manganese-zinc, cobalt-zinc, tin-zinc, and magnesium-zinc. The important ternary system zinc-lead-cadmium and the zinc corners of other ternary systems have been investigated in connection with this work but will not be dealt with here. Zinc does not form a single homogenous zinc-rich solid solution over any considerable range of concentration with any of the metals mentioned. A limited range of solid solubility is said, by previous investigators, to occur in several cases and certain effects on the properties of zinc are attributed (with varying degrees of consistency among different writers) to the presence of certain other metals dissolved in zinc. The increasing use of rolled zinc and the possibilities offered by zinc as a casting alloy in certain fields have made it essential to determine precisely these equilibrium relationships. In carrying out this investigation reliance was placed chiefly on two methods, conductivity measurements and microscopic analysis. The first method proved valuable in determining the existence and extent of solid solubility. The second method stands alone as a means of determining structural characteristics and supplements the first method in the measurement of solid solubility. The scleroscopic hardness of all conductivity specimens was measured partly for its value from the point of view of mechanical properties and partly as a check on the conductivity curves in indicating the limits of solid solubility. No hardness curves are included in this paper, for in no case were they important in arriving at the constitution of any system. Conductivity measurements were in all cases made on cold-rolled strips 0.020 in. thick and 0.5 in. wide, both as cold rolled and after an

Jan 1, 1923

By W. M. Peirce

The present work has been done in an endeavor to correlate and complete the data on the constitution of alloys of zinc with other common metals, dealing exclusively, however, with the zinc-rich alloys in which the zinc content is between 90 and 100 per cent. This investigation has included the systems lead-zinc, cadmium-zinc, iron-zinc, copper-zinc, aluminum-zinc, nickel-zinc, manganese-zinc, cobalt-zinc, tin-zinc, and magnesium-zinc. The important ternary system zinc-lead-cadmium and the zinc corners of other ternary systems have been investigated in connection with this work but will not be dealt with here. Zinc does not form a single homogenous zinc-rich solid solution over any considerable range of concentration with any of the metals mentioned. A limited range of solid solubility is said, by previous investigators, to occur in several cases and certain effects on the properties of zinc are attributed (with varying degrees of consistency among different writers) to the presence of certain other metals dissolved in zinc. The increasing use of rolled zinc and the possibilities offered by zinc as a casting alloy in certain fields have made it essential to determine precisely these equilibrium relationships. In carrying out this investigation reliance was placed chiefly on two methods, conductivity measurements and microscopic analysis. The first method proved valuable in determining the existence and extent of solid solubility. The second method stands alone as a means of determining structural characteristics and supplements the first method in the measurement of solid solubility. The scleroscopic hardness of all conductivity specimens was measured partly for its value from the point of view of mechanical properties and partly as a check on the conductivity curves in indicating the limits of solid solubility. No hardness curves are included in this paper, for in no case were they important in arriving at the constitution of any system. Conductivity measurements were in all cases made on cold-rolled strips 0.020 in. thick and 0.5 in. wide, both as cold rolled and after an

Jan 1, 1923

By C. H. Li, R. J. Stokes, T. L. Johnson

The effect of alumina particles on the nucleation and growth of cracks through a silver- chloride matrzx has been investigated. It has been found possible to promote fibrous cracking in dispersion-strengthened silver, chloride under notch-impact conditions at temperatures at which silver chloride alone cleaves brittlely The modification) of fracture beIzavzor is thought to be due to the relaxation of hydrostatrc stress beneath a notch by the nucleation of cavities near alumina particles. In recent years, composite or dispersion-strengthened materials have been studied primarily to understand their high resistance to plastic flow particularly at elevated temperatures. Dislocation models have been developed with which it is possible to deduce with fair success the effects of interparticle distance, particle size, temperature, upon yielding and creep behavior.l-4 Much less attention has been paid to the fracture behavior of these materials (with the notable exception of common structural steels) and little is known experimentally about the manner in which inclusions affect the nucleation and growth of cracks through a matrix. Nevertheless a beginning has been made in connection with fibrous cracking in ductile matrices where inclusions appear to play an essential ro1e.5-7 During the severe localized plastic deformation which accompanies necking in a tensile test, cavities are believed to develop at inclusions; these cavities subsequently grow and coalesce by plastic flow until separation is complete. It is of interest to consider whether inclusions can affect fracture behavior under loading conditions which restrict the plasticity of the matrix itself (for example, cleavage under conditions of a high imposed strain rate at low temperatures). It is particularly interesting to study these effects in a solid which shows a spectrum of behavior ranging from fully ductile to semi-brittle behavior. Such a solid is silver chloride whose mechanical behavior depends sensitively upon temperature and strain rate.&apos;," The present paper is concerned with a study of the influence of inclusions (in the form of alumina particles) on the fracture behavior of silver chloride loaded uniaxially at low strain rates at room temper- ature and also under notch impact conditions over a wide range of temperature. In particular, it will be shown that the alumina particles can exert a startling effect on the ductile-brittle transition temperature of notched silver chloride and that the magnitude and nature of the effect depends upon both the quantity of alumina and the shape of the alumina particles. 1. EXPERIMENTAL PROCEDURE 1.1 Materials Used. Silver chloride powder of analytical reagent (AR) quality having an average particle size 6 was supplied by the Mallinckrodt Chemical Works (st. Louis, MO.). Acid washed 900 mesh alumina powder, designated A38-900, was supplied by the Norton Co. (Cambridge, Mass.). This powder was added to silver chloride in two forms: a) the as-received condition in which the individual particles were of random irregular shape; their statistical average size was 7; b) in a condition in which each particle was spherically shaped by a fusion technique. In this case, the statistical average particle size determined with the optical microscope was approximately the same (about 5p) but electron micrographic evidence indicated that many ultra fine particles were present in the spheroidized powder. 1.2 Preparation of Composite Materials. Silver chloride-alumina composites containing 2.5, 5, and 15 pct by volume of alumina were produced by the extrusion of mechanically mixed powders blended in a ball mill for 24 hr at room temperature. The mixtures were compacted at 50,000 psi at room temperature in the form of billets 3/4 in. in diameter and 1 in. long which were then extruded with a 16:l reduction ratio at 370°C through a radius-type steel die having a 5 deg lead-in angle. An extrusion temperature of 370°C was selected to ensure that all composites had sufficient plasticity to be extruded. Apart from this general requirement, the choice was arbitrary. 1.3 Microstructure of Composites. Attempts were made to check the distribution of alumina metallo-graphically by polishing transverse and longitudinal sections of the extruded rod. Specimens were wet-ground to 600 emery paper and lapped successively with 5 and 0.25-p grades of diamond paste. They were etched for 10 sec in 10 pct sodium thiosulfate solution and lightly polished in concentrated ammonium hydroxide. The most effective way to render the alumina particles and grain boundaries visible was to radiate the surface with intense white light to decorate the grain boundaries and the particle-matrix interfaces photolytically.

Jan 1, 1962