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By K. E. Brown, G. H. Fancher

An 8,000-ft experimental field well was utilized to conduct flowing pressure gradient tests under conditions of continuous, multiphase flow through 2 3/8-in. OD tubing. The well was equipped with 10 gas-lift valves and 10 Maihak electronic pressure recorders, as well as instruments to accurately measure the surface pressure, temperature, volume of injected gas and fluid production. These tests were conducted for flow rates ranging from 75 to 936 B/D at various gas-liquid ratios from 105 to 9,433 scf/bbl. An expanding-orifice gas-lift valve allowed each flow rate to be produced with a range of controlled gas-liquid ratios. From these data an accurate pressure traverse has been constructed for various flow rates and for various gas-liquid ratios. A comparison of these tests to Poettmann and Carpenter's correlation indicates that deviations occur for certain ranges of flow rates and gas-liquid ratios. Numerous curves are presented illustrating the comparison of this correlation with the field data. Poettmann and Carpenter's correlation deviates some for low flow rates and, in particular, for gas-liquid ratios in excess of 3,000 scf/bbl. These deviations me believed to be mainly due to the friction-factor correlation. However, Poettmann and Carpenter's correlation gives excellent agreement in those ranges of higher density. This was as expected and predicted by Poettmann. He pointed out that their method was not intended to be extended to those ranges of low densities whereby an extreme reversal in curvature occurs.l As a result of these experimental tests, correlations using Poettmann and Carpenter's method were established between the friction factors and mass flow rates which are applicable for all gas-liquid ratios and flow rates. Definite changing flow patterns do not allow any one correlation to be accurate for all ranges of flow. INTRODUCTION The ability to analytically predict the pressure at any point in a flow string is essential in determining optimum production string dimensions and in the design of gas-lift installations. This information is also invaluable in predicting bottom-hole pressures in flowing wells. Although this problem is not new to industry, it has by no means been solved completely for all types of flow conditions. Versluys,2 Uren, et al, 3 Gosline,4 May,5 and Moore, et al,6,7 were all early investigators of multiphase flow through vertical conduits. However, all of these investigations and proposed methods were very limited as to their range of application. Likewise, many are extremely complicated and therefore not very useful in the field. Only in the last decade have any significant methods been proposed which are generally applicable. The most widely accepted procedure in industry at the present time is a semi-empirical method developed from an energy balance, proposed by Poettmann and Carpenter8 in 1952. Their correlation is based on actual pressure measurements from field wells. Accurate predictions from this correlation are limited to high flow rates and low gas-liquid ratios. Although this method will be discussed in detail later, it should be pointed out that two important parameters, namely the gas-liquid ratio and the viscosity, were omitted in their correlation. The viscosity was justifiably omitted since their data was in the highly turbulent flow region for both phases, and most wells fall in this category. The gas-liquid ratio was incorporated to some extent in the gas-density term. In 1954, Gilbert9 presented numerous pressure gradient curves obtained from field data for various flow rates and gas-liquid ratios for the determination of optimum flow strings. However, no method is presented for predicting pressure gradients except by comparison to these curves. Baxendell, et al,10 proposed a method based on Poettmann and Carpenter's procedure

By W. W. Mullins

The development, by the mechanism of volume diffusion, of a grain boundary groove on an interface separating a solid phase and a saturated fluid phase is calculated under the following assumptions: 1) isotropy of the interfacial free energy 's, 2) applicability of the Gibbs-Thompson formula relating curvature and chemical potential, 3) a nearly planar groove surface. The groove profile is found to have a .fixed shape and linear dimensions that are proportional to (time)1/3. The constant of proportionality is evaluated and involves ?s in such a way that the latter my be evaluated from grooving kinetics. A grain boundary that intersects an interphase interface will tend to produce a groove along the line of intersection (Fig. 1). The ultimate motivation for the formation of the groove is the reduction in interfacial free energ that occurs as the grain boundary contracts. Smith has discussed the way in which the free energy of the interfaces determines their dihedral angles at the groove root and has given a detailed analysis of the effect of the dihedral angles upon the nature the microstructures developed in polyphase alloys. Herring2 has extended the considerations to the case in which the free energy of an interface depends on its orientation and has thus added torque terms to the condition for interface equilibrium. Although the grain boundary and the interphase interface may quickly achieve the proper equilibrium angles where they intersect, as determined by the balance of equivalent tensions and torques,"2 the groove will generally continue to grow (though with decreasing speed). Thermodynamically, this continued growth reflects the fact that the lowest free energy cannot be achieved until the entire grain boundary has been eliminated; mechanistically, the growth occurs in response to inhomogeneities of chemical potential that are caused by the constraint of fixed dihedral angles at the groove root. The latter point is illustrated in Fig. 1, which shows that atoms* near the groove are on the convex side of a cylindrically curved surface and therefore have a higher chemical potential than atoms on the flat interface beyond. Thus atoms tend to leave the curved groove shoulders and force the groove to deepen. When both phases are solid additional chemical potential gradient may arise from whatever strain fields are necessary to insure continuity of material across the interface. In the discussion that follows, this complication due to strain will not occur since we always assume one phase to be a fluid and the other a solid. The transport processes that may operate to permit growth of the groove are surface (interface)* diffusion, volume diffusion in the phase on either side of the interface, and evaporation-condensation when one phase is gaseous. (Also a melting-freezing process is responsible for groove enlargement on a solid-melt interface as discussed in Sec. VI). The theory of grain boundary grooving has been discussed in detail for the processes of surface diffusion and of one type of evaporation-condensation.3'4 The theoretical predictions for the mechanism of surface diffusion have been confirmed in an experimental study of grooving kinetics in copper.5 In this paper, the theory of groove development by volume diffusion will be presented. Volume diffusion can occur either by atomic migration in the solid S or by diffusion of S atoms in the fluid phase, or solvent, adjacent to the groove surface. As discussed in Sec. V, volume diffusion in the solid should be less important than surface diffusion in forming a groove. Apart from verifying this statement then, the main interest of the present analysis centers on diffusion in an external solvent. The solvent may be either a liquid (e.g., water, or-

Jan 1, 1961

By Nicholas J. Grant, H. C. Chang

Microscopic observations during creep tests were made on AI-20 pet Zn, 80 pet Ni-20 pet Cr, and 25 and 3S aluminum specimens. All these materials failed in an inter-crystalline manner under certain stress and temperature conditions. Particular atten-tion was given to the initiation and propagation of intercrystalline cracks in coarsegrained AI-20 pct Zn specimens. The geometry of the grains and grain boundaries in these specimens was known before the tests. On the basis of the observations and a knowledge of the interaction between grains and grain boundaries, a mechanism of intercrystalline fracture and propagation of the fracture has been proposed. METAL, and alloy fracture occurs essentially in two ways: transcrystalline and intemrystalline. In the past most of the work done in this field was centered on the determination of stress criteria for fracture. The specimens used for these studies were tested under varying conditions of stress state, temperature, and strain rate. Unfortunately, very little attention was given to the initiation and propagation of the fracture, whereas the nature of fracture was examined closely only after failure. Several extensive reviews of these studies have been published by Orowan, Smith, Barrett, and Petch.1, 4 It is well known that a material which exhibits a ductile and transcrystalline fracture can be made to exhibit a brittle and intercrystalline fracture by modifying its composition and by heat treatment. This modification may or may not result in microscopically observable precipitation in the grain boundaries." In the creep of any one alloy the transition of transcrystalline to intercrystalline fracture is a function of stress, strain rate, and temperature." The tendency for intercrystalline fracture to occur increases as the strain rate decreases and the testing temperature increases. Extensive work on high purity aluminum (99.995 pet) under creep conditions showed the importance of the interaction between grains and grain boundaries, and the different responses of grain and grain boundaries to the variables: stress, strain rate, and temperature.7, 8 It was also shown that grain boundary deformation necessarily has to be accommodated in the grains by various deformation means as. for example, fold formation. The type of fracture resulting from the creep of high purity aluminum was invariably found to be transcrystalline. On the other hand, 2S and 3s aluminum were, under certain conditions, found to fracture in an intercrystalline manner." One reason given for this was that the grains could accommodate to a lesser extent the deformation of the grain boundaries.19 It was decided to examine this line of reasoning in greater detail and to investigate the particular interactions between grains and grain boundaries that result in the incidence and progression of inter-ct,ystalline fracture. It is also the purpose of this paper to show where and how intercrystalline cracks start and how they propagate to result in fracture. Several alloys—Al-20 pct Zn, 80 pet Ni-20 pet Cr, 2S and 3s aluminum-— were used for this study, but attention was paid mainly to the behavior of an A1-20 pet Zn alloy, since its general creep behavior has been established." From the results of this study a mechanism of intercrystalline fracture is proposed. Experimental Procedure The experimental procedure was similar to that used in previous work and has been detailed elsewhere.' Two parallel flat surfaces were milled from an originally round specimen, giving a gage portion which was 1x0.09X0.17 in. Some round specimens, 1/4 in. round by 1 in., were also tested. The A1-20 pet Zn specimens. which were annealed at 1030°F for 24 hr, showed two to four grains across the width of the test bar, and most of the grains occupied the whole thickness of the specimenu. Before some of the specimens were subjected to creep, the grain arrangement was mapped out in a development drawing, Fig. 1. The initiation and

Jan 1, 1957

By I. F. Jackson, H. L. Hartman

Hard-metal inserts have received considerable attention in the mining industry recently for a variety of excavating and penetrating purposes. Their use in percussive drilling and in coal cutting machines is well known, but attempts to utilize them in cutting materials such as dimension stone have been discouraging because of excessive tool wear and failure. Particular attention is given to those properties of hard-metal inserts that affect their resistance to wear. A consideration of the actual wear mechanism shows the importance of correct mounting of the inserts and of the selection of suitably powered driving motor so as to achieve minimum tool wear and maximum tool life. Comparisons are made between the performances of types of hard-metal inserts, relating their inherent properties with results obtained in laboratory tests. As part of a broad program to improve the quarrying and processing of industrial minerals, The Pennsylvania State University has been investigating the machinability of slate under laboratory and field conditions. It should be emphasized that the results of the research presented in this paper are also applicable to other natural structural materials, and particularly to the more workable ones such as limestone and sandstone. Improvements which accrue in cutting and sawing should prove of benefit to all the dimension stone industry. Further, it may be pointed out that the results reported here are applicable to rotary drilling (with drag bits) as well as to cutting and sawing of rock. INVESTIGATIONS IN RELATED FIELDS The investigation was initiated with an extensive survey of available literature related to metal cutting and to rotary drilling. The following similar features between metal cutting and slate cutting became evident: 1) Hard-metal inserts are widely used as a cutting tool in both cases. 2) The forces acting on the tool may be resolved into normal and tangential components. 3) Rate of penetration and tool wear are important criteria in each case. On the other hand, important differences also exist: 1) Most metals, exhibit plastic behavior, while slate (and most rock) is a brittle material under normal conditions. 2) In metal cutting the component of force acting parallel to the surface of the workpiece is considerably greater than the force holding the tool against the workpiece. 111 slate cutting, this situation is reversed. Similarities between drag-bit rotary drilling and slate cutting are as follows: 1) In both casts, a tool, usually of the hard-metal insert type, is used to penetrate a brittle material. 2) The drilling forces and related variables, such as rotation speed, are similar. 3) Chip formation in each case is essentially the same. 4) The shape of the tool is similar in rotary drilling and slate cutting. Important differences are also apparent: 1) The objective of drilling is to produce a directed hole, while in cutting it is to form a kerf. In core drilling, however, a kerf is also produced. 2) The horizonta1 component of force in rotary drilling decreases from the center to the outside of the tool, whereas in slate cutting the component is almost uniformly distributed across the width of the tool. 3) The power absorbed in the drill rod is greater in rotary drilling. 4) The clogging action of chips, if excessive power is applied to the tool and if flushing is insufficient, is more serious in rotary drilling. Because of the striking similarities between metal cutting and slate cutting, and between rotary drilling and slate cutting, it was considered that the findings of investigators in those fields would serve as a guide for experimental studies of slate cutting. The following is thus devoted to a discussion of those aspects of metal cutting and rotary drilling pertinent to the present investigations.

Jan 1, 1962

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By L. Luini, E. Lee

An exploratory survey of the heat treatment response of commercial titanium alloys (Ti-150A, RC-130B, and MST 3AI-5Cr al-loys) shows a wide range of possible hardness and microstructural characteristics. The hardening is primarily dependent on the solid state transformation of the phase. An age hardening reaction which apparently is associated with ß decomposition and precipitation has been shown. Brittleness and notch sensitivity appear to be characteristic of age hardening to high hardness. Ductility, tensile strengths, and elongations are given. A NUMBER of commercially produced titanium-base alloys have been made available by the titanium metals industry. These alloys were developed to combine the light weight of titanium with increased strength through alloy additions. Usually the properties of these alloys are reported for material in the hot rolled and annealed condition. Since the production of commercial titanium has preceded the investigation of titanium-base alloy systems, the potential of these alloys is not well known. Although heat treatability has been indicated for these alloys, data on the response to heat treatment are quite limited. The heat treatability of titanium is based on the allotropic transformation of the high temperature, body-centered cubic ß structure to the low temperature, hexagonal close-packed a structure at approximately 1625 °F. This transformation in the pure metal is of little practical significance in heat treatment since the high temperature phase is not amenable to controlled transformation. Alloy additions serve to alter the transformation kinetics and permit control of the transformation by heat treatment variables. The effects of different alloys on the allotropic transformation in titanium classify them in two general categories,1 a stabilizing and ß stabilizing elements. The a stabilizers, represented by aluminum and oxygen, raise the temperature limits of the low temperature phase and introduce a two-phase a + ß temperature range. The ß stabilizers, represented by molybdenum and columbium, lower the equilibrium temperature of ß and give rise to an extended temperature range where both a and ß phases are stable. Another type of ß stabilizer, represented by iron, chromium, and manganese, introduces a eutectoid reaction. Some commercial titanium alloys belong to complex multiple element systems. Based upon the phase diagrams of the binary systems, the general effect of commercial compositions is to vary the stability of the high temperature phase and significantly alter its transformation characteristics. Therefore it is expected that the characteristics of alloyed titanium can be altered by heat treatment. The present investigation was undertaken to survey the variations in hardness, microstructure, and mechanical properties as affected by heat treatment variables. Commercial Alloys lnvestigated The commercially available titanium-base alloys selected for this investigation and obtained as 3/4 in. diameter hot rolled and annealed bars are listed in Table I. The producer did not determine the chemical composition of the Ti-150A heats X1052 and L685. The early heats of Ti-150A, prefixed with the letter X, were melted with tungsten-tipped electrodes and cast in approximately 500 lb ingots 12 in. in diameter. The heats prefixed with the letter L were melted under a revised melting practice yielding approximately 1300 lb ingots 16 in. in diameter. The final annealing treatment was at 1200" to 1250°F for 1 hr. The MST-3A1-5Cr alloy was melted in an induction furnace and cast in 7 in. diameter ingots. This practice produces high carbon material and some variation in the amount of carbides was found in different sections of the same bar. The RC-130B alloy was melted with a carbon arc. This alloy showed approximately 2 pct carbides. No large segregation effects were observed.

Jan 1, 1955

By Y. Kondo, A. M. Gaudin

A combined method for sizing in the sub-micron range was developed using centrifugation and gamma emission. Its essential features are: 1) Centrifugation of suspended mineral in water carried out at 4°C where water has its maximal density and zero temperature gradient of density 2) Gamma activition of the sample suspension induced by irradiating it in a nuclear reactor prior to centrifugation 3) Measurement of the activity of a beam of suspension as it is sedimenting in the centrifuge, using a scintillation counter provided with a discriminator. Albite, the sodium feldspar, was used as feed to the comminution step, and the induced gamma activity of Na24 was measured. Dissolved sodium ion caused a a non-settling activity in the measurement. Other "noise" is due to scattered gamma radiation from albite particles in the centrifuge outside of the line of sight. These two activities were obtained sep arately and subtracted from the total activity counted. The relative solid concentration in the suspension under the collimating slit is proportional to this net activity. The cumulative weight per cent of undersize particles was calculated and plotted against size on logarithmic scales. The relationship was found to be linear down to about 30 mµ. The specific surfaces calculated from particle size distribution agree with those measured by krypton gas adsorption. The measurement of particle size distribution of comminution products has been of interest in clarifying the mechanism of the process. The Gaudin-Schuhmann equation1,2 relates the cumulative percentage undersize, y, to relative particle size x/k. The particle size, x, and the size modulus, k, together with the distribution modulus, m, characterize the particle size distribution, m is the slope of a plot of log (y) against log (x/k). This equation has been verified for ground particles down to 1 micron in size.3'4 For particle sizes smaller than a few microns, the precision and facility of sedimentation and microscope techniques become questionable. Use of a centrifuge which shortens settling time from weeks to hours is attractive. Many centrifugal methods have been proposed; however, determination of the solid concentration of the suspension at a reference level as a function of time is difficult, and sampling the suspension is likely to introduce errors. Measurement of particle size distribution by X-ray absorption in gravitational5 and in centrifugal6 sedimentation have also been tried. In these methods, the absorption coefficient for the solid is independent of size, since the wave lengths of the X-rays and gamma-rays are orders of magnitude smaller than the particles. Radiometric techniques7 in size distribution measurement have been developed within the last several years. They offer advantages over usual gravimetric and optical methods. PRINCIPLE OF METHOD The combined method of centrifugation and gamma emission for sizing in submicron range described in the present paper has the following essential features. 1) Centrifugation is carried out at 4 ± 0.1°C. Convection currents in the water phase due to density changes caused by temperature variation may disturb completely the settling system. To avoid this difficulty, the unique property of water having zero temperature gradient of density at 4°C is used. 2) Prior to size measurement the sample suspension is irradiated in a nuclear reactor and gamma activity induced. The gamma activity of the particles sedi-mented radially is measured by a scintillation counter provided with a discriminator. By this method, interruption of centrifugation by withdrawing samples is avoided and the counting rate at any time represents the solid concentration in the suspension at the level of the collimating slit of the centrifuge at the particular time at which the measurement is made. 3) By proper selection of the feed material and of the comminution device, gamma activities of foreign

Jan 1, 1964

By W. F. Rogers, J. A. Stewart, P. J. Kalish, E. O. Bennett

Detailed descriptions are given of materials, apparatus and the experimental procedure used to study the effect of bacteria on sandstone permeability. The factors affecting permeability during injection of bacterial suspensions which have been investigated are: (I) concentration of bacteria; (2) core permeability and median pore size; (3) species of bacteria, mode of aggregation and relative size; (4) injection rate or pressure differential; (5) mean pressure; and (6) depth of penetration of bacteria. The investigation demonstrated that bacteria cannot reduce core pertneability to zero and that their effect on permeability is subject to definite limitations. Remedial or permeability restoration studies also were made. Acidization in combination with reverse flow war found to be an effective method for restoring permeability In cores partially plugged with bacteria. The relationship between the bacterial quantities in the laboratory tests and those found in field operations is discussed. The linear laboratory flow data have been translated into terms of field radial systems; these data indicate the most practical methods of maintaining injection rates in the presence of bacteria are to increase injection pressures or hydraulically fracture the formation. INTRODUCTION It has long been known that various bacteria flourish in the above-ground components of oil field water-injection systems. The presence of these bacteria has led to the suspicion that they might enter into the causes for reduction of injection well permeability, but only recently has an attempt been made to describe the effects quantitatively.1 Biocides are used in many cases without a firm knowledge as to whether the bacteria are killed, or if they are, whether the dead cells affect formation permeability. This project was undertaken as part of a study to determine the effect of bacteria, residual oil and precipitated solids such as iron sulfide or calcium carbonate on the permeability of sandstones and to learn whether any of these materials adversely affect brine injectivity in secondary recovery or disposal operations. This report deals with that portion relating to the effect of bacteria. MATERIALS CORES Three different permeability ranges of Berea sandstone cores were used in the study. The range of initial, absolute brine permeabilities kj were: high — 278 to 400 md: medium—130 to 162 md; and low—17.7 to 48.3 md. The permeability data for the cores used in the tests are included in Table 1. All cores were cut to a nominal 1 in. diameter. Following air permeability determinations, they were molded with an epoxy resin in 1.5 in. ID aluminum sleeves. The sleeves had drilled and tapped holes for intermediate pressure connections along the length of the cores. After molding, the high- and medium-permeability cores were trimmed to 4 in. in length and the low-permeability cores to 2 in. These lengths resulted in pore volumes of approximately 10.9, 10.4 and 4.4 ml, respectively, for the high-, medium- and low-permeability cores. Pressure-transmitting channels were drilled through the plastic into the core proper, using the sleeve holes as drill guides. Width and depth of channel penetration into the core proper were approximately 0.03 in. and 0.05 in., respectively. Three pressure taps were used with all cores; for the high- and medium-permeability cores the taps were spaced 1 in. apart; for the low-permeability cores the taps were spaced 0.4, 0.8 and 1.2 in. from the inlet end. Pore size distributions were calculated from restored-state capillary pressure curves for representative cores in each of the three permeability ranges. In each case the pore size range with the greatest percentage of the pore space included the very small pores up to 0.5 micron in radius. The median pore radii were in the 5.5 to 6 micron range for the high-permeability cores; in the 4.5 to 5 micron range for the medium-permeability cores; and in the 3.5 to 4 micron range for the low-permeability cores.

Jan 1, 1965

By L. H. Robinson

Triaxial compression tests on Indiana limestone indicate that chemical additives in the pore fluids can increase or decrease the strength in plastic failure but not in brittle failure. Tests using a series of the sodium salts of dicarboxylic acids show that odd-number carbon-atom chains decrease the yield strength as much as 3.0 x 10 3 psi, and even-number carbon-atom chains increase the yield strength as much as 9.0 x 102 psi. ,The most effective chemical (sodium citrate) decreased the yield strength of Indiana limestone from 16.0 x 103 to 12.0 x 103 psi. The chemical additives investigated have no influence on microbit drilling rate when drilling with zero differential pressure. However, when drilling at a 2.0 x 103-psi pressure differeniial and using an odd-number carbon chain compound as the circulating fluid, the roller bit drilling rates were slower than with water whereas the drag bit drilling rates were faster. One even-number carbon chain compound added to the circulating fluid produces the opposite effect: the roller bit drilling rate is slightly faster than with water and the drag bit slower than with water. INTRODUCTION A Russian book by Rehbinderl published in 1944 generated much interest in the possibility of aiding and accelerating the destruction of solids by the action of a liquid in which the solids are deformed. This book describes a process in which microcracks are generated during elastic deformation. To describe this process, the rock is divided into three zones: (1) the zone in which the destruction takes place, (2) the predestruc-tion zone (an affected area immediately below the destroyed zone) and (3) the undisturbed specimen. Consider a load applied normally to a surface of an infinite slab of rock. Immediately below the point of application of the load, the rock is destroyed by compression or shear forces. Below this area of destruction, because of a great number of discontinuities ranging from defects to weak points in crystals of discontinuities in crystal latices, very small cracks are created in or between the crystals (often referred to as microcracks). Upon removing the load, the broken rock in the destroyed zone could be removed. In the lower predestruction zone, however, the microcracks in and between the crystals could disappear by the process of rehealing, i.e., the molecular attraction from one side of the crack to the other side being sufficient to completely eliminate the crack. Thus, a large number of these microcracks possibly exist only for a relatively short period of time. The concept of small cracks being generated within the crystals of a rock is not unreasonable. If the rock matrix is deformed below the yield point, some of the defects present within the crystalline structure could start small cracks through the interior of the grains. Upon removal of the load, these microcracks reheal (or the newly generated surfaces come back together) so that all evidence of cracks completely disappears. Under various types of loading, and in various types of fluids, the rehealing of these cracks would be time dependent. If a liquid adhered to the surface of a rock, it could penetrate into the microcracks and thus delay or prevent the rehealing process. This suggests that the prevention of healing of the microcracks may be dependent upon the wetting characteristics of the solid. Thus, rocks which are water-wet should be more easily destroyed in water than in nonpolar hydrocarbon liquid. Adsorption of a liquid could also reduce the free surface energy which could explain the decrease in strengths of materials under nonrepetitive-type loading. Rehbinder's work prompted Boozer, Hiller and Serdengecti 2 to examine the effects of pore fluids on the deformation of rocks subjected to triaxial compression over a range of confining pressures, temperatures and strain rates. Fluids which strongly adsorbed on the rock grain surfaces decreased the strength of sandstone and limestone, which deformed plastically. For certain strain

By A. S. Odeh

ABSTRACT A simplified model was employed to develop mathematically equations that describe the unsteady-state behavior of naturally fractured reservoirs. The analysis resulted in an equation of flow of radial symmetry whose solution, for the infinite case, is identical in form and function to that describing the unsteady-state behavior of homogeneous reservoirs. Accepting the assumed model, for all practical purposes one cannot distinguish between fractured and homogeneous reservoirs fram pressure build-up and/or drawdown plots. INTRODUCTION The bulk of reservoir engineering research and techniques has been directed toward homogeneous reservoirs, whose physical characteristics, such as porosity and permeability, are considered, on the average, to be constant. However, many prolific reservoirs, especially in the Middle East, are naturally fractured. These reservoirs consist of two distinct elements, namely fractures and matrix, each of which contains its characteristic porosity and permeability. Because of this, the extension of conventional methods of reservoir engineering analysis to fractured reservoirs without mathematical justification could lead to results of uncertain value. The early reported work on artificially and naturally fractured reservoirs consists mainly of papers by Pollard,l Freeman and Natanson,2 and Samara.3 The most familiar method is that of Pollard. A more recent paper by Warren and Root showed how the Pollard method could lead to erroneous results,4 Warren and Root analyzed a plausible two-dimensional model of fractured reservoirs. They concluded that a Horner-type pressure build-up plot of a well producing from a fractured reservoir may be characterized by two parallel linear segments. These segments form the early and the late portions of the build-up plot and are connected by a transitional curve. In our analysis of pressure build-up and drawdown data obtained on several wells from various fractured reservoirs, two parallel straight lines were not observed. In fact, the build-up and drawdown plots were similar in shape to those obtained on homogeneous reservoirs. Fractured reservoirs, due to their complexity, could be represented by various mathematical models, none of which may be completely descriptive and satisfactory for all systems. This is so because the fractures and matrix blocks can be diverse in pattern, size, and geometry not only between one reservoir and another but also within a single reservoir. Therefore, one mathematical model may lead to a satisfactory solution in one case and fail in another. TO understand the behavior of the pressure buildup and drawdown data that were studied, and to explain the shape of the resulting plots, a fractured reservoir model was employed and analyzed mathematically. The model is based on the following assumptions: 1. The matrix blocks act like sources which feed the fractures with fluid; 2. The net fluid movement toward the wellbore obtains only in the fractures; and 3. The fractures' flow capacity and the degree of fracturing of the reservoir are uniform. By the degree of fracturing is meant the fractures' bulk volume per unit reservoir bulk volume. Assumption 3 does not stipulate that either the fractures or the matrix blocks should possess certain size, uniformity, geometric pattern, spacing, or direction. Moreover, this assumption of uniform flow capacity and degree of fracturing should be taken in the same general sense as one accepts uniform permeability and porosity assumptions in a homogeneous reservoir when deriving the unsteady -state fluid flow equation. Thus, the assumption may not be unreasonable, especially if one considers the evidence obtained from examining samples of fractured outcrops and reservoirs. Such samples show that the matrix usually consists of numerous blocks, all of which are small compared to the reservoir dimensions and well spacings. Therefore, the model could be described to represent a "homogeneously" fractured reservoir. la this paper, the fundamental equation of flow

Jan 1, 1966

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.' Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts' Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg's method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By D. Harker, W. E. Seymour

CERTAIN alloys of iron and nickel, when rolled and annealed, possess a preferred crystal orientation: (001) in the rolling plane and [loo] in the rolling direction, when recrystallized at 850" to 1050°C after approximately 98 pct cold reduction. Since the preferred orientation makes a direction of easiest magnetization coincide with the rolling direction, these alloys, especially a 50 pct iron in nickel alloy, have found wide application in the electrical industry' for choke coils and special types of transformers. The rate of the recrystallization reaction was studied at temperatures ranging from 500° to 600°C. The heat of activation for the reaction was calculated from the observed rates, and crystal orientation determinations were made before and after re-crystallization. A vacuum melted iron-nickel alloy* analyzing 49.6 pct nickel, 0.018 pct carbon, and 0.30 pct manganese was used for the experiments. The alloy was cold-rolled 98 pct into strips 1/2 in. wide by 0.002 in. thick. Specimens 1 in. long were sealed under a vacuum (approximately 10-8 mm Hg) in 1/2 in. ID pyrex glass tubes. For heat treatment these tubes were fastened to Nicrohm wires and submerged in a molten salt bath controlled to ±2°C. (The maximum measurement error was within 3°C.) The time at temperature was varied logarithmically from one sample to another, and runs were made at 500°, 525", 550" and 575°C. A molten lead bath was used for a run at 600°C which was controlled to the same accuracy. To determine the extent of recrystallization after a particular time at a given temperature, a method was used suggested by the work of Decker, Asp, and Harker.3,4 This method employs an X-ray spectrometer whereby X rays are diffracted from crystallites whose diffracting atom planes are parallel to the rolling plane of the specimen. The intensities of the diffracted rays are measured by a Geiger counter. The counter can be rotated through a range of angle, and can be motor driven through this range at a speed of 2" per min. The measured intensities are plotted vs. angle by a potentiometer recorder. In a 50 pct iron-nickel alloy it was found that only (200) reflections were obtained from the rolling plane with recrystallized material, and that only (220) reflections were obtained from the rolling plane with unrecrystallized material. No other reflections were obtained under these conditions over a range of Bragg angle of 0 to 45" using either type of specimen. As a consequence, the intensity of the (200) reflections from the rolling plane was taken to indicate the amount of recrystallized ma-terial present in a specimen, and the corresponding intensity of the (220) reflections was taken to indicate the amount of unrecrystallized material present. To insure flatness and proper alignment of the reflecting specimen in the spectrometer, the sample was laid in a slot 1/2 in. wide x 0.001 in. deep which was machined in a 3/4x2x1/2 in. steel carrier. The specimen then was taped down with cellophane tape. This steel cradle was mounted vertically in the specimen holder of the spectrometer so that the bottom edge of the carrier rested against a horizontal shoulder. Intensity data used in plotting the percent of recrystallized material vs. time at temperature were obtained by directly counting the diffracted beam of nickel filtered copper Ka radiation used throughout the work. The X-ray spectrometer was employed also in obtaining pole figure data to be used for orientation determinations. At the beginning of this investigation a transmission pole figure holder was used." As a thickness of 0.002 in. of this alloy was found to be opaque to the copper Ka radiation, it was necessary to reduce the thickness of the pole figure specimen. A cold-worked sample was etched in a 50 pct HCl solution for 5 min and was found to transmit a

Jan 1, 1951

By L. C. Brown, A. J. Stewart

Phase transformations have been studied in Ag-Zn alloys quenched from the high-temperature bcc 0 phase and lying in the composition range 37.4 to 50.0 at. pct Zn. On quenching, the alloy with the lowest zinc content transformed to massive a (fcc); all other alloys formed the ordered (3' phase. On deformation, a martensitic reaction took place forming a close-packed structure. At Lou' zinc contents transformation to this structure was complete. However, above 43 at. pct Zn a p.rogressively increasing amount of ß' was retained following deformation. The close-packed structure was fcc at lower zinc contents (under 47 at. pct Zn) and either hcp or a mixture of fcc and hcp at high zinc concentrations. The structures produced by cold working were unstable and on aging transformed to the ß' phase or the complex hexagonal to phase. For low zinc contents (under 43 at. pct) the fcc st-ructure transformed directly to the equilibrium To phase. With higher zinc contents, some 13' was retained following defownation, and on aging the amount of this phase relative to the close-packed structure increased. On further aging both structures transformed cornpletely to PO. Metallographic examination indicated that the nature of the deformation product depended very markedly on the mode of deformation. Tensile deformation gave a microstructure characteristic of thermal martensite. KING and Massalski1 have shown that an alloy of Ag-50 at. pct Zn quenched from the high-temperature bcc ß phase undergoes a low-temperature ordering reaction forming ß' which can be retained to room temperature. On deformation an hcp phase is produced, although this is unstable and the structure reverts completely to ß' on aging. In the present paper, the work of King and Massalski is extended to cover a wide composition range in the p phase, observations being made of the structure of the quenched 13 and of the effects of deformation and aging. The relevant portion of the Ag-Zn phase diagram is shown in Fig. 1. King and Massalski have shown that close to stoichiometry the ß' phase is the equilibrium structure at low temperatures. The approximate composition range of this phase, taken from a recent paper by Pops and Massalski,3 is shown on the phase diagram. The locations of atom sites are very similar in the ß' and to structures, and the 4, structure can be derived from the 0' structure by a small movement of atoms mainly in the direction of the cube diagonal.4'5 However, the probability of filling any particular atom site by a silver or a zinc atom is markedly different in the two structures. The structure can be considered partly ordered but the arrangement of the ordered atoms is completely different from that in the p' structure and transformation from ß' to requires a large fraction of the atoms to change position. It has been shown that the ß' transformation is thermally activated involving normal nucleation and growth processes.5,8 Massalski and Barrett7 have shown that in the Cu-Zn binary the (3 phase can be retained in the ordered state to room temperature over a wide composition range. On deformation a new close-packed phase is produced, the structure varying from fcc to a mixture of fcc + hcp to hcp alone with increasing zinc concentration. It appears that an ordering reaction is necessary to retain the bcc phase to room temperature. In CU-Ga,8 the bcc phase cannot be retained to low temperatures as it transforms by a massive reaction above the ordering temperature of the ß phase. The structure of the massive phase is very similar to that in Cu-Zn, varying from fcc to fcc + hcp to hcp with increasing zinc concentration. Similar structures have also been observed in CU-A1,9 Ag-Cd,10,11 and Ag-Al.12 EXPERIMENTAL The alloys were prepared by melting fine silver (99.99 pct purity) and electrolytic zinc (99.999 pct

Jan 1, 1969

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull's suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin's observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin's studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several ' strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r' phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By G. R. Speich

The precipitation of the Feab and Fe,Ti Laves phases (MgZn, type, C14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been studied in the temperature range 500" to 800°C using hardness measurements, light and electron microscopy, and X-ray and electron diffraction. The Fe-Nb alloys contained 0.96, 1.67, and 3.80 pct Nb and the Fe-Ti alloys 3.5, 5.8, and 8.8 pct Ti. In both systems only the equilibrium Laves phase is formed, with nucleation occurring at grain boundaries, at dislocations, and in the matrix. No cellular precipitation or transition phases were observed. The precipitation of the Laves phase in a fine dispersion leads to significant hardening in both systems. The hardness of the aged alloys is proportional to the reciprocal of the square root of the interparticle spacing. The maximum solid solubility of titanium in a! iron is 9.0 pct Ti at 1280°C. THE precipitation of the FezNb and FezTi Laves phases (MgZn2 type, C 14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been investigated as part of a continuing study of the mechanisms of precipitation from ferritic binary iron-base alloys. The iron-rich portions of the Fe-Nb and Fe-Ti phase diagrams are shown in Fig. l(a) and l(b). The Fe-Nb diagram is essentially that given by ansen' with the more recent work of Hume-Rothery and Gibson2 added. Goldschmidt3 indicates that the FezNb Laves phase has a solubility extending from 32 to 55 wt pct Nb. The Fe-Ti diagram is also essentially that reported by Hansen.l The recent results of Nishimura and kamei, Murakami, Kimura, and Nishimura,' indicate that the FezTi Laves phase has a solubility extending from 22.5 to 30.5 wt pct Ti. The L/6 + FezTi eutectic temperature of 1298°C indicated by Kornilov and oriskina' has been adopted. The addition of niobium or titanium to iron lowers the 6 — y transformation temperature and raises the y — a! transformation temperature. This results in a closed y field in the Fe-Ti system, but the lower solubility of niobium in a! (6) iron results in a eutec-toid, 6 — y + FezNb, at 1200°C, and a peritectoid, y + FezNb —-a, at 989°C in the Fe-Nb system. The maximum solubility of niobium is reported to be 4.5 wt pct in 6 iron,' 1.0 wt pct in y iron,7 and 1.8 wt pct in a iron.' Some results from the present work indicate that the maximum solubility in a! iron is actually less than 0.96 wt pct Nb. The maximum solubility of titanium in a! (6) iron is somewhat uncertain since the early work of To faute and Butting-haus indicated a value of 6.0 wt pct while later work of Kornilov and Boriskina6 yielded a value of 14.0 wt pct. The present work indicates that the maximum solubility is actually 9.0 wt pct. In both systems the phase in equilibrium with the iron-base solid solutions is a Laves phase (Mg znztype, C14), FezNb or FezTi. Both of these Laves phases have a wide range of Solubility. The precipitation-hardening behavior of Fe-Nb or Fe-Ti alloys has not been studied extensively. Genders and Harrison' reported that binary Fe-Nb alloys hardened upon aging. Peter and Fisher7 studied the mechanical properties of Fe-Nb and Fe-Ti alloys quenched from different phase fields.

Jan 1, 1962

By S. J. Matas, R. F. Hehemann, R. H. Goodenow

The hot-stage metallographic method has been employed to determine radial growth rates of upper and lower bainite. Lower bainite appears to grow as individual plates that increase in both length and thickness while upper bainite grows as sheaves of closely spaced plates or needles. A discontinuity in the temperature dependence of the growth rate appears to be associated with the transition from upper to lower bainite and stepped quenching experiments suggest that lower bainite will not continue to grow when the temperature is raised to the upper range. Thus, a single process does not appear to control the growth of both upper and lower bainite. A tentative model based on the forces acting on a dislocation interface is proposed to account for the slow growth of bainite. It has been recognized since the early studies of Davenport and Bain that a close relationship exists between the martensite and bainite transformations in steels. However, diffusion of carbon during the transformation has lead to considerable controversy concerning the reaction mechanism.1-7 Many studies4,5,7-9 have emphasized the structura and kinetic aspects of the bainite reaction and, in particular, the difference observed between the two forms of bainite—frequently termed upper and lower bainite. A kinetic difference between the two types of bainite has been revealed in the activation energy determined from the overall reaction;4,5 however, many difficulties arise in an interpretation of these activation energies since a number of temperature dependent factors contribute to the kinetics of the overall reaction. The displacive surface relief10 accompanying the bainite reaction permits a separation of the nuclea-tion and growth contributions to the reaction and allows the kinetics of the growth process to be examined. Several investigations of this type have been conducted; however, they have been restricted to the low temperature range.3'6'11 Here, bainite plates are observed to grow slowly in both length and width. The present investigation extends such studies to include the upper bainite range. MATERIALS AND PROCEDURE Materials. The composition of the steels studied in this investigation are presented in Table I. The range of composition permitted a study of the effect of carbon content on the growth rate of upper bainite in the 9 pct Ni steels and consideration of both upper and lower bainite in the higher carbon steels. These steels were received as hot-rolled rounds and were forged to approximately 1/2 in. thick plates for preparation of metallographic specimens. In order to produce an essentially zero carbon steel, Steel A was decarburized in wet hydrogen at 1550°F for 15 days with the result tabulated as Steel AD. Experimental Procedure. In order to study the slow growth of the displacive transformation product, a commercially available Leitz hot stage was modified to permit heating of the specimen by its own resistance in a manner similar to that employed by other investigators.6 The furnace chamber was maintained at a pressure of 2 to 3 X 10-5 mm Hg prior to austenitizing at 2000° ± 12° F for 5 min. Samples could be cooled from the austenitizing to the transformation temperature in approximately 15 sec and the progress of transformation was recorded with a 9 cm by 12 cm single frame camera or a 16 mm movie camera. RESULTS AND DISCUSSION Growth Characteristics. The general growth characteristics observed in this investigation were analogous to those reported previously.3,6,11 Typical growth sequences for the high temperature and low temperature forms are illustrated in Figs. 1 to 5. In both temperature ranges, bainite plates increase in length at slow, temperature dependent rates until interrupted by a grain boundary, another plate, or

Jan 1, 1963

By J. O. Brittain, E. Lautenschlager

Yield point measurements were made on polycrys-talline specimens of a iron deformed various amounts at 770, 1950, or 273°K, aged, and redeformed at 77: 195°, or 273°K. When the prestrain temperature is lower than that subsequent to aging, the yield point return is suppressed relative to specimens deformed at the same temperature both before and after aging. The degree of suppression is a function of both the magnitude of prestrain at the lower temperature and the difference between the deformation temperatures before and after aging. It is proposed that the suppression is caused by the formation of dislocation barriers during the initial low-temperature deformation. The aging kinetics of polycrystalline a-iron wires deformed at 77o or 303oK were studied at 44 " and 64 "C using internal friction measurements. No change was noted as a result of the difference in prestrain temperature. IN an earlier investigation1 it was observed that the return of the yield point was suppressed when a poly-crystalline specimen of a iron was plastically deformed at 77oK, aged at room temperature, and subsequently tested at room temperature. In order to investigate this observation, a research program was undertaken to measure the effect of prestrain temperature on the strain aging of a iron.' According to Thomas and Leak,3 return of the yield point and internal friction are similar measures of strain aging since both are dependent on solute atoms leaving the solid solution. The decrease in internal friction as a function of aging time is indicative of the removal of solute atoms from the solution, while the return of the yield point as a function of aging time gives the rate of arrival of solute atoms at the dislocations. According to Cottrell and Bilby,4 the solute atoms create an "atmosphere" which locks the dislocations and causes a return of the yield point upon restraining. In this experiment, both methods of measuring strain aging were employed in order to have two independent measurements of the strain aging phenomenon. In a previous study,5 the strain aging kinetics of a similar lot of a iron were measured for specimens which were prestrained and tested at the same temperature over the range of 77" to 273°K. Although some differences were found in the correlation of the two methods employed for measuring strain aging, the kinetics of strain aging were unaffected by the change of prestrain and test temperature. In another study,6 dislocation line tension and the density of the solute atmosphere were found to contribute to the return of the yield point when ingot iron specimens were prestrained at 303°K and tested at a lower temperature, namely 77°K. This paper is concerned with changes in strain aging kinetics produced by pre-straining at 77" to 303°K and testing at either the prestrain temperature or at higher temperatures up to 273°K. EXPERIMENTAL PROCEDURE The polycrystalline a iron specimens used in both the tensile and internal friction tests were 0.033-in. diam ingot iron wires, wet hydrogen treated and re-carburized. A more detailed procedure for processing a 3/16 in. ingot iron rod (nominal wt. pet composition: Fe - 0.013; C - 0.0125; Mn - 0.023; Si -0.005; P - 0.0023; S - 0.11; Cu - 0.004 N) to 0.033 in. diam specimens containing approximately 0.020 wt pet C and no detectable nitrogen with a grain diameter of 0.033 to 0.040 mm is given elsewhere.5 Immediately prior to testing, specimens were solution treated for 15 min at 700o ± 2°C in a static vacuum of less than 50 ?. of Hg and rapidly quenched into an ice-water bath while still enclosed in a 3 mm quartz vial. The internal friction specimens had 8-in. gage lengths and the tensile specimens had 2-in. gage lengths. The wires used as tensile specimens were first run as internal

Jan 1, 1962

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,' and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson' determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12'13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By R. J. Teitel

The Pb-U system has been investigated by X-ray, thermal, and microscopic analyses. Two pyrophoric intermetallic compounds were found; UPb3 and UPb. The crystallographic structure of UPb3 is reported. A phase diagram was drawn for the system showing three eutectic and one syntectic reaction. AS a result of the interest in uranium metallurgy, the Pb-U system has been investigated. Practically no quantitative data appears in the literature concerning this system. Chips were machined from bars of high-purity uranium obtained from Ames Laboratory and the lead was 99.9 pct high-purity grade from Bel-mont Smelting & Refining Co. The chips were pickled in a dilute solution of nitric acid, washed in water and then alcohol, and dried prior to use for alloy preparation. The lead was simply sheared from the pig with no chemical treatment. Lead and uranium were placed in graphite crucibles and loaded into an induction furnace. In order to insure good alloy formation, the lead was loaded above the uranium to wash the uranium chips into the melt. After the charge was held at the desired preparation temperature for 15 to 30 min, it was allowed to cool in the crucible. The entire melting operation was accomplished in an atmosphere of helium (double charcoal refined grade with no further treatment). The procedure was to outgas the furnace by first evacuating it to 10-% m Hg, admitting helium to 8 psi gage and sealing the furnace off. An optical pyrometer focused on the charge through a hole in the crucible cover was employed for thermal measurements. Usually a 50° to 70°C correction had to be added to the instrument value. The most suitable alloy preparation temperature range was found between 1220° and 1280°C. The reason for this is explained by the phase diagram, Fig. 7. Above this temperature range two liquids separate preventing alloy formation upon cooling at a reasonable rate. On the other hand, below this range the uranium was coated with a layer of both compounds and the rate of reaction was diminished by diffusion processes. The fastest reaction rate occurred in this narrow range of temperature because only UPb coats the uranium and it evidently does not protect the uranium as well as UPb,. Apparatus and Procedures The development of apparatus and techniques was determined by the peculiar properties of the alloys. All the alloys were pyrophoric, and, consequently, the alloys had to be protected from oxidation by handling them in a dry box or inert atmosphere furnaces. Other operations performed outside of this equipment had to be done as quickly as possible. Thermal analyses were conducted in a furnace and arrangement similar to that described by the author.' Graphite crucibles having a thermocouple well in the bottom were used to contain the prepared alloy, while a helium atmosphere protected the melt from oxidation. The furnace was outgassed by pumping a 10-3 mm Hg vacuum until the furnace had been heated to 400°C. Then helium was admitted and the furnace sealed under 8 psi gage pressure. Chromel-alumel thermocouples were used for thermal analysis and the accuracy of thermal measurements was judged to be k 5°C. At first, an attempt was made to use platinum-platinum-rhodium thermocouples, but evidently lead vapors attack it at high temperatures forming low melting alloys. These lead vapors had direct access to the thermocouple because the graphite crucible was porous. A differential temperature control was used to regulate thermal analyses. The thermal gradient across an alundum tube placed between the windings and the crucible was maintained constant by a controller.

Jan 1, 1953