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By B. N. Bose, M. F. Hawk

SINCE Davenport and Bain' introduced the isothermal transformation technique for the study of austenite decomposition in steels, a new field of investigation has opened up. Extensive research has been carried out on many different steels, but relatively little work has been done on eutectoid transformations in analogous alloy systems. The researches of Smith and Lindlief,² Mack,³ and Klier and Grymko²0 on the beta-phase transformation in copper-aluminum alloys, of Hibbard, Eichelrnan, and Saunders4 and Smith5 on the kappa-phase transformation in copper-silicon alloys, of Chaudron and Forester6 on the decomposition of "FeO," and of Wasserman7 on similarities between the iron-carbon, copper-aluminum, copper-tin, and copper-beryllium systems essentially comprise the field. The iron-nitrogen system, in view of its remarkable similarity to the iron-carbon system, is particularly attractive for the study of eutectoid decomposition. The present investigation is concerned with the study of isothermal transformation, proceeding by the familiar nucleation and growth processes, and of martensitic transformation characteristics of pure iron-nitrogen alloys. The kinetics of transformation and the morphology of the transformation products have been investigated, for these must be the factors determining the properties and behavior of the final product. The Iron-Nitrogen System he binary iron-nitrogen phase diagram has been a matter of considerable disagreement among vari01.1s investigators. However, the phase diagram according to Eisenhut and Kaupp8 and Lehrer10 is now considered essentially correct as reproduced in fig. 1. The important values, 2.35 pct nitrogen and 591°C, for the co-ordinates of the eutectoid point (obtained from this diagram and used in the re- search to be described) were confirmed in a concurrent study of Paranjpe, Cohen, Bever and Floe." The eutectoid decomposition involves the transformation of the ? face-centered cubic interstitial solid solution of nitrogen in iron to the a body-centered cubic interstitial solid solution of nitrogen in iron and the ?' nitride of iron. This nitride is essentially the compound Fe,N; it also possesses a face-centered cubic lattice but a considerably larger one than the ?; the nitrogen atoms in ?' are arranged in an ordered way in the centers of the unit cubes.8,10,11 A martensitic structure has also been reported8,12 in iron-nitrogen alloys and was studied in the research to be described here. Materials and Methods The specimens used in this investigation were prepared by nitriding "pure" iron. This iron was supplied by the Westinghouse Research Laboratories and is the product bearing their trade name "Puron"; it contains about 0.04 wt pct total impurities, the major portion of which is oxygen. Specimens were ribbons several inches long, a tenth of an inch wide, and 0.125 mm thick; this was the

Jan 1, 1951

By F. V. Lenel

INTRODUCTION Two years ago in Chicago a seminar was held on the theory of sintering of pure metal powders As an introduction to this seminar Dr Rhines1 gave an excellent survey of the literature on this subject His method of presentation was to summarize the experimental observations on sintering and from them to develop a composite theory of sintering in which he combined all the important contributions to the theory into one organic whole In contrast to the mechanism of sintering of pure metal powders, which, of course, always takes place in the solid phase, sintering in the presence of a liquid phase, cannot be treated as one unified mechanism, such as the sintering mechanism of pure metals The reason is that there are really several mechanisms depending upon the type of alloy system which is sintered and the field of its constitutional diagram in which the sintering takes place Two mechanisms have been investigated and will be reviewed in this paper In the first mechanism the liquid is present during the entire time while the compacts are at the sintering temperature In other words they are sintered between the liquidus and the solidus of the alloy System and are heterogeneous during the entire sintering cycle The second mechanism applies to alloys in which the liquid phase is formed during the sintering process, but disappears before the sintering process is completed through diffusion and formation of a solid solution These alloys are therefore homogeneous at the end of the sintering cycle This second mechanism is more complicated because of the two stages of sintering, the liquid and the solid, as they may be called It is therefore not surprising that the few detailed investigations of sintering in the presence of a liquid phase have been concerned with heterogeneous sintered alloys, namely the tungsten-nickel-copper alloys, which is the so-called "heavy alloy," and the cemented carbides The mechanism of sintering of these systems is characterized by the fact that theoretical or near theoretical density is attained during sintering, while simultaneously a distinct grain growth takes place through solution of the smallest grains of the solid phase in the liquid phase and reprecipitation on the larger grains In the first part of the survey this sintering mechanism which is called for short the heavy alloy mechanism is treated in detail In the second part of the survey experimental observations for the sintering of homogeneous sintered alloys where the liquid phase disappears before the completion of sintering are discussed Much less systematic work has been done on these alloys to which the commercially important porous bronzes and the iron-nickel-aluminum permanent magnet alloys belong Emphasis will be laid throughout this survey upon the microstructural and density changes during sintering because the sintering mechanism can usually be described directly by these changes Other

Jan 1, 1948

By B. M. Larsen, T. E. Brower

For some years we have been carrying on a rather comprehensive investigation of the occurrence of oxygen in liquid open-hearth steel. This investigation was interrupted by the war emergency and is therefore incomplete, with many questions still answered only partially, if at all; yet it seemed worth while to present a report of progress on this difficult field of research, if for no other reason than to promote discussion and further investigation of this important problem. The significance of such studies depends in large measure upon the accuracy of measurements of oxygen content in liquid steel while it is still in the furnace or as it flows into the ladle, or thence into the mold and there is, as we shall show, good reason for believing that the main source of uncertainty is in the sampling, not in the analytical method as such. The difficulty arises from the fact that any method of sampling is of itself apt to alter the amount of oxygen in solution in the liquid steel, because this oxygen is in a readily reactive condition. On the one hand, being usually present at a concentration appreciably in excess of that corresponding to equilibrium with the carbon then present, it may decrease rapidly in percentage by reaction with carbon and evolution of CO, especially if the liquid metal is in any way shaken or brought in contact with a cooler solid surface. On the other hand, it may increase rapidly by ab- sorption of oxygen from a slag, a furnace atmosphere, or from air. These circumstances, which are inherent in the problem, as well as our conclusion that, despite the considerable amount of careful work already done, there is still no method of sampling liquid steel acceptable as an unquestioned standard, ed us to undertake systematic comparisons of oxygen content of large numbers of samples taken: (I) by a single method at different positions and levels in the bath; (2) at the same place by different sampling methods; and (3) from bath, tapping stream and pouring stream. The different sampling methods yield somewhat different values and there is as yet no way to tell with certainty which is the most accurate. But the general reproducibility and consistency of the results give us some confidence in certain inferences we draw from them: namely, that the "spoon" method of sampling, properly carried out, gives somewhat more consistent results than the "bomb" method, as it has usually been practiced; that, in the bomb method, an aluminum cap is preferable to a steel cap; that the oxygen content of liquid steel in a finished heat is substantially the same all over the bath at the same level, and tends to decrease at lower levels further from the slag interface; also that it tends to decrease, and to decrease erratically, from furnace bath to tapping stream entering the ladle. Accordingly it seemed desirable to report these observations in detail as a first step, so that the reader may judge their significance as a contribution towards solution of the main problem, which is to find a means of pre-2

Jan 1, 1945

By L. K. Oliver, Marshall

The use of model studies for the development of invasion patterns for cycling is .illustrated by model studies obtained with a recently developed apparatus in the solution of actual cycling problems. Introduction Depletion of a gas reservoir by cycling under pressure maintenance may be divided into three general phases. In the first phase, injection of dry gas is used to move all possible wet gas to producing wells prior to breakthrough of appreciable quantities of dry gas into producing wells. In the second phase, injection moves additional wet gas to producing wells while moderate quantities of dry gas are being produced. The third phase consists of production without injection to deplete the commercial gas reserve which remains after the cycling operation. Thus, in the first phase, a portion of the reservoir is invaded by dry gas, and the dry gas usually displaces something less than 100 pct of the wet gas from the invaded portions of the reservoir. The second phase enlarges the invaded portion of the reservoir and, at the same time, increases recovery from that zone invaded by dry gas in the first phase of the cycling operation. The result is an early yield of a substantial quantity of the liquefiable hydrocarbons in the reservoir with a minimum of the retrograde losses which occur in some reservoirs. The overall recovery from such an operation is usually high. The summation of the paths taken by dry gas in a cycling operation can be termed an invasion pattern. The use of electrical models to predict invasion patterns has been the subject of several contributions to the literature.1-3 The results of such model studies as applied to actual cases has been discussed by Kelton4 and Miller and Lents.= Recently, an improved apparatus for conducting potentiometric model studies has been developed, as described by Lee.V he purpose of this paper is to present model studies or invasion patterns obtained with this instrument in the solution of actual cycling problems. The percentage of displacement of wet gas within the invaded portion of the reservoir in cycling, increase in recoveries of wet gas by continuing cycling after dry gas breakthrough, recoveries of wet and dry gas by production after cycling, or economic factors in cycling are beyond the scope of this paper. Discussions which follow will be limited entirely to the development of suitable invasion patterns for cycling under pressure maintenance and the use of model studies therein. Discussion OF Results In using model studies to predict invasion patterns in cycling, some factors which influence the results are the following:

Jan 1, 1948

By Marshall, L. K. Oliver

The use of model studies for the development of invasion patterns for cycling is .illustrated by model studies obtained with a recently developed apparatus in the solution of actual cycling problems. Introduction Depletion of a gas reservoir by cycling under pressure maintenance may be divided into three general phases. In the first phase, injection of dry gas is used to move all possible wet gas to producing wells prior to breakthrough of appreciable quantities of dry gas into producing wells. In the second phase, injection moves additional wet gas to producing wells while moderate quantities of dry gas are being produced. The third phase consists of production without injection to deplete the commercial gas reserve which remains after the cycling operation. Thus, in the first phase, a portion of the reservoir is invaded by dry gas, and the dry gas usually displaces something less than 100 pct of the wet gas from the invaded portions of the reservoir. The second phase enlarges the invaded portion of the reservoir and, at the same time, increases recovery from that zone invaded by dry gas in the first phase of the cycling operation. The result is an early yield of a substantial quantity of the liquefiable hydrocarbons in the reservoir with a minimum of the retrograde losses which occur in some reservoirs. The overall recovery from such an operation is usually high. The summation of the paths taken by dry gas in a cycling operation can be termed an invasion pattern. The use of electrical models to predict invasion patterns has been the subject of several contributions to the literature.1-3 The results of such model studies as applied to actual cases has been discussed by Kelton4 and Miller and Lents.= Recently, an improved apparatus for conducting potentiometric model studies has been developed, as described by Lee.V he purpose of this paper is to present model studies or invasion patterns obtained with this instrument in the solution of actual cycling problems. The percentage of displacement of wet gas within the invaded portion of the reservoir in cycling, increase in recoveries of wet gas by continuing cycling after dry gas breakthrough, recoveries of wet and dry gas by production after cycling, or economic factors in cycling are beyond the scope of this paper. Discussions which follow will be limited entirely to the development of suitable invasion patterns for cycling under pressure maintenance and the use of model studies therein. Discussion OF Results In using model studies to predict invasion patterns in cycling, some factors which influence the results are the following:

Jan 1, 1948

By S. Shapiro, G. Krauss

RECENT investigations1 3 of the products of marten-sitic transformation in Fe-Ni and Fe-Ni-C alloys have made use of light microscopy to describe mar-tensitic fine structure. The application of conventional metallographic techniques to this problem was possible because of the similarity of distributions of parallel striations developed by etching polished surfaces to distributions of transformation twins which are positively identified in thin films by transmission electron microscopy. The surface striations frequently are not well-defined, and could also be due to, for example, rows of etch pits which are not resolved by the light microscope. This note describes the etching effects revealed by examination of surface replicas of mar-tensite in the electron microscope. The application of a replica technique both extends the observations of fine structure made with the light microscope and allows the results of conventional metallography to be used with more confidence. Samples of an Fe-33 wt pct Ni alloy were used for this study because of the detailed knowledge of the fine structure of martensite which has been developed'-4 for alloys of about this composition. Samples transformed to martensite at -120°C, and transformed samples heated to 340°C to effect a small amount of reversal of martensite to austenite, were examined. Surfaces were first prepared for replication by elec-tropolishing in a chromium oxide-acetic acid electrolyte at a current density of 0.1 amp per sq cm and a temperature of 15°C or a perchloric acid-acetic acid electrolyte at a current density of approximately 2 amps per sq cm and a temperature of 15°C. The polished surfaces were then etched for 4 to 7 sec by immersion in a solution of equal parts HC1, HNO,, and H20. Application of the etchant for this period of time produced discrete attack of certain features without loss of resolution due to overlapping of areas most susceptible to etching. The etched surfaces were replicated by 1) preshadowing with Pt-Pd alloy at an angle of 20 to 30 deg, 2) depositing a thin carbon film, and 3) stripping the film and shadowing material by immersion in a 5 pct nital solution. Two types of etching effects were observed by examination of the surface replicas in the electron microscope: l) continuous striations centered at the bottom of long grooves or the tops of pyramidal elevations on the sample surface, and 2) high densities of fine etch pits. Examples of both types of features are shown in Figs. 1 to 4. The striations are in each case continuous and have the same characteristic configurations as do transformation twins in martensite. Fig. 1 shows that the density of grooves decreases toward the edge of a martensite plate and Fig. 2 shows a region where the striations are of varying length. Similar examples of transformation twin arrangements determined by transmission electron microscopy of thinned foils of martensite have been shown in the literature,'~ and, based on these similarities, the striations and their associated grooves or mounds are considered to be evidence for the presence of transformation twins. The transf~rmation twins in martensite are on the order of l00 A thick, much too fine for resolution by the light microscope. It appears that orientation-dependent etching of the matrix martensite about the twins results in grooves or surface elevations which

Jan 1, 1967

By W. A. Koehler, M. E. Hinkle

THE oxidation of pyrites and marcasite in coal-mine strata to produce discolored acid mine drainage has long been explained by chemical reactions occurring in three stages: 1. The iron sulphide minerals are oxidized by air in the presence of water to produce a nearly colorless solution of ferrous (iron) sulphate and some sulphuric acid. 2, The ferrous sulphate and part of the sulphuric acid combine with additional oxygen to form ferric (iron) sulphate. 3. The ferric sulphate hydrolyzes to form a reddish-brown precipitate and additional sulphuric acid. Nevertheless, chemical data alone are not sufficient to explain all observed facts. The first stage seems to proceed more slowly in the chemical laboratory than in nature. The second and third stages normally occur to a marked extent within a few days with raw mine water. However, the visible discoloration that characterizes these latter stages will not develop for months if the mine water is sterilized. By means of bacteriological techniques, two organisms have been isolated from acid coal-mine drainage. These are believed to have a part in promoting the chemical reactions summarized above. One organism is considered to be Thio-6aciZZus thiooxidans, which is known to be able to convert elementary sulphur or sodium thiosulphate to sulphuric acid. Its relation to the formation of acid mine drainage has not Yet been established. Apparently it does not Promote the oxidation of ferrous iron compounds in mine drainage to the ferric state. The second organism has not been identified by name but is described as " Gram negative, non-spore-forming rods approximately 0.4 micron wide by 0.8 to 1.0 micron long." A pure culture of this when added to sterile mine water will cause the latter to become amber and develop the typical rusty precipitate. However, it has not been found to convert sulphur compounds to sulphuric acid. Further research is planned to determine whether or not these microorganisms play a significant part in the first stage of oxidation whereby pyrites and marcasite minerals go into solution. Some of the conditions found in abandoned sections of coal mines, such as a reduced Percentage of Oxygen and increased percentage of carboll 'dioxide in the air, as well as the existing temperature and acidity ranges, will be tolerated by and may even be favorable to these organisms. Acid Coal Mine Drainage Acid coal mine drainage has been the concern of coal mine operators, industrialists, sportsmen and public officials for many years. The amount of acid flowing into our streams in the coal-producing areas varies considerably from mine to mine and from

Jan 1, 1949

By Mohamed Mortada

A practical analytical method is developed in this paper which provides the practicing reservoir engineer with a handy method for analyzing oilfield interference problems. The procedure employed entails the principle of superposition of individual eflects. A set of charts has been developed and can be used to evaluate the individual effects. The charts represent non-steady state pressure distribution in an extensive aquifer due to a constant rate of production from an oilfield which can be approximated by circular geometry; they are constructed from solutions to the diffusivity equation considering a circular sink as distinguished from a point sink. The solutions are obtained partially from mathenlatical considerations and partially from analog and digital computations. By virtue of the method of images, the charts can be used also to treat the case of production near a fault. In addition, provisions are made for treating oil fields, which are produced by partial water-drive. Treating an actual field case is deferred to a subyequent writing; however, illustrative example is presented to demonstrate the method of application. The pressure distribution in linear and limited radial aquifers is currently under study. INTRODUCTION With the increasing difficulty of discovering new oil reserves, attention is necessarily focused on the efficient development and production of existing reservoirs. Efficient production depends on the availability of reliable means for predicting the pressure-production behavior of oil fields. The prediction is usually performed by analytical methods or computers. Analytical methods are often limited to systems which can be approximated by simple geometry. However, analytical methods have the distinct advantage of being readily performed without special equipment. Analog and digital computers lend themselves to a variety of problems, but are not always locally available and consequently their use is limited. One particular situation in which analytical techniques are needed involves studies of multiple, water-drive oil fields sharing a common aquifer. Such oil fields are in hydrodynamic communication. Therefore, production from any of the oil fields is accompanied by a pressure decline which is transmitted through the aquifer to the other oil fields and manifested as pressure interference. The rate of propagation of the pressure decline is such that the pressure may be significantly reduced many miles away from a producing pool. An example of pressure interference is found in the Woodbine formation in East Texas. There. a dozen or more pools, including several of major size, draw on the Woodbine formation for water drive. The pressure in the water-bearing portion of the formation has been significantly reduced over an area of several thousand square miles. This reduction of pressure has been such that when the Hawkins pool was discovered in 1940, the pressure in it had already been reduced 280 psi below the initial value in the aquifer. This resulted from prior production from other Woodbine sand pools, including, in particular, the East Texas field some 20 miles to the east of Hawkins.' The above example indicates that the interference effect can be significant and should be taken into con-

Jan 1, 1956

By Ronald W. Klusman, Erik B. Nelson

The Front Range portion of the Colorado Mineral Belt is an extensive area of mineralization with mining activity dating from 1859 with the discovery of large gold deposits. After an initial boom period and gradual diminishing production, present activity is restricted to molybdenum in Clear Creek County, uranium in Jefferson County, and several small operations extracting gold and silver in Clear Creek and Gilpin Counties. Gold and silver have dominated the production in the Front Range, though the complex mineralization created milling and smelting problems and it is postulated that considerable amounts of precious metals remain in the mine dumps. This area is plagued by a severe mine drainage problem, with Clear Creek most impacted by many draining mines and tailings in the basin. Boyles et al. Moran and Wentz, Wentz, Wildeman et al., have examined various aspects of the impact of mine drain¬age in the Clear Creek basin. The primary objective of this study was to collect data on the tailings, drainages, and leaching experiments in order to make preliminary suggestions for reducing the impact while recovering metal values to offset treatment costs. A variety of leaching experiments were performed on tailings from the Nevada Gulch area in the Central City mining district. Leachings were performed in vertical tubes indoors and wooden boxes exposed to the outside environment. In the leaching experiments, the leaching solution, grain size, and residence times were varied, while forced aeration was used in some experiments. Bacterial nutrient 9K° and mine drainage were used in some of the experiments. A total of 14 additional tailings samples were analyzed for base and precious metals. The composition of the mine drainage and tailings used in the leaching experiments, as well as data on the additional samples are shown in [Table 1]. Leachate samples were taken periodically for analysis until compositions leveled off. Results and Discussion Leaching with distilled water was used as a control and best illustrates the basic behavior of the leaching process for zinc in a vertical tube [(Fig. 1)]. More acidic leachings increased concentrations of metals as did smaller grain sizes, though the time required increased significantly. Mine drainage with its high concentration of dissolved iron sometimes decreased the heavy-metal concentration in the leachate due to oxidation of Fe 2 and precipitation of Fe(OH)9 which absorbs some of the dissolved heavy metals. In the larger scale experiment carried out in the simulated leaching pad, substantial concentrations of metals were attained in the final leachate after one month. In this experiment the leachate was not recycled, but allowed to saturate the tailings continually with evaporation loss made up by additions of Quartz Hill drainage and nutrient 9K. The concentration of the metals in the leachate and the increase over the input solution are given in [Table 2]. Heap leaching of low-grade copper and uranium ores is successfully carried out in many districts, enhanced by the metabolism of autotrophic bacteria of the Thiobacillus-Ferrobacillus group. These ubiquitous organisms enhance metal leaching, and general aspects of heap leaching are discussed by Malouf, Trudinger, Pings, and Duncan et al. Conclusions and Recommendations Returning to the primary objective, how to reduce the mine drainage impact and recover metal values, we need to consider how the data may suggest avenues toward this objective. Boyles, et al., considered various

Jan 1, 1977

By R. M. Waterstrat

The phase VPt has been reported to have a crystal structure of the B19 (AuCd) type at low temperatures.''' A recent investigation3 has indicated that this phase forms by an ordering reaction from the disordered fcc Pt(V) solid solution which is stable at high temperatures. olander4 has shown that there exists a close structural relationship between the orthorhombic B19 structure and a fcc structure possessing the L1 , (CuAu) type of atomic ordering. One may derive the B19 structure by a shear-like displacement of the atoms in the (002) plane of the ordered fcc lattice along the (010) direction through a distance equal to one eighth of the unit cell dimension, see Fig. 1, followed by an orthorhombic distor; tion of the cube axes such that a = 2.693A. h = 4.413A. and c =4.767A (estimated uncertainty 0.005A). Filings of this phase were produced by grinding a VPt alloy having the B19 structure with a diamond dental grinding disc. When these filings were subjected to X-ray diffraction examination, a pattern of a severely cold-worked fcc structure was obtained. higher solution temperature used (1200 C) or to a much lower oxygen pressure than he reported, due to transfer through many bends and tubes in his complicated apparatus. An interesting observation was made when an oxygen addition was attempted in a cylindrical sample of columbium in the cold worked condition rather than in the annealed condition. The interior of the sample re-crystallized during the oxygen addition at 900°C. The periphery, however. (1 mm) did not recrystallize. A similar sample without oxygen recrystallized throughout the entire cross section. It appears that the re-crystallization is hindered by interstitial oxygen. Presumably, the interior recrystallized before appreciable oxygen could diffuse into the core. This work was supported by the United States Atomic Energy Commission. When the filings were annealed in a high vacuum furnace for 15 min at 110O0C, however. they returned to the B19 structure perhaps as a result of reordering. Subsequent less-severe cold-working of these filings by grinding in a hardened steel mortar and pestle at room temperature produced a transformation into a cold-worked L1, structure which was slightly tetragonal. Thus it appears that the degree of deformation may influence the final structure. Considerable line-broadening was observed in X-ray diffraction patterns obtained from the cold-worked filings and therefore no attempt was made to obtain accurate lattice parameters. Vacuum annealing treatments at 1100'C intended

Jan 1, 1970

By P. van Meurs

This paper describes a technique which permits visual observation of oil displacement processes througlrout the interior of a porous structure as thick as 2 in. A model having glass walls is filled with finely powdered glass. Such a model becomes completely transparent if the powdered glass pack is saturated with an oil having the same refractive index as the glass. When water or gar, with a refractive index different from that of the oil (glass) is injected, the model becomes opaque in the space occupied by the water (gar). visual observation and photography of these displacement processes are thus rendered possible. The following processes have been studied: (I) displacement of oil by water (linear drive) in a homo-geneous formation and in a stratified formation, (2) water flooding (five-spot well pattern), (3) solution gas-drive process, and (4) oil-bank formation. INTRODUCTION Most of the scaled model experiments heretofore carried out in the Koninklijke/Shell Laboratorium, Amsterdam, have been done in steel containers, in which oil-saturated sand packs represented the oil-bearing formation. In such experiments, for instance those on the displacement of oil by water, the cumulative oil production was measured as a function of the cumulative water injection. In order to interpret the measured production data, a need has for some time been felt for a means of observing visually what happens in the course of such experiments. Some information of this kind was obtained earlier by observing the water-oil distribution in various cross sections of the sand after the conclusion of the experiment.' However, the technique used did not guarantee that the fluid distribution remained undisturbed. Moreover, the procedure was somewhat elaborate and the information obtained limited. Therefore a new technique has been developed, which is described below. DESCRIPTION OF EXPERIMENTAL TECHNIQUE AND APPARATUS Glass models simulating part of an oil reservoir are filled with ground Pyrex glass of a specific grain size, representing the porous structure of the prototype. Before an experiment is started, the porous formation has to be saturated completely with an oil having exactly the same refractive index as the Pyrex glass powder. All light-scattering surfaces of the glass grains become invisible and the formation is then transparent. If the oil is displaced by another fluid (e.g. by water in a water-drive experiment, or by gas liberated from the oil in a solution gas-drive experiment) the formation becomes opaque in the region where the oil is expelled from the rock.* The back of the apparatus is painted black and illumination is from the front; therefore, in the photographs of the experiments, the oil-bearing formation appears black, whereas the water- or gas-invaded areas are white.

Jan 1, 1958

By T. M. Geffen, R. E. Gladfelter

Lipson1 has recently presented a technical note wherein theoretical considerations were used to demonstrate. that the adsorption us saturation relation for a linear absorption method is not necessarily a single valued function of saturation.1 It was concluded that the absorption us saturation relationship is subject to the same hysteretic effect as is the flow behavior between the drainage and imbibition systems. It is the purpose of this note to show, by experimental results, that for the manner in which fluids are distributed in porous materials during fluid flow, the relative X-ray absorption us saturation relationship is single-valued regardless of the saturation history. The design of the apparatus used to measure relative X-ray absorption of cores undergoing fluid flow tests is similar to that described by Morgan, McDowell and Doty. A few modifications have been incorporated in the design to increase sensitivity and simplicity of measurement. The sensitivity is such that for usual types of cores a recording pen movement of approximately 12 linear in. is occasioned between the recording of the core dry and when it is completely full of an absorbing liquid, a solution of approximately five per cent by volume of iodo-benzene in a close-cut hydrocarbon fraction, or a solution of 50,000 ppm sodium iodide in water. Two types of experiments were conducted, one in which the liquid was inside the core, and the other with the liquid outside the core. Tests with the liquid inside the core were run to cover the saturation range encountered in both the drainage (gas drive) and imbibition (liquid flood) flow systems. It is pointed out that the same core was used, but the tests were conducted at different times with the recording mechanism balanced at a different position. Therefore, the absolute values of relative X-ray intensity at any saturation are not the same in each test. In the second type of test the same core was used, but this time its pore space cmtained only gas, and various thicknesses of oil contained in plastic cells were placed in front of the dry core. As before. the relative X-ray ah- sorption was measured and compared to the quantity of oil in front of the core. The arrangement of the fluids with respect to the path of X-rays in these two types of tests represent fluid distributions of a wider difference than can be expected between that established in a core just due to imbibition and drainage saturation flow histories. Thus any deviation from a straight line relationship of the log of the relative X-ray intensity us saturation calibration should be readily apparent. Results of the laboratory tests are given in Fig. 1. A schematic diagram showing the position of the fluids with respect to the path of the X-ray beam is given for the two cases investigated. In the case where the oil existed outside the core (Case B), the log of the X-ray intensity (log, I/I,) is related directly to the cell thickness (amount of oil in X-ray beam path). This correlation is in full agreement with X-ray theory. In the case where the oil or water existed inside the core (Case A) which covers both drainage and imbibition types of flow processes, again the relationship between absorption and saturation (amount of oil in X-ray beam path

Jan 1, 1952

By C. M. Wayman, G. R. Srinivasan

A metallographic study of the isothermal products formed between 750° and 285°C was made in an Fe-7.9 wt pct Cr-1.11 wt pct C alloy, and a time-temperature-transformation diagram was determined. The study shows that the austenite decomposes into three different products: pearlite above 540°C, ferrite and carbide between 540° and 300°C, and lenticular bainite below 300°C. No upper bainite forms in this alloy. The results are discussed in terms of carbon diffusion models for upper bainite formation. AUSTENITE transforms into several products depending on the temperature, composition, and rate of cooling, and the various transformation products have been a source of controversy for a long time. Since the classical study of Davenport and ~ain' extensive work has been carried out. The present study concerns the isothermal transformations in an alloy which was used for a detailed investigation of bainite crystallography and provides information supplementary to the work of Lyman and Troiano who studied austenite decomposition in steels containing 1 pct C and varying amounts of chromium. Their work showed that increasing the amount of chromium in high-carbon steels had the effect of depressing the B, temperature and of shifting the TTT curves to longer times and lower temperatures. They further found that if the chromium content is increased in a 1 pct steel to about 9 pct no bainite would form even after a period of 100 days. However, a preliminary investigation by the present authors showed that bainite plates do form in steels containing about 8 pct Cr and 1 pct C. In view of this and some results from a thin-foil electron microscope investigation of the bainite formed in the present alloy: it was considered desirable to investigate the other isothermal products as well. EXPERIMENTAL PROCEDURE The alloy used in the present investigation was obtained from a triply vacuum-melted ingot prepared from high-purity materials. Chemical analysis for the alloy verified the composition to be Fe-7.9 wt pct Cr-1.11 wt pct C. Metallographic observations were made on i by i by « in. specimens which were aus-tenitized at 12 50°C for 50 to 60 hr in evacuated quartz capsules and then water-quenched. Since the M, temperature for this alloy is below room temperature, the homogenizing treatment produced a completely austenitic structure consisting of very coarse austenite grains (ASTM #0-1). Several samples of the austenitized specimens were metallographically prepared and observed for any proeutectoid carbide separation. It was found that all the carbon was in solution. The water-quenched specimens were upquenched and given isothermal treatments at temperatures between 285" and 750°C for varying periods in molten salt or lead baths. The specimens were then water-quenched, and those showing less than 5 pct transformation were used for plotting the beginning of the austenite decomposition. To ensure the removal of the disturbed layer, the mechanically prepared specimens were electropolished in a 1:6 HzS04, CHSOH solution for 10 to 15 sec at 20 v. Final polishing was done with a vibratory polisher using 0.05-p alumina. Various etchants including nital, ferric chloride, and hot ferricyanide (Murakami's reagent) were used to bring out details in the different transformation products. The ferricyanide etch was used whenever the preferential etching of carbides was desired.

Jan 1, 1969

By G. R. Countryman, G. H. Thomas, I. Fatt

Procedures are described for scaling up turbulent friction pressure drops of inelastic fluids and laminar friction pressure drops of inelastic/elastic fluids in circular ducts. The laminar scale-up calculation method does not require the use of arbitrarily defined flow models, and can be performed directly from laminar capillary viscometry data, or by means of a numerical solution of the integral equation for Poiseuille flow, inputing true shear rate-shearing stress data from other simple shearing experiments. e.g. Couette and plane Poiseuille flows. The turbulent scale up procedure, based on the Dodge-Metzner correlation for inelastic fluids, requires evaluating the characteristic rheological parameters at the existing wall stress under laminar flow conditions. Since the wall stress is the quantity sought in a pipe flow scale-up problem, a trial-and-err or solution is indicated, and therefore a calculation method has been developed and programmed for a medium-size magnetic-drum-memory digital computer. Laminar flow data from other somces may also be adapted to this turbulent scale-upmetbod for inelastic fluids. Comparisons between predicted and experimentally observed friction losses for generalized Reynolds numbers ranging from 3 — 32.000 indicate an error band width of less than 10 per cent in circular tubes ranging in size from 0.5 to 1.89 in. in diameter. INTRODUCTION Considerable effort has been devoted to the problem of establishing an accurate procedure for predicting the laminar and turbulent flow behavior of non-Newtonian materials in pipes from data obtained with small scale laboratory or pilot plant equipment, as evidenced by the variety of reviews on the subject.1-3 Although there does not appear to be a universally accepted scale-up method for laminar flow, the various methods currently employed can be divided into two principal categories depending upon whether a functional relationship between shear rate and shearing stress is assumed, or whether a generalized correlation is adopted. The methods of Hedstrom4 and of Weltmann are typical of the first category, while the generalized correlation of Metzner and Reed6 illustrates the second category. Under appropriate conditions either approach yields a reasonably satisfactory description of laminar flow behavior. In contrast, the prediction of non-Newtonian transitional and turbulent friction losses is much more complex. For example, certain types of materials have been observed to sustain laminar flow at much higher flow rates than Newtonian liquids. When turbulence does develop, the level of agitation is damped to such an extent that the friction factor is lower than that of the original low viscosity Newtonian medium. Extremely broad transition regions and "diameter effects" have also been noted in the turbulent flow of certain chemically complex materials.' Aside from the latter complications, which are attributed in part to viscoelasticity, the existence of a variety of scale-up procedures for predicting transitional and turbulent friction losses is due principally to the chioce of viscosity parameter used in the definition of the Reynolds number. In contrast, Dodge and Metzner have demonstrated that the friction factorReynolds number relationship for inelastic fluids can be satisfactorily generalized provided the fluid property parameters are evaluated at the existing wall shearing stress.* However, the quantity usually sought in a pipe flow scale-up problem is the wall stress, and hence a trial-and-error procedure is required when dealing with non-power law materials. In this report we discuss two calculation methods: (1) for determining the wall stress, and hence the friction pressure drop, for inelastic fluids under conditions of turbulent flow by means of an iterative procedure, and (2) for predicting laminar friction pressure drops without recourse to arbitrarily defined flow models.

By R. Taggart, D. H. Polonis, J. C. McMillan

Thin foil electron microscopy techniques have been used to study the micros tructure of a Ti- 7.5 wt pct vanadium alloy in the quenched and aged cond_itions. Selected area diffraction has identified a (1011) twinning mode accompanying the martens ite t9.an.sfo?rn~ation. Precipitation of the 0 phase during the aging of quenched alloys has been obsevced to occuv in the form of plates and needles with preferential growth along the (1120) direction in the a' matrix. In the present work, the micro structures of quenched and aged alloys of the 0 isomorphous Ti-V system have been investigated by means of thin-foil electron-microscopy techniques. Most of the previous studies of martensitic phases in titanium-base alloys have utilized optical microscopy and X-ray diffraction techniques. The application of transmission electron microscopy is more recent, and only a few such studies have been reported.1-5 This paper is concerned particularly with the crystallographic nature of substructures formed in the martensitic a' plates. The early stages of aging or tempering have also been examined to determine the modes of precipitation from the martensitic solid solutions. Such information is essential in studying strengthening mechanisms and in determining the feasibility of high-strength rnartensitic alloys based on titanium. Liu and Margolin6 reported several types of substructures within the martensitic plates of quenched Ti-Mn alloys. It was later suggested by Liu7 that the structure of martensitic plates might be very complex and not single crystals as normally assumed. The sub-markings could not be identified with the two possible habit-plane orientations {334}ß and {344}ß, and it was not positively determined whether they are associated with mechanical twinning. The recent studies by Armitage5 on titanium martensites in a variety of commercial alloys have indicated that twinning does not generally accompany the transformation. This observation is in accordance with the Mackenzie and Bowles model for the transformation in pure titanium8 which suggests that twinning is not to be expected. However, a number of other recent investigators have reported twinlike substructures in the martensitic plates of several titanium systems including commercia1 titanium,2,3 Ti-Cu,5,9 Ti-Ta,1 and the commercial alloy Ti-8A1-1Mo-1V. Blackburn* has reported that the structure of quenched Ti-8A1-1Mo-1V depends on the prior solution temperature. He identified two types of martensitic structures, one of which is described as a heavily faulted hcp or twinned fcc structure and the other an hcp structure with a high internal dislocation density. The latter type exhibited some twinning with a (1011) twin plane. EXPERIMENTAL PROCEDURES AND RESULTS The alloy used in the present work was a 7.5 wt pct V alloy that was prepared by conventional arc-melting techniques. This alloy composition was selected

Jan 1, 1968

By W. B. Gogarty

With flow of non-Newtonian fluids in porous media, effective viscosities are needed for use in the Darcy equation. These viscosities depend on the rock parameters and flowing conditions. In this investigation, rheological and flow results were correlated to develop an expression for calculating effective viscosities. Surfactant-stabilized dispersions of water in hydrocarbon were used with consolidated sandstone cores of different permeabilities. The average shear rate in a core was related to the permeability and porosity of the core and the frontal velocity through the core. By using the correlation obtained for determining effective viscosity, experimental and theoretical values were compared for each fluid system by determining average and maximum errors. For the fluid system showing the largest average error, the correlation fit 38 experimental points with an average and maximum percentage error of 4.3 and 14.8, respectively. For the fluid system showing the least error, average and maximum percentage errors of 1.8 and 4.3, respectively, were calculated using 29 experimental points. INTRODUCTION Use of non-Newtonian fluids in the petroleum industry is not new. Fluids of this type have been used for many years as fracturing agents and drilling muds. Recently, attention has focused on the use of high molecular weight polymer solutions for secondary recovery. Results have been reported on studies relating to the flow behavior of polymer solutions in porous media.1-4 Each study gives the viscosity in the Darcy equation as a function of the rheological properties of the fluid, the characteristics of the porous medium and the pressure gradient. The functional forms of the reported expressions differ somewhat in each study. The first three studies used unconsolidated porous media while the fourth used a single consolidated core. Because of the limited information available on the flow of non-Newtonian fluids in porous media, further investigation was undertaken in this area. We selected non-Newtonian fluids that did not contain high molecular weight polymers in order to minimize core plugging. The over-all objective was to gain a better understanding of the flow behavior of non-Newtonian fluids in consolidated porous media. Specifically, our goal was to determine the relationship between the average shear rate in a core and the frontal velocity. Because of this goal, it was necessary to determine the effect of permeability on the shear rate-frontal velocity relationship. We wanted to replace the viscosity in the Darcy equation with an expression relating to the average shear rate in the core and the rheological properties of the non-Newtonian fluid. THEORY For a time-independent, non-Newtonian fluid, the apparent viscosity is a function of the shear rate. This relationship is given by µ = F(v')...........(1) With Eq. 1, a single value of shear rate determines the apparent viscosity at that shear rate. With flow in porous media, a spectrum of shear rates occurs at any average throughput. An average shear rate v' can be used to represent the spectrum of shear rates that exists within the core. By using v' and the rheological data given by Eq. 1, an effective viscosity is determined for the flowing fluid. If v' is the correct average, µe becomes the appropriate viscosity for use in the Darcy equation. Under these conditions, flow rate-pressure drop relationships can be determined for non-Newtonian fluids. HOW the correct average shear rate might be related to the frontal velocity through the core and the characteristics of the porous media will now be considered. Later, the experimental data are presented that indicate the validity of these

By L. J. Dijkstra, R. J. Sladek

IN earlier work the effect of manganese on the general behavior of nitrogen in iron was the subject of a careful examination by Fast.' Part of the investigation was made, in collaboration with one of the present authors (L.J.D.), by using the internal friction method. This technique, which has been described elsewhere,' showed some significant changes in the properties of Fe-N alloys by the addition of a small amount of manganese namely: 1—Under standard conditions the maximum of the nitrogen peak in pure iron appears around 20 °C and the half width is about 27 °C. By addition of 0.5 atomic pct Mn a general broadening of the internal friction peak occurs. The half width is increased by about 9°C. Moreover, a shift of the maximum of about 5°C toward a higher temperature takes place, Fig. 2. 2—The precipitation of nitrogen from the supersaturated solution, measured, e.g., at 200 °C, was inhibited by the addition of the amount of manganese given in effect 1. The broadening of the nitrogen peak was confirmed in more recent work3 on samples which were prepared from Westinghouse Puron iron. The effect of manganese on the rate of precipitation, however, was much less striking than in the earlier work' based on Philips high purity iron. Theory To explain the first change in properties just referred to, effect 1, the following two assumptions were made:' First, every manganese atom in sub-stitutional solid solution creates around it six interstices located between an iron and a manganese atom, as is evident from Fig. 1. These interstices, conveniently called Fe-Mn interstices, have for nitrogen a free energy level which is AG* lower than the normal Fe-Fe interstices between two iron atoms. For such low concentrations of manganese as 0.5 atomic pct, the possibility that two manganese atoms will be nearest neighbors can be disregarded. Second, it is assumed that in addition to the normal relaxation time TFe at least one new relaxation time, Mn, Fe, enters in the phenomena which is associated with the elementary diffusion jumps between a Fe-Mn interstice and an adjacent Fe-Fe interstice. Fig. 1 gives schematically the free energy for a nitrogen atom as a function of its position along the line ABC. A tentative analysis of the nitrogen peak in a 0.5 pct Fe-Mn alloy based on these assumptions has been made in Fig. 2. The dotted curve with a maximum at 22°C is caused by jumps between Fe-Fe interstices, the dotted curve with maximum at 32°C by jumps between an Fe-Mn and an Fe-Fe interstice. The two effects added together give the dash-dot internal friction curve for the alloy. In the following these two components will be referred to as the normal peak at 22°C and the abnormal one. (The small secondary peak at

Jan 1, 1954

By M. A. Dayananda

Based on the Kirkendall frame of reference, a method is proposed for the determination of atomic mobilities of all the diffusing species in a multicorn-ponent system with a single diffusion couple. The method is based on an atomic mobility model developed on the concept of negligible interactions among the intrinsic fluxes. It is shown in the model that mobilities can be obtained directly from the cumulative intrinsic fluxes past the Kirkendall interface. The proposed method replaces the need for a prior determination of interdiffusion coefficients far the calculation of mobilities. Relations between intrinsic diffusion coefficients and mobilities are derived and the mobility calculations are illustrated with diffusion data in Cu-Zn-Mn alloys at 850°C. ThE concept of "intrinsic flux" with respect to a fixed lattice was introduced "i Darken1 to explain toa Kirkendall effect2 demonstrated by the motion of inert markers during isothermal diffusion in single-phase binary solid solutions. Based on this concept, intrinsic diffusion studies have been made in various binary metallic systems3,4 employing such a lattice frame of reference, commonly referred to as the Kirkendall interface. Similar approaches, both theoretical and experimental, have been presented5"10 to study intrinsic diffusion in multicomponent systems. Based on the direct integration of Fick's law extended to multicomponent diffusion, Philibert and Guy8 proposed a method for the determination of intrinsic diffusion coefficients. For an n-component system, this procedure requires an experimental study with (n — 1) diffusion couples, all having their Kirkendall interfaces at the same compositio;, where n(n — 1) intrinsic diffusion coefficients are defined. This technique has been employed for ternary diffusion studies by Dayananda and Grace" and Guy and Leroy.11 A different approach is recommended by Ziebold and Cooper,12 who have derived relations between interdiffusion coefficients and atomic mobilities employing fluxes referred to the local center of volume. Their analysis is based on the simplifying assumption of negligible interactions among intrinsic fluxes. This assumption has been considered satisfactory for dilute solutions.5"7 The use of this analysis for the calculation of mobilities requires an initial determination of interdiffusion coefficients with a set of diffusion couples having intersecting diffusion paths. It is the purpose of this paper to propose a method that would permit a direct determination of mobilities of all components of a multicomponent system from a single diffusion couple. This method is based on a mo- bility model developed with diffusion fluxes referred directly to the Kirkendall interface, generally identified by inert markers. gen erall, like that of Ziebold and Cooper,12 employs the simplifying assumption that the flux of each component relative to a fixed lattice is caused only by the driving force of its own chemical potential gradient. THE KIRKENDALL INTERFACE Inert markers are employed in diffusion couples to locate experimentally the position of the Kirkendall interface. They are initially placed at the weld interface for "sandwich" couples, or at the original vapor-solid interface for vapor-solid couples. Studies of marker motion in binary systems3'4 with both types of couples indicate that markers remain in a plane of constant composition and move with this plane para-bolically with time. Parabolic marker movements were also observed in ternary Cu-Zn-Mn couples by Dayananda and Grace.10 It is reasonable to expect a similar marker behavior even for diffusion couples with a higher number of components.

Jan 1, 1969

By D. H. Woodard

One of the principal uses of polarized light in metallurgy is to show the granular structure of metals by contrasting reflections. This use is confined largely to anisotropic metals, such as beryllium, tin, magnesium, and the like.1 Recently, Hone and Pearson2 have extended the use of polarized light to include the isotropic metal aluminum. This was made possible by the formation of an anodic film that was optically anisotropic and that had a fixed and reproducible structural relationship to the grains in the substrata. With their method, it was possible to indicate localized textures in annealed aluminum sheet. In the course of an investigation of plastic deformation at the National Bureau of Standards, it was found that the isotropic single phase alloy Monel could be made optically anisotropic by treatment with the usual Monel contrast etchant. Experiments soon showed that dif- , ferences in orientation could be detected easily. Previous investigations involving the use of polarized light have been restricted to annealed metals. In this paper it will be shown that inhomo-geneous plastic deformation which results in lattice bending and development of deformation bands, experienced by individual grains in polycrystalline Monel, is revealed in the microstruc-ture. This interpretation of the micro-structure was confirmed by a study of slip lines formed after prior plastic strain. Materials and Procedure The material used was Monel, the chemical composition of which was C—0.17 pet, Mn—1.28 pet, Fe—1.61 pet, S—0.009 pet, Si—0.17 pet, Cu— 30.70 pet, Ni—66.04 pet. The material was divided into 2 lots which were treated as follows: Lot A was heated at 1700°F for 3 hr to produce a fully annealed, coarse grained structure. Lot B was heated at 1400°F for 1 hr to produce a close approximation of a fully annealed structure without appreciable increase in the grain size of the original material. After each of these heat treatments the material was cooled in air. Samples for metallographic examination were cut from tensile and compression test specimens and were prepared by grinding on lead-tin laps, followed by electrolytic polishing, † Etching and the development of ridges were avoided by keeping the voltage above 3.8 and by preventing contamination of the polishing solution with water. Monel, when polished and treated with most etchants, is optically isotropic. However, when given a light etch for about 4 sec with the Monel contrast solution the surface of the metal becomes optically active. The microstructure when observed under crossed nicols* appears different from that viewed by ordinary light. This is shown by a comparison of micrographs made of the same area of a plastically deformed specimen using polarized light (Fig la) and white light (Fig 16). If Monel, which has been lightly treated with the contrast etchant, is slightly deformed by compression, rectangular figures are apparent over the specimen. However, within too short a period to be photographed, these rectangles become circular, probably because of surface tension effects within the etched film. The two observations,

Jan 1, 1950

By Charles R. Simcoe

The stress-strain curves in the microyield region for various Fe-C solid solutions shown by Davies and Ku are typical examples of parabolic curves defined by the expression a = kEn 111 These data, when replotted on log-log coordinates, as shown in Fig. 9, exhibit three essentially parallel straight lines. It is apparent that carbon increases the flow stresses, but does not affect the exponent n. In other words, the only factor in Eq. [1] affected by in in carbon content is the constant k. As Eq. [1] is written k is the stress at a strain of 1.0. This is unsatisfactory for examining data in the microyield region. Therefore, the equation can be altered to the form: to permit the use of the authors' microyield stress at a strain of 10-6 as k. Extrapolating the curves in Fig. 9 to a strain of 10-6 gives stress values of 2000, 3200, and 5400 psi for 0.008, 0.014, and 0.02 pct C, respectively. These values do not agree exactly with the authors' measured values, but this will not affect the following discussion. The effect of carbon content on the slopes of the stress-strain curves shown in Fig. 2 of the paper by Davies and Ku can be analyzed by differentiating Eq. [2] with respect to strain. Thus: where n is always less than 1.0. Since n is essen- tially constant as a function of carbon content for the data under discussion, the slopes of the stress-strain curves depend only on k and E. If the slopes are examined at various selected Plastic strains. i.e., 10-6, 10-5, and so forth, it follows from Eq. [3] that the dif-ferent slopes for the different carbon contents depend only on the different values of ke=10-6. Thus, the larger ke=10-6, the steeper the linear stress-strain curve will rise with increasing plastic strain. This

Jan 1, 1969