Search Documents

By J. C. Uy, A. A. Burr

IN the primary solid solutions of zirconium-base alloys, there is a striking regularity of the effect of solute valence on the stabilization of the allotropic phases.1 The valences derived by pauling2 are for elements as they are bonded in the solid metallic state. Effects of variations in isotopes, alloying elements, and allotropes on their valences are difficult to determine and such data are presently unavailable. Pauling's values are somewhat empirical and approximate, but if some definite correlations can be found between those values and experimental observations, this will lend support to the tacit assumption that the possible variations in valence mentioned above are small. Pauling has amassed a large amount of evidence of such correlations. It is the purpose of this technical note to show another application of the Pauling valences and to offer a possible explanation for this observation. The relationship between the Pauling metallic valence of the solute and the stabilization of allotropic phases in zirconium is shown in Table I, which has been compiled from available data in the literature3 plus the results of work done at Rens-selaer Polvtechnic Institute.' The chemical valences are included for comparison. It can be seen that a solute whose metallic valence is lower than that of the solvent tends to stabilize the a phase while one whose metallic valence is higher than that of the solvent tends to stabilize the 0 phase. It should be noted that, inasmuch as the Pauling valences are periodic with atomic number, this is tantamount to saying that the elements in groups I-A, 11-A, III-A, III-B, IV-B, V-B, and VI-B are a stabilizers while those in groups IV-A, V-A, VI-A, VII-A, VIII-A, I-B, and 11-B are ß stabilizers. The chemical valences do not show such consistency. Although the zirconium-rich end of the Zr-Au diagram is not available, it call be expected that gold, having a metallic valence of 5.56, would stabilize the ß phase. At absolute zero, the Fermi energy level is the criterion of equilibrium, i.e., the structure having the lower Fermi level will be more stable. Conse- quently, allotropic transformation occurs in a metal when thermal excitation raises the Fermi level to a point at which the atoms can be better accomodated by a different structure which yields a lower Fermi level.4-6 Thus in allotropic transformation, a change in structure occurs as a result of the change in the energies of the bonding electrons. Since the Pauling valence is the number of bonding electrons per atom, and these are the only electrons whose energies are affected by thermal excitation,* it can be inferred that the introduction of a solute which has a higher Pauling valence than that of the solvent raises the initial Fermi level; consequently, the transformation temperature is lowered. The converse is also true. The fact that at the transformation temperatures this statement is still fairly valid implies that the contribution due to the difference in specific heat terms of the two allotropes is comparatively small.

Jan 1, 1962

Sec. 1. This Division shall be known as the Institute of Metals Division of the American Institute of Mining and Metallurgical Engineers. Sec. 2. The object of the Division shall be to furnish a medium of cooperation between those interested in the metallurgy, fabrication and uses of the nonferrous metals and their alloys; to represent the A. I. M. E. in so far as nonferrous metallurgy is concerned, within the rights given in A. I. M. E. By-law XI., Sec. 1, and not inconsistent with the Constitution and By-laws of the A. I. M. E.; to hold meetings for social intercourse and the discussion of nonferrous metallurgy; to stimulate the writing, presentation and discussion of papers of high quality on nonferrous metallurgy; to reject or accept such papers for presentation before meetings of the Division. Article II—MembeRs Sec. 1. Any Member, Associate, or Junior Associate of the A. I. M. E. in good standing may become a Member, Associate or Junior Associate of this Division upon registering in writing a desire so to do, but without additional dues. Sec. 2. But no one who has been continuously indebted to the A. I. M. E. or to this Division for more than three months shall be entitled to vote or to receive publications to which, as a member of the Division, he would be entitled. Article III—Funds Sec. 1. The expenditure of the funds reccived by the Division shall be authorized by the Executive Committee of the Division. Article IV—Meetings Sec. 1. The Division shall meet at the same time and place as the annual meeting of the A. I. M. E., and at such other times and places as may be determined by the Executive Committee subject to the approval of the Board of Directors of the A. I. M. E. Sec. 2. The annual business meeting for election of officers shall be held within a few days before or after the annual business meeting of the A. I. M. E. Sec. 3. At any meeting of the Division for which notice has been sent to the members of the Division through the regular mail at least one month in advance, a business meeting may be convened by order of the Executive Committee, and any routine business transacted not inconsistent with these By-laws or with the Constitution or By-laws of the A. I. M. E. Sec. 4. For the transaction of business, the presence of a quorum of not less than 25 members of the Division shall be necessary. Article V—Officers and Government Sec. 1. The officers of the Division shall consist of a Chairman, two Vice-chairInen, Secretary and Treasurer. The office of Secretary and Treasurer may be combined in one person, if desired by the Executive Committee. Sec. 2. The government of the affairs of the Division shall rest in an Executive Committee, in so far as is consistent with the By-laws of the Division and the Constitution and By-laws of the A. I. M. E. Institute of Metals Divisiori

Jan 1, 1931

By R. A. Swalin, B. W. Roberts

ONSIDERABLE controversy has centered about the existence of an order-disorder transformation in alloys in the composition vicinity of 75 atomic pct Ni and 25 atomic pct Cr. All the evidence to date for such a transformation is of a rather indirect nature, since direct X-ray confirmation is difficult to obtain as a result of the small difference in X-ray scattering factors between nickel and chromium. As a result, superlattice lines would be very faint if present. Several investigators1-5 have observed anomalies in the electrical resistivity vs temperature curves of alloys in the vicinity of 25 atomic pct Cr. The observed change is characterized by a rather broad resistivity peak at about 540°C. A discontinuous drop in resistivity is normally associated with ordering. However, Taylor and Hin-ton4 have rationalized that the discrepancy could conceivably be caused by changes in the Brillouin zones upon ordering. The same investigators measured the specific heat as a function of temperature and have also observed anomalies in the vicinity of 540°C. Nordheim and Grant5 have proposed, because of the absence of superlattice lines and the absence of a discontinuity in the resistivity vs temperature curve, that long-range order is improbable and that the results could be better explained by short-range ordering. To date, however, the question has not been resolved satisfactorily. Neutron diffraction techniques provide a method for partially resolving the question since nickel and chromium have considerably different atomic scattering factors in the case of neutrons and, therefore, superlattice peaks, if ordering occurs, should be readily discernable. The results of a neutron diffraction investigation* coupled with a dilatometric in- vestigation are reported here. An alloy containing 28.0 atomic pct Cr was prepared from carbonyl nickel and electrolytic chromium in the form of a 1-in. diam x 10-in. ingot. Melting was done in an alumina crucible and casting in a graphite mold. The ingot was homogenized at 1250°C for seven days, after which a 5-in. long piece was cut into shavings in order to obtain a suitable neutron diffraction sample. Hardness samples and samples suitable for dilatometric analysis (% in. diam x 2 in.) were prepared from the remainlng piece. The neutron diffraction sample, along with a hardness sample, was annealed at 501°C for seven days, at which time the temperature was lowered to 479°C and held at this temperature for twenty-four more days. The hardness was observed to increase from 133 to 147 Vhn during the course of the annealing treatment, in qualitative agreement with Nordheim and Grant." Neutron diffraction traces taken at room temperature and at 42 °K are shown in Fig. 1. The insert shows the trace taken at room temperature with short counting times and thus only fair statistical accuracy. No evidence for superstructure reflections of Cu3Au-type ordering is observed. The statistical accuracy of the 4.2°K trace was improved by using longer counting periods. Several weak intensities are observed at small angles, including an aluminum reflection from the cryostat assembly and a very

Jan 1, 1958

• Pellets of concentrated iron ore have been smelted in the blast furnace by Armco and the results proved satisfactory. Various percentages of pellet burdens were tried and it has been found that charges up to 70 pct pellets are workable. •In the reorganization of the Department of the Interior, two new assistant secretaries were appointed and the work divided between the four assistant secretaries. C. Girard Davidson will head a division of mineral resources including the Bureau of Mines, Geological Survey, Division of Oil and Gas and Division of Geography. •Germanium, one of the rarest of metals and a wartime strategic material, has been discovered almost in the shadow of the Capitol. The only catch is that the scattered nature of the deposits makes profitable recovery extremely doubtful. Nevertheless, experts have tabbed the concentration in the District of Columbia area the world's second richest known concentration of the element. • Cakes of mica, weighing up to 500 lb, have been formed at the Colorado School of Mines by a new "cool hearth" method. The process avoids use of crucibles and contains the molten mica in a basin of unmelted raw mixture from which the melt was derived. Crystallization takes place in this melting basin which forms a center pool surrounded by a solid cool mass of the unmelted raw mixture. • William 1. Baxter, of the International Economic Research Bureau, predicts a period of deflation because of war-essential restrictions on consumer credit and materials use. He stated; "the recent prosperity was based mainly on the sales boom in autos, homes, and household accessories." •Two subsidiaries of United States Steel have decided to build four new ships immediately to augment iron ore and limestone carrying capacity on the Great Lakes to meet demands created by the national defense emergency. •The Norfolk and Western Railway is making a complete change over to coal to drive its locomotives. •A national roster of scientific personnel similar to the one used in the last war will be established by the Office of Education, by agreement with the National Security Resources Board. The new unit, the National Scientific Register Project, will make studies of the Nation's scientific manpower supply and recommend steps to increase the numbers of skilled personnel where needed. •National Lead Co. will start construction immediately of new facilities at St. Louis, Mo., for production of titanium pigments for paints. Producers of titanium pigments have been under considerable pressure to meet all demands from paint manufacturers, particularly for titanium dioxide. •The basic criteria for deferment of reservists in civilian occupations are (1) the Department of Labor List of Critical Occupations, and (2) the Department of Commerce List of Essential Activities, both of which were announced Aug. 3. Fundamentally, the reservist deferred must be engaged in a critical occupation which is necessary to a highly essential activity, and he will be deferred only until he can be satisfactorily replaced in that occupation. A delay in call to active duty, it was emphasized, may not be considered as an indefinite exemption from military service.

Jan 9, 1950

By D. C. Hilty

C. E. SIMS*—This is a most interesting and important paper. It is important from two standpoints. First, it has as-spects of being highly accurate and therefore extremely useful to the operating man in showing how far he can go in oxidizing carbon from a steel bath while retaining chromium and the effect of temperature on this limit. Fig 5 is undoubtedly the highlight of the paper, and in checking it against available data, it seems capable of predicting actual results. The other important aspect is the apparently significant fact that reactions within a steel bath, such as between carbon and an oxide, are homogeneous reactions which do not require equilibrium with an external phase. In this case, it seems obvious that the reaction and the equilibrium established were between dissolved carbon (or carbide) and dissolved CrO. The classic reaction which requires equilibrium with solid Cr2O3, did not fit the data. It was recognition of this principle that made Fig 5 possible. G. R. FITTERER*—It might be in assuming the CrO is dissolved in the metal that you are actually approaching the correct factor for activity. If that is true and if the percentages that were used represent an equilibrium constant, this would mean, in effect, that the minimum temperature at which chromium would be reduced by an equivalent percentage of carbon would be about 2400°F from your equation. I believe that is in line with my experience particularly if you deal only with low percentages. J. CHIPMAN†—The author in discussing the equilibrium of the reaction offers two choices of explanation. One postulates an effect of chromium on the activity coefficient of carbon; it would require perhaps more data than are available to us at the present time to test this thoroughly. The other postulate which he offers is a reaction with CrO. This explanation is consistent with physical and chemical principles provided that a solid phase CrO is present, and that is essentially what he is postulating. If that oxide were present one would expect and, I think, almost require the kind of results that he obtained. The weakness of that postulate lies in the lack of confirmatory evidence regarding the presence of solid CrO as such. This should offer an interesting subject for further study. It seems a pity that the theoretical arguments revolving around CrO should have obscured for a moment the very real excellence of this paper. E. CARTER*—I think there is a problem that presents itself in practical application where the metal temperature is from 3200 to 3300 and the temperature desired in pouring is considerably less. B. M. LARSEN†—I get the impression from some of the work that was done earlier that there is probably a localized zone of high temperature at the slag metal interface which effects the removal of the carbon. Without that I wonder if the effect is possible to have a localized superheat and an equilibrium there favorable to low carbon content and

Jan 1, 1950

By John T. Galey

A combination of two factors in addition to the current Federal drilling and price regulations reduced by 120 from I942 the number of new wells completed in southwestern Pennsylvania during the year. No new prospective area was found comparable to the Armbrust gas pool, Westmoreland Co., which accounted for a seventh of the last year's drilling, and it is considered doubtful whether, even if such a field had been discovered, the drilling contractors, who have been seriously affected by the manpower shortage, could have drilled many more wells than they did during the year. New wells totaling 445 were completed for a combined footage of over 1,250,000 Dry holes numbered 131 and had a footage of nearly 400,000. Old wells drilled deeper total 55, of which 17 were found nonproductive. Shallow Development Oil Oil completions yielded an initial of only slightly over one hundred barrels from 21 wells for about the same per well average as that of a year ago. However, 65 bbl. of this total came from two wells in two new strikes. The footage drilled of nearly 33,000 gives an average of nearly I00 ft. less per well than a year ago. Two old wells drilled deeper had a combined initial of only 4 bbl. The largest oil well of the year, 40 bbl., was found in the Speechley (U. Dev.) sand at a depth of 3492 ft. in German township, Fayette County. The location is several miles east of the nearest oil production hut as the area that could be occupied by a pool is fairly well delimited by drilling, the extent of this production would not appear to be large. The other notable oil production was found in the Dunkard (Penna.) sand, Cumberland township, Greene County, at a depth of 1065 ft. Here the first well had an initial of g bbl. and the second 25 bbl. However, a third proved dry, and as this area is also delimited by drilling, the pool doubtless will be of small area. Gas Gas completions yielded an initial of slightly over one hundred million cubic feet per day and new wells, totaling 303, account for all but four million of this volume. Old wells drilled deeper, numbering 35, found gas. The per well average in new drilling of approximately 320 M cu. ft. is nearly 165 M cu. ft. less than a year ago and the total footage is slightly over 830,000, which is about a quarter of a million feet less than in 1942. Average rock pressure of new completions is approximately 365 lb. per sq. in. The entire volume of new production is from the Upper Devonian or higher stratigraphic horizons. In Allegheny County, the grestest activity was in Forward and Plum townships. Wells there account for more than one half the completions. One large well was drilled in Forward township and an open flow of 3.623 million cubic feet was found in an old Gantz (U. Dev.) sand area. The top of the sand was encountered

Jan 1, 1944

By H. K. van Poollen, H. C. Bixel

A treatment is given of the transient pressure behavior of a well located at the center of a circular region surrounded by a radial discontinuity. On either side of the discontinuity, the values of permeability, viscosity, compressibility and porosity are uniform but may be different from those on the other side of the discontinuity. The results are obtained by solving a pair of finite difference equations. The numerical solution to these equations is obtained using a digital computer. The results are compared with previously published, approximated analytical solutions to the same problem. Solutions, presented graphically, show pressure decline for constant rate fluid production. The range of variables studied include dimensionless time from '0.001 to 100 and storage capacity ratio from 0.001 to 1,000. The well behaves as if it were in an infinite reservoir for dimensionless times less than 0.25. Reservoir properties near the well can be estimated in the usual manner. An overlay technique is used to match an experimental curve with one of the theoretical curves. It is possible to estimate the distance to a discontinuity by substituting the actual time t and the corresponding dimensionless time tD at which a match occurs into the equation a = (0.000264 tk1/tD , µ1 cI)I/2 where kI/ I µI cI is the diffusivity near the well, and may be estimated from data taken at early time. Several buildup curves are computed. These curves show that for early shut-in times, correct values for transmissibility are obtained from conventional analysis. However, erroneous values of static reservoir Pressure are obtained unless data at large shut-in times are taken. INTRODUCTION A mathematical treatment of the transient pressure response of a well located at the center of a region bounded by a circular discontinuity is given. Within a region (Fig. 20) the properties of both the rock and the fluid are considered to be constant on either side of the discontinuity. While these properties are considered constant, they may be different on opposite sides of the discontinuity. A discontinuity of this type could be a fluid-fluid contact or a sudden change in rock characteristics such as thickness, porosity or permeability. Analytical solutions to this problem are available. 1-3 However, they are so involved that they are of little practical use. An approximate solutionl is available but the range of times over which it is valid has not been specified. A numerical solution to a pair of finite difference equations is used to obtain the solution given in this paper. PREVIOUS WORK One of the first solutions to the problem was published by William Hurst.1 Hurst considered unsteady-state flow of fluids through two sands in series with different mobilities in each sand. He used Laplace transforms to obtain a solution for a single well located at the center of the circle enclosing the first of the two sands. In this case, the solution for the pressure change in Region I (Fig. 20) is2

By Robert E. Green

Experiments were performed in order to investigate the influence of magnitude of driving force, recouery, and previous heat treatment on grain boundary migration in deformed aluminum crystals. The frequency of occurrence of strain-free grains possessing Preferred crystallographic orientations was studied both as a function of heat treatment and as a function of amount of deformation of the matrix crystal. Aluminum of such composition as to exhibit precipitation-hardening behavior was used. CONSIDERABLE work has been devoted to the factors influencing grain boundary migration in metals.1'52 Aust and Rutterl-9 have studied grain boundary migration into matrix crystals containing a striation substructure, which provided a thermally stable driving force during the course of the migration experiments. These authors state that, while variations in the striation pattern were sometimes observed, it was possible to obtain reasonably uniform and reproducible striation structure by careful control of the solidification conditions. Admittedly, this source of driving force is a unique one and has served well in numerous experiments. However, although the striation substructure provides a thermally stable driving force, the subject of its reproducibility from crystal to crystal is questionable. In fact, Aust and Rutter3 attribute the scatter shown in some of their experimental points and several anomalies in boundary migration rates to variations in the substructure driving force along a single specimen. A further limitation on striation-induced driving force is that the driving force cannot be varied over wide ranges in a controlled manner. More often used as a source of driving force is the strain energy stored in a crystal during plastic deformation. This type of driving force has the disadvantage that it is not thermally stable due to recovery taking place simultaneously with the grain boundary mobility measurements. On the other hand, this strain-induced driving force is very reproducible from crystal to crystal since it is very easy to grow single crystals possessing the same purity and crystallographic orientation and then to strain them identically. In order to measure grain boundary migration rates two different methods are primarily used. Most often the technique employed is the heat-cool-etch method1' which involves thermal cycling, while the other technique, developed by Graham and Cahn11 using an X-ray diffractometer and goniometer furnace, involves continuous heating only. Thus the influence of thermal cycling vs continuous heating is a factor to be considered in grain boundary migration rate measurements, particularly in cases where the source of driving force is the strain energy stored in the deformed matrix, and recovery is likely to occur. Numerous recent investigations have shown that extremely small impurity additions to zone-refined metals exert a marked effect on grain boundary migration rates1-5, 9, 12-27 and a few have considered the effect of the distribution of impurities.28-35 The concentration of impurities and their distribution as influenced by heat treatment must also be taken into account in migration-rate studies. In the present article consideration is given to the influence of the magnitude of driving force, recovery, and previous heat treatment on grain boundary migration rates. In order to vary the driving force over a large range it was necessary to use as a source of driving force the energy stored in the matrix crystal during plastic deformation. A majority of the investigations were performed on aluminum specimens which were of such compositions as to exhibit precipitation-hardening behavior.

Jan 1, 1965

By S. J. Burns, W. W. Webb

The dislocation arrangements formed during unsteady propagation of cleavage fractures on (010) planes in LiF have been investigated by high-resolution etch-pit techniques and by X-ray diffraction topogvaphy. In impurity-hardened crystals, cracks propagating in any direction on (010) planes at velocities of about 103 cm per sec are usually accompanied by light plastic deformation which is enhanced wherever the crack is allowed to hesitate. Dislocations with [011] type Burger's vectors are often formed looped around the crack tip. They are dragged along with the crack tips leaving edge dislocations lying nearly parallel with the clearage surface about 5µ from it. These dislocations are easily overlooked since they may initially intersect with the cleavage surface infrequently and later may disappear from the crystals due to image forces during aging at room temperature. Although the plastic work associated with these dislocations is only comparable with the reversible (010) surface energy, an instability in crack propagation appears due to a limit of the velocity with which dislocations can be dragged along with the crack. Transition to a fully brittle nonplastic fracture mode occurs when the crack velocity exceeds the velocity with which dislocations can be moved by the stress field of the crack. TRANSITIONS between brittle and ductile modes of fracture appear to be common processes in the behavior of materials in which the flow stress is close to the stress at which brittle cracks can propagate. High-strength engineering alloys fit into this category and the transition from ductile to brittle modes of crack propagation may be associated with catastrophic failures in these important materials. The methods of theoretical mechanics indicate the geometrical conditions in which these processes may occur but the detailed mechanisms controlling the generation of dislocations in the initiation of the plastic mode and the process by which the loss of plasticity occurs on transition to the brittle mode are not yet clear. Since these mechanisms are not amenable to direct observation in engineering alloys we have chosen a semi-ductile alkali halide LiF as a model system in which to observe transition mechanisms between plastic and brittle modes of crack propagation. Cleavage cracks in this system are known to undergo a plastic-elastic transition at velocities between 103 to 104 cm per secl and dislocation configurations in LiF are amenable to study by optical-microscopic observation of dislocation etch pits2 and by X-ray diffraction topography.3 We have been able to identify a dislocation mechanism responsible for the transition from brittle to slightly plastic modes of crack propagation in LiF. A model based on this mechanism permits calculation of the critical crack-propagation velocity for this transition and indicates the importance of the stress dependence of dislocation velocity in determining the critical crack velocity. Of course, this model cannot be carried directly over to more complex materials but it is quite possible that its qualitative features are generally applicable. Dislocations intersecting fresh cleavage surfaces in LiF were reported by Gilman,4 by Forty,5 and by Wash-burn et a1.6 Such dislocations were construed to have been nucleated where the cleavage crack hesitated or stopped, near stress concentrators, such as cleavage steps, on the crystal face. The loci of such dislocations deposited On the cleavage plane in bands were called "stop lines" or "deformation zones". Gilman, Knudsen, and walshl measured the velocity of cleavage cracks in lithium fluoride by evaporating thin resistive strips on the crystal side and recording

Jan 1, 1967

By J. F. Breedis

The morphology and crystallography of marten -site formed during quenclzing were examined by transmission electron microscopy in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pet Ni and Fe-33 wt pet Ni. Depending upon composition, four types of transformation products were observed in this portion of the Fe-Cr-Ni system. Three of these products are denoted as lath, plate, and surface martensite. The hcp structure found in association with martensite it? certain higlz-clzromium stairzless steels does not influence the transformation crystallogyaphy and cannot he Considered to act as a transitional structure in the transformation from austenite to martensite. DISTINCT changes in the characteristics of mar-tensitic transformations are produced by the partial replacement of nickel by chromium in austenitic iron alloys. Large, discrete martensite plates form in Fe-30 pct Ni, while aggregates of small crystals form in sheets parallel with (111)A austenite planes in stainless steels containing in the vicinity of 18 pct Cr and 8 pct Ni. These transformation structures are termed plate and lath martensite, respectively. In addition, an hcp structure (E) has been observed in certain high-chromium stainless steels in association with martensite. It has been suggested that the E structure acts as an intermediate step in the nucleation of martensitel-' and influences the morphology and crystallography of the final transformation product. However, this structure may be the consequence of the deformation of austenite arising from the shape distortion accompanying the transformation to bcc martensite.' An hcp stacking of atoms is produced in an fcc lattice by the introduction of an intrinsic stacking fault on alternate (111)A planes. At present, the arguments behind each explanation for the E structure are based on circumstantial evidence. This investigation seeks to determine the importance of the hcp structure to the martensitic transformation, and to examine the crystallography and morphology of the structures produced in bulk samples by quenching in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pct Ni and Fe-33 wt pct Ni. These aspects of the martensitic transformations occurring in these alloys have been studied by electron metallography and selected-area diffraction of foils examined in transmission in the electron microscope. EXPERIMENTAL METHODS The alloys have been prepared from thoroughly mixed powders of pure iron (99.6+ pct, 0.06 max pct C, 0.15 max pct N), chromium (99.9+ pct), and nickel (99.9+ pct). After sintering in an Ar-H2 atmosphere, the mixtures were melted by induction heating in recrystallized alumina boats under purified argon. The ingots were cold-rolled to 0.4-mm sheets (100 pct reduction in thickness) after the removal of at least 1.5 mm from their surfaces by grinding. Three-millimeter discs were punched from the cold-rolled sheet and annealed at 1150°C for approximately 24 hr in evacuated quartz capsules. The average grain size was 40 µ Thin foils for examination in transmission in the electron microscope were prepared from discs quenched to liquid-nitrogen temperature. A depression was first jet-machined into the center of a disc and a thin area (less than approximately 3000A in thickness) was produced at the base of the depression by electropolishing. Electron-microscope studies utilized the RCA EMU-3 and the Philips EM-100B microscopes operating at 100 kv. X-ray examination of the polycrystalline alloys was performed either in a diffractometer or in a

Jan 1, 1964

By C. S. Matthews, G. L. Stegemeier

In one field in South Texas, approximately 72 per cent of the pressure build-up results show a characteris-i.rtic "hump" (i.e., the pressure builds up and then falls off) which makes interpretation by. standard methods impossible Correlation of size and time of hump with formation permeability. well productivitv index, and method of completion led to the tentativc, conclusion that the humps were caused by segregation of gas and oil in the wellbore after closing-in"'. This conclusion was confirmed by performance of simple laboratory bubble-rise experiments, by theoretical bubble-rise time calculations, and by a detailed calculation of PVT behavior in the well of a particular well Oil which accurate Surface and bottom-hole pressure measure-ments were untile. The hump behavior has since been found to occur in many other fields. The cause, however, is not the mine in all cases. In some of these the hump is trace-ahie to leaks in the tnbing which allow influx from the annulus after closing-in. In other cases the hump is traceable to leaks in the device separating pay horizons in dually completed wells. It is concluded that the recording of both surface and bottom-hole pressures is desirable in wells which show an anomalous build-up behavior. A number of field examples is discussed where use of both sets of measurements enables the cause for anomalous behavior to he found, (and a reasonable interpreation of bottom-hole pressure to be made. INTRODUCTION Theoretically the pressure build-up in an infinite reser-voir should be a linear function of In [(t + at)/nere t is the production time and At a the closed-in time. Some of the variations from this behavior arc well known, such as the curved portion immediately after shut-in which results from after-production and skin effect, and the flattened end portion which results from boundary effects in a limited reservoir. The effect of stratified producing zones and irregular geometrical drainage patterns may also contribute unusual characteristics to build-ups. However, the effect of still another phenomenon—that of movement of fluids within the wellbore—has been neglected in most build-up studies to date. Fluid movements within the wellbore after shut-in occur as a result of after-production, packer failures, leaks in the casing or tubing, or buoyancy of the gas phase when both gas and liquid are present in the well. Each of these movements can influence the pressure build-up, sometimes sufficiently to negate use of the data for computing permeability or stabilized build-up pressure. Examples of each of these phenomena are discussed below. FIELD OBSERVATIONS ON HUMP BUILD-UPS In approximately 75 per cent of the wells in a medium-sized field in South Texas the pressure build-up curves rise to 3 maximum and then decline to what appears to be a stabilized reservoir pressure as shown in Fig. I. Similar behavior has also been observed in wells in other fields in Texas and Louisian:,. Because of the possibility of such behavior being a mechanical failure of the pressure bomb. the bombs were run in tanden into one well which had been known to exhibit this behavior. When both bombs recorded identical curves with the characteristic hump, it was inferred that the unusual build-up is a result of well or forma-

By M. E. V. Plummer, F. E. Beamish, J. C. Hole, J. M. Kavanagh

Prior researches have shown that the iron-copper-nickel content of platinum concentrates may be reduced by carbon to form a collecting alloy for the platinum metals in a manner exactly analogous to the formation of the lead fire assay button. The nature of the iron-copper-nickel alloys with the platinum metals has been investigated. Palladium and probably some of the other platinum metals form solid solutions with this alloy. ONE of the greatest known reserves of the platinum metals is to be found in the nickel, copper, iron sulphide deposits of Northern Ontario. The very large tonnage of copper-nickel ore processed makes the Sudbury district a significant world source of the platinum metals, the latter being recovered as byproducts in the electrolytic refining process for copper and nickel. Chalcopyrite, pentlandite, and pyrrhotite are carriers of the platinum metals;' these minerals contain from 0.03 to 2.0 ppm of the noble metals. The analysis of the above ores for the platinum metals necessitates an initial concentration of the minute quantities present in the ore. The method usually employed involves the extraction of the noble metals by molten lead with or without small proportions of silver. The lead is then separated from the precious metals by cupellation, a process which involves absorption by the cupel and volatilization of lead oxide, leaving the precious metals collected in a silver bead on the surface of the cupel. The collection by lead is probably achieved by a process of dissolution followed by some degree of segregation in the lead alloy since the cold button is seldom uniform in composition. With silver-lead alloys this process of liquation has been used to re- cover pure lead since, during the cooling period, crystals of pure lead separate and silver becomes concentrated toward the center of the solid.' Platinum and gold liquate in a manner similar to silver which may account for the successful recovery of platinum by fire assay even though it is considered insoluble in a solid lead medium. 3 In the case of iridium the liquation process may be a disadvantage in that the iridium may appear in the outer areas of the button and thus be lost mechanically during the handling processes. In any case the deficient alloying characteristics of lead for the platinum metals encouraged attempts to find an improved collecting alloy, and by analogy with aqueous extractions, preferably one in which solid solutions would be readily formed. Since, beyond a certain minimum solute to solvent ratio, the formation of a solid solution is accompanied by a lattice distortion, one would expect some relationship between the atomic diameters of any two metals and their tendency to form a solid solution. In one survey5 the hypothesis was put forward that when the atomic diameter of the solute differs by more than about 15 pct from the solvent, the "size factor" is unfavorable and the formation of a solid solution is restricted. On the other hand, when the atomic diameters are within this limit the size factor is favorable and solid solutions are readily formed, e.g. the transition metals of Group VIII having similar radii form solid solutions over wide ranges of composition.6 Even with a favorable size factor, elements having different crystal structures cannot form a continuous series of solid solutions. Cell dimensions alter as the concentration of the solute increases, causing a

Jan 1, 1962

By M. P. Tixier, F. Segesman

Explanations bused on theory and laboratory tests tire offered for certain unusual features of SP logs which may befog their interpretation, namely the "sawtooth" SP and the reduction or increase of SP with time. The sawtooth SP is frequently seen in SP recordings of thick, very permeable watcr. sands of the Louisiana Gulf Coast. Using SP data from a resistor network analog, this anomaly is explained on the basis of a thin shale streak within the sand. under which the invading filtrate accumulates by gravity segregcitiorr. The electromotive force then appearing across the shale streak gives rise to the anomalous SP. Reduction of the SP on successive logging runs Ira often been observed in very permeable sands when as indicated by the resistivity curves, the invasion depth has been reduced to practically zero. Laboratory results verify that this phenomenon may be due, to the presence of air electromotive force, across the mod rake when the fluids on either side differ in activity. Also, there is, in some cases; an increase of SP deflection on successive logging runs, because the emf initially present across the mud cake disappears as the somewhat saline water just behind the mud cake is progressively flushed out by the invading filtrate.. Field example and laboratory data are presented. I N T R ODUCT1ON Some unusual features are frequently observed on certain SP logs which make interpretation difficult. The purpose of this paper is to offer explanations of several cases of interest. All of these arc related to the conditions of invasion. The cases to be discussed are as follows. 1. The sawtooth SP anomaly which is frequently seen within the thick, highly permeable saltwater sands of the Louisiuana Gulf Coast 1. Reduction of the SP deflection from the usual sand line in very permeable sections when the depth of invasion is practically nil. As will be explained, such a reduction is attributable to a membrane electromotive force across the mud cake. 3. An increase of the SP with time just after the iormation is drilled as a result of progressive flushing of the invaded zone. FUNDAMENTALS OF SP PHENOMENA An explanation of SP phenomena must begin with the following basic ideas. 1. The SP log derives its character from ohmic potential differences in the hole produced by currents flowing through the mud.' These currents are driven by electromotive forces which are primarily electrochemical in origin. Other possible types of SP-producing electromotive forces may be disregarded for the purposes of this paper. 2. The electrochemical emf's associated with permeable formations are now understood to consist of liquid-junction emf's and membrane emf's.',' As schematically shown by thc battery symbols in Fig. 1, the liquid-junction emf, E,,,, exists at the contact between waters of different chemical activities, a,,,, (mud filtrate) and tr,,. (formation water); the shale membrane emf, lS.sn. exists across the adjacent shales whcn they separate waters of different activities. The emf's just cited are additivc in producing SP currents (arrowed circles of Fig. I). Thus, neglecting for the moment any possible membrane emf across thc mud cake, the total electrochemical emf, E,, will be given by their sum, where K,., -! K,q,, = 12 + 59, or 71 at 75 °F. In the log interpretations the SP of a thick sand (i.e.. the static SP) is generally related to the activities of the filtrate and formation water through Eq. 1. by setting the static SP equal to - E,.

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951

By S. Korman, S. B. Tuwiner

THE purpose of this study is to investigate the effect of agitation upon the flotation of chal-cocite. It is believed that the concentration of collector which is required to produce a water-repellent surface upon the mineral is determined among other things by the rate of collector diffusion through an impeding film of more or less stagnant fluid. Its thickness depends upon the intensity of agitation. In the first part of this study a method is developed for determining the thickness of the fluid film upon a polished surface of synthetic chalcocite. The film thickness is then determined as precisely as possible under three readily reproducible condi-tions of agitation intensity. These determinations serve as a quantitative evaluation of agitation. In Part 2 it is demonstrated that in solutions of lime at PH 10.5 and in the absence of air or dissolved oxygen the concentration of collector required to develop water-repellency upon the surface in any given time is a function of the fluid film thickness, and that after about 10 min the relation becomes linear. This points to the possibility that the collector ions may be involved in a diffusional process through the fluid film. In Part 3 it is shown that where air is present more collector is required to produce water-repellency than for the case in which air is excluded. Next, it is shown that for the latter case the most minute amount of sodium sulphide suffices to preclude development of water-repellency. Both oxygen and sulphide are in a sense, therefore, depres- sants for chalcocite in a lime solution at PH 10.5. When oxygen and sulphide are present simultaneously there is a region of minimum critical collector concentration for water-repellency which is very markedly lower than the concentration where oxygen alone or where sulphide alone is present. Moreover, this minimum appears to be identical with the collector concentration which is required where sulphide and oxygen are both excluded. This would appear to indicate that in certain ranges of concentration of oxygen and sulphide, each cancels the effect of the other. The range of concentration of solution for this effect in solutions saturated with oxygen is a function of the agitation intensity. Thus we are led to believe that a chemical reaction involving sulphide and oxygen occurs at the surface of the chalcocite. Part 4 of this study is a further development of this idea and some of its consequences from an electrochemical standpoint, while in Part 5 the disappearance of sulphide from pulps of several minerals is noted with an indication that both dissolved oxygen and the mineral are necessary, the reaction being catalytic or pseudocatalytic. Part 1. Determination of Fluid Film Thickness The Fluid Film Concept: The hindrance to the diffusion of collector to the surface of the chalcocite is a barrier of stagnant fluid in the vicinity of the surface. It is the same barrier that limits the rate of transfer of heat, the rate of solution of dissolving crystals, or any of the other rates pertaining to chemical engineering unit operations in which the film resistance to diffusion plays a principal role.' Fluid films are present upon the surface to an extent which varies with the geometry and intensity of agitation. They result from the fact that in the region within the fluid near a surface, motion is entirely parallel to it. From the standpoint of transfer to or away from the interface the effect is as though the fluid were stagnant. Outside of the film, movement of the fluid may be streamline or turbu-

Jan 1, 1951

By A. T. Chatas

A description of the geometrical characteristics of spherical reservoir systems, a discussion of unsteady-state flow of such systems and examples of engineering applications are presented as backgmund material. The fundamental differential equation, a description of average spherical permeability and the introduction of the Laplace transformation serve as theoretical foundations. Engineering concepts are investigated to indicate particular solutions of interest, which are analytically obtained with the aid of the Laplace transform. These are numerically evaluated by computer, and presented in tabular form. INTRODUCTION A tractable mathematical analysis of unsteady fluid flow through porous media generally requires incorporation of a geometrical symmetry. The simplest forms include the linear, cylindrical (radial) and spherical. Most analytical endeavors have concentrated on cylindrical symmetry because it occurs more often in petroleum reservoirs. Nevertheless, some reservoir systems do exist that are better approximated by spherical geometry. Review of technical literature revealed but a single reference to unsteady spherical flow in petroleum reservoirs.l The motive and purpose of the present work was to remove this gap in technical information, and to provide the practicing engineer with some useful analytical tools. The mathematical details associated with the particular solutions of interest involved use of the Laplace transformation. Hurst and van Everdingen previously demonstrated the efficacy of this operational technique, and in many respects the present treatment was patterned after their earlier work.2 PRELIMINARY CONSIDERATIONS GEOMETRICAL CHARACTERISTICS Geometrically, a spherical reservoir system is defined at any instant of time by two concentric hemispheres whose physical properties of interest vary only with the radial distance. Every physical property is thus restricted to be a space function of only one variable: the distance along a radius vector emanating from the center. Such a system is composed of an outer region and an inner region, separated by a defined internal boundary. The inner region simply extends inward from this boundary, whereas the outer region extends outward from it to an external boundary. The position of the internal boundary is presumed fixed, so that the size of the inner region remains constant. On the other hand, the position of the external boundary at any given instant of time is determined by the distance into the system that a sensible pressure reaction has occurred, Thus, the external boundary may change position with time. It initially emerges from the inner region and advances outward to its ultimate position. When this ultimate position coincides with a geometric limit, the reservoir system is said to be limited. When it coincides with points subject to pressure gradients furthest removed from the internal boundary, yet short of a geometric limit, the system is said to be unlimited. In this investigation two different boundary conditions are imposed at the ultimate boundaries of limited systems. The first requires that no fluid flow occur across this boundary; the second that the pressure remain fixed at this boundary.3-5 UNSTEADY-STATE FLOW In a strict sense virtually all flow phenomena associated with a reservoir system are unsteady-state. The transient behavior of these phenomena requires accounting, however, only when time must be introduced as an explicit variable. Otherwise, steady-state mechanics may be used. Analytically, steady-state conditions prevail in a reservoir system only over that portion of its history when this relation is satisfied:

Jan 1, 1967

By A. L. Barnes, A. M. Rowe

A heat transfer study was made of hot gas injection into oil shale through wells interconnected by vertical fractures. This analysis involved the simultaneous numerical solution of a nonlinear, second-order partial differential equation that describes two-dimensional conduction heat transfer in oil shale and a nonlinear first-order partial differential equation that describes convection heat transfer in the fractures. Three nonlinear, temperature-dependent coefficients were used in this work; they are thermal conductivity, thermal capacity and retorting endothermic heat losses of oil shale. Vertical fractures were considered to be of finite height. Although vertical conduction heat transfer was not considered, an estimate of the error resulting from this limitation was made. The effects of injected gas temperature, injection rate, system geometry, cyclic injection and time upon retorting efficiency were investigated. Results from this study show that the rate of retorting oil shale is a direct function of both injection temperature and rate, and the theoretical producing air-oil ratio:(AOR) is an inverse function of temperature. Retorting rates are constant until "breakthrough" of the 700 F isotherm at the producing well, assuming constant injection parameters. Retorting rates for bounded systems are higher than the analogous unbounded systems and likewise AOR's are less. The use of an alternating injection-soak routine with high injection rates is less efficient than continuous injection at lower rates. These results indicate that injection temperatures on the order of 2000F or greater may give theoretical AOR's in the economic range. INTRODUCTION Over half of the known oil shale reserves are located in the U.S., and most of them lie in the Piceance Creek basin of Western Colorado. The Colorado oil shale outcrops on the edges of the Piceance Creek Basin. At the outcrops the shale beds are relatively thin, from 25 to 50 ft thick. In the center of the basin the oil shale is as great as 2,000 ft thick and is covered with 1,000 ft of overburden. It has been estimated that there are over 1,000 billion bbl of oil in shales having an oil content over 15 gal/ton in this basin. Oil shale does not contain free oil but an organic matter called kerogen. Kerogen yields petroleum hydrocarbons by destructive distillation. It must be heated to approximately 700F, at which temperature it decomposes into shale oil, gases and coke. The U.S. Bureau of Mines and, more recently, oil companies have conducted considerable research on surface retorting methods to economically recover oil from this shale. Another approach to exploit the oil shale deposits, in particular that portion having 1,000 ft of overburden, is to retort the oil shale in place and produce the liquid and gaseous hydrocarbons through wells drilled into the shale. Some research has been done on this approach.l,2 There are several variations to the in situ retorting approach. These variations fall into one of two groups, depending upon the geometry of the system: (1) retorting in a highly fractured or broken up matrix; (2) retorting from single fractures between production and injection wells. The latter is the group studied. Several investigators,3-6 using various assumptions, have studied flow of heat through horizontal systems. The objective of this work was to make a heat transfer study of in situ retorting oil shale by hot gas injection through wells interconnected by single vertical fractures of finite height. The oil shale thermal conductivity, thermal capacity and retorting endothermic heat losses were considered to be functions of temperature. A knowledge of the

Jan 1, 1969

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations. Geology Composition and Morphology Diatomaceous silica qualifies as a. mineral of organic origin in much the same way that aragonite and collophane do. The silica of the fossilized diatom skeleton closely resembles opal or hydrous silica in composition (SiO2 • nH2O) .4, 12, 203 The silica is of acute biological significance, not only for the cell wall component, but also for the basic life process.45, 51 Without silica, cell development ceases .31 In addition to bound water, varying between 3.5 and 8%, the siliceous skeleton may also contain, in solid solution, or as part of the Si02 complex, small amounts of associated inorganic components-alumina, principally-and lesser amounts of iron, 46, 49, 55 alkaline earths, alkali metals, and other minor constituents.59, 63, 67 Boron is reported to be an essential element for diatom growth .52, 58 Since diatomaceous silica is not pure hydrous silica but contains other intimately associated elements, there is good reason to consider it a distinct type or variety.4 Associated with the diatomaceous silica, and integrated as part of the diatomite, may be variable amounts of organic matter, soluble salts, and particles of rock-forming minerals that were syngenetically deposited or precipitated with the diatom frustules. Sand, clay, carbonate, and volcanic ash are typical common contaminants. Other contaminating minerals may be present, such as feldspar, mica, amphiboles, pyroxenes, rutile, zircon-the result of weathering, then transporting, and subsequent redeposition of surrounding land masses. Commercial diatomite may also contain fragments and particles of

Jan 1, 1983

By D. Dever, E. S. Fisher

Measurements of the temperature dependence of the elastic moduli in single crystals of hep ruthenium, rhenium, cobalt, dysprosium, and erbium were carried out for various temperature ranges so as to investigate the correlation, suggested by prior work, between the shear anisotropy ratio, A = C44/C66, and the occurrence of the hcp — bee phase transformation. These measurements confirm the suggestion that A has a positive temperature dependence in that group of hcp metals that undergo thermally induced transfornzations to the bee structure and a negative or zero temperature dependence in the other hcp metals. It appears, from indirect evidence, that the hcp -fee transformation in cobalt is preceded by a highly negative temperature dependence of A. These results indicate that elastic anisotropy is an important factor in determining the temperatures at which martensitic phase transformations occur. Two possible roles for elastic anisotropy are proposed: 1) the shear-modulus ratio within the habit planes must be nearly similar for the two phases and 2) a large anisotropy decreases the stress necessary for the movement of the transfornzation dislocations. FUCHS' calculations of the elastic moduli in the alkali metals have shown that the high shear-anisotropy ratios, c/c', in certain bee metals and alloys are the result of large negative contributions to c' = (c11 - c12)/2 arising from the nearest-neighbor repulsive forces.' On this basis, and following Zener,2 the association between high c/c' ratios and the martensitic phase transformations that occur upon cooling certain bee metals is explained as a unique characteristic of the bee structure. Recent measurements of the elastic moduli in hcp titanium and zirconium show, however, that a high elastic anisotropy also exists in these hcp structures at the temperatures at which they transform to bee upon heating3. If there exists a direct and consistent correlation between the elastic anisotropy in close-packed structures and the occurrence of transformations to the bee phases then there is evidently a need to re-examine the conclusions of Zener theory. Elastic anisotropy may also be the result of the effects of temperature on the stability of the low-temperature close-packed structures or it may play an important role in the mech- anism of the martensitic transformations. The present measurements were aimed at establishing the phenomenological correlation between elastic shear anisotropy in hcp structures and the thermally induced hcp —bee transformations that occur in the majority of the twenty-three hcp metals, as shown in Table I. Prior to the present work the temperature dependence of the anisotropy ratio, A = c44/c66, was known at various temperatures for nine of the metals listed. The data showed a negative temperature dependence of A for cadmium, zinc, magnesium, and cobalt, which do not transform to bee, and a positive temperature dependence of A for thallium, zirconium, titanium, hafnium, and yttrium. The correlation was, however, ambiguous in that these two groups of metals are also separated with respect to the c/a ratios as noted in Table I. There remained the possibility that the temperature dependence of A is a function of c/a and not consistently associated with the transformation. The measurements of the elastic moduli in rhenium and ruthenium, in which hcp —bee transformations do not occur, were needed to help decide this question. The studies of dysprosium and erbium were undertaken to determine whether the correlation holds for the heavy rare earth metals.

Jan 1, 1968

By R. R. Goddard

By use of the frequency response method with a radioactive tracer, it was possible to determine fluid dispersion and distribution in a natural consolidated and an unconsolidated medium. Measurements were made in a linear flow system at oleic saturations of 69 per cent in the consolidated medium, and 100 per cent in both media. Dispersion and distribution were obtained by measuring the amplitude attenuation and the phase velocity of sinusoidal waves with a dual monitor apparatus. The gamma ray emissions permitted in situ measurements at any distance along the porous samples. One result of importance was that the effective diffusivity increased as the wave length increased. As a consequence, a dispersion coefficient appropriate for the injection of large slugs might exceed the value measured by use of small slugs. Since flow models based solely on fluid velocity and an effective diffusivity coefficient imply that the diffusivity should be independent of frequency, such representations were not adequate for the data of this study. A comparison was made with a capacitance model of porous media with deadend PVs, but even this model was not completely adequate. By using attenuation and phase velocity data, fluid dispersion can be predicted without postulating a differential equation satisfied by the tracer concentration, thereby eliminating the need of a complicated model to represent dispersion. INTRODUCTION The flow of similar miscible fluids through a porous medium can be fairly adequately described by two parameters: the average fluid velocity and the effective diffusivity.1-3 It has been pointed out recently, however, that significant discrepancies exist between this representation and the experimental data.4-7 An improved agreement can be obtained by introducing additional parameters based on the concept of dead-end pores. The purpose of the present investigation was to find out whether the frequency response method could be used to measure the relevant parameters. The method was used in the following form. A stream of fluid was flowed at a constant rate through a sample of porous material and the concentration of a radioactive tracer in the fluid was varied sinusoidally at a fixed frequency. The effects of flow through a porous medium are a decrease in the amplitude of the concentration wave and an increase in the velocity of the peaks of the waves above the average velocity. Attenuation and phase veIocity of the waves were measured as a function of frequency and fluid velocity. The simple two-parameter model implies that the diffusivity should be independent of frequency. Data reported in this paper show that the diffusivity decreases as the frequency increases. Hence, as shown also by many others, the two-parameter model is not completely adequate. Coats and Smith 5 used two additional parameters in their model: the volume of the dead-end pores and the rate of mass transfer between dead-end pores and the flowing stream. Their capacitance model of a porous medium containing some stagnant fluid, to which transfer occurs by molecular diffusion, did not explain the dispersion results of either the present study or of theirs. Instead, the capacitance effect can be better described as the result of extreme velocity variations within the pores of the medium, with transfer between the velocity zones by convection. EXPERIMENTAL PREPARATION OF POROUS MEDIA Data reported here were obtained with a natural Berea sandstone, and with two packings of 20/25 mesh sand. Pertinent information about these media is listed in Table 1. The sandstone core was first sealed with a non-

Jan 1, 1967