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By J. O. McCaldin, P. Duwez

ALLOTROPIC transformations between 1000° and 1900°C have recently been reported for several metallic elements. Since the proposed transformations are based on limited evidence, it was decided to examine the elements in question as well as some refractory metals by thermal analysis with a photoelectric technique similar to that described by Hug-gins, Roll, and Udin.1 In this method, a lead sulphide cell was used to detect thermal radiation from an electric-resistance heated strip specimen. A thermocouple spot welded to the specimen was used to calibrate the temperature of the system under steady temperature conditions, and recording was accomplished with a cathode ray oscilloscope. In the method used by the present authors, the temperature calibration was omitted and the cathode ray oscilloscope was replaced by a recording galvanometer. This technique, in which electric current passing through the specimen heats it, will be referred to henceforth as Method 1. Another arrangement was required for those cases where the specimen could not be formed into a wire or strip suitable for resistance heating. In such cases the specimen was a sintered compact heated by thermal radiation from a hot tungsten strip, Fig. 1. The specimen was insulated from the heating strip with a thin layer of thoria powder or suspended on 0.004 in. tungsten wires. The take-up spring had just sufficient tension to prevent buckling of the heating strip due to thermal expansion. This technique will be called Method 2. Both methods were tested with specimens of iron and titanium and the well known allotropic transformations, a toy and ? to 8 in iron and a to in titanium, were very clearly detected. Fig. 2 shows one of the records obtained for titanium. For this particular experiment, the iodide titanium specimen was a square rod 0.080 in. on an edge and 3 in. long.

Jan 1, 1955

By Austin E. Dwight

IT has been shown by Oelsen and Wever' that the effect of a solute element on the allotropic transformation in iron is dependent upon the quantity

Jan 1, 1957

By W. Rostoker

IN the course of the development of the phase equilibrium diagram for the system Zr-Cr,' the structure of an as-cast allov having the composition ZrCr2 was analyzed and established to be isomorphous with MgZn2 (C14, hexagonal lattice, 12 atoms per unit cell). In a recent paper on the same system, Hayes, Roberson, and Davies' report for the ZrCr2 phase an isomorphy with MgCu2 (C15, cubic lattice, 24 atoms per unit cell). It appeared that this conflict might be resolved by assuming a high and low temperature modification for ZrCr2. That this was the case with the phase TiCr2 has recently been demonstrated by Levinger." Specimens of ZrCr2 annealed at 1200°, 1100°, 994", 900°, 834", 800°, and 700°C, respectively, and subsequently quenched were examined by X-ray diffraction analysis. It was successfully demonstrated that a transition from the MgZn, structure at lower temperatures to the MgCu, structure did occur at some temperature between 900" and 994°C. Table I lists the observed structures at the various annealing temperatures. In Table II, a summary of line spacings and intensities is given for each of the allotropic modifications. The first six lines of the MgCu2 structures have been located in the table to illustrate the close similarity between the patterns. Lattice parameters of the two modifications were calculated by a least squares solution of equations for interplanar spacings for a series of high angle lines. The results are as follows: MgZn2 type - c = 8.262 kX, A = 5.079 kX. MgCu2 type — a = 7.195 kX. It is interesting to note that TiCr2 behaves in reverse fashion yn that the MgCu, structure is the low temperature modification and the MgZn2 structure is the high temperature modification. References lR. F. Domagala, D. J. McPherson, and M. Hansen: This issue p. 279. 'E. T. Hayes, A. H. Roberson, M. H. Davies: Trans. AIME (1952) 194, p. 304; Journal of Metals (March 1952). 3B. W. Levinger: Trans. AIME (1953) 197, pp. 195-196; Journal of Metals (February 1953).

Jan 1, 1954

By J. B. Clark, F. N. Rhines

THE A1-Mg phase diagram in the composition range from 30 to 60 pct Mg remains uncertain. Four intermetallic compounds are reported in this composition range. All of the published diagrams are in agreement as to the existence of intermediate phases near 37 and 52 pct Mg (Mgl,A1,). Confusion exists, however, as to the number and identity of the intermetallic phases present in the intervening composition range from 37 to 52 pct Mg. Mikheeva and Kurnakovl denote the existence of a phase e near 42 pct Mg. Kawakami," Reiderer? and Laves report a phase near 48 pct Mg. Eickhoff and Vosskuhler, from a critical survey of the literature, composed the diagram shown in Fig. 1, with the exception of the eutectoid horizontal of the e-phase shown at 210°C. RaynorV n a similar survey discounts the existence of the phase proposed by Ka-wakami et al.' at 48 pct Mg and reports a composite diagram similar to that of Eickhoff and Vosskuhler." This uncertainty as to the number of intermetallic phases in the A1-Mg system may be eliminated by annealing a diffusion couple of pure aluminum and

Jan 1, 1958

By P. H. Scott, Walter Rose

Recent papers by S. T. Yuster have called attention to the largely ignored concept that there will be a transfer of viscous forces across fluid-fluid interfaces during the flow of immiscible fluid phases through porous media. This leads to the implication that the relative permeability us saturation function, as applied to each of the fluid phases of the system, will in some way be dependent on the viscosities of all the other fluid phases which are contiguous to the flowing fluid of interest. In fact, Yuster has selected and analyzed the properties of a capillary-tube model of the reservoir-prototype flow systems and concludes from his studies that relative permeability values will be very markedly influenced by the viscosity ratio in two-phase systems. On the other hand, relative permeability data have been reported in the literature for more than 20 years; and where these data are consistent at all, they consistently how no dependence on viscosity ratio (cf. chapter 7 of Muskat3 for a resume of past experiniental work). This paradoxical situation has prompted us to re-evaluate Yuster's work. The major flaw we find has to do with the properties of the model Yuster employed to give qualitative support to his predictions. This model is defective in that important surface area parameters characteristic of the prototype-reservoir flow system have not been propertly scaled. Fig. 1 shows how we believe Yuster's model should be modified to circumvent this difficulty. It depicts the capillary tube of radius R and length L, comprised of two elements in series. The first part of length, L has the nonwetting phase flowing centrally out to a radius distance r, where an interfacial boundary exists with the wetting phase which flows in the concentric annular pace of the tube. The second part of length, L-L,. has the

Jan 1, 1953

By A. G. Allten

EXAMINATION by metallographic and X-ray diffraction means of an austenitic steel containing 0.06 pct C, 1.26 pct Mn, 0.38 pct Si, 21.15 pct Ni, 18.72 pct Cr, 3.07 pet W, and 9.14 pet Mo indicated that a - phase, which had not been reported in the literature, existed in this steel. Both the s and car-bides of the M6 C type were present in the as-forged steel. The carbides dissolved completely in the aus-tenite at approximately 2200°F (1205°C). The s, however, was present at all temperatures up to the solidus temperature of the steel at approximately 2375°F (1300°C). Ferrite was not found in any condition of the steel. The faintness of some of the s lines in X-ray patterns obtained from samples of the steel made it desirable to isolate the s prior to verification of its entire pattern. It was found that the s phase could be separated from samples of the steel which had been water quenched from 2250°F (1230°C) by dis-

Jan 1, 1955

By C. A. Fothergill

An improved blotter model is described which makes use of a plastic sheet as base for the blotter field and pins to represent the input wells. The model is simple to construct and adapt and is particularly useful for demonstration purposes. Operational details are given. INTRODUCTION The blotter model was first applied to the investigation of oilfield problems by Wyckoff, Botset and Mus-kat,' primarily in order to demonstrate the flood patterns which could be expected from various arrangements of input and output wells in waterflooding projects. In recent years the model has been largely superseded for analog studies by the potentiometric and electric analog models which are more refined and versatile, since they can simulate the form, and, in certain cases, permeability variations which it is not possible to do with the blotter model. However, the latter is still used for analog studies where the reservoir can be represented as being uniform in thickness and permeability, and where a visual record of the flood advance is required. Ramey andNabor,2 for example, have applied the model to the investigation of areal sweeps in oil recovery by in-situ combustion. Because of its limitations, the blotter model can be used in general for only very simple arrangements of input and output wells, but within these limitations it has a definite advantage over all other types, in that it provides a picture of the advancing flood using the simplest and most easily constructed apparatus, by contrast with the gelatin model, for example, which requires more elaborate equipment. Moreover, the experiments can be quickly repeated and modified if necessary, whereas considerable time is required to prepare a gel field, compared with that required for the preparation of sheets of conducting blotting paper. For these reasons the blotter model can be very useful for demonstration and teaching purposes, enabling the student to experiment for himself with different arrangements of input and output wells. A model has been constructed for this purpose which is simple to operate and adapt. The model (Fig. 1) consists of a base platform or box, approximately 12-in. square, on top of which are screwed three lathes of 1/2 -in. square section to form three sides of a square 6 in. in length. This forms the support for a sheet of Cobex, transparent plastic, thickness .003 in., on which is carried the blotting paper representing the field. The plastic is flexible and relatively soft, and can be attached to the support by cellulose tape so that it can be easily removed when required. The input wells are represented by brass drawing pins pressed through the plastic sheet from the underside until the points are just projecting through the top; these are connected in the circuit as shown in Fig. 2. The sheet of blotting paper of required shape and size is saturated with a solution of 0.2 n-potassium sulfate to which has been added a saturated alcohol solution of phenol-phthalein at a strength of 10 cc/liter of stock solution. The surplus water is removed and the blotting paper placed in position on the plastic sheet making contact with the drawing pins and the sheet (which is an insulator). The anode consists of a second sheet of blotting paper cut as shown and saturated with the same solution. This is suspended from a laboratory stand, being connected to the conducting wire by means of a crocodile clip and making contact with the horizontal blotting paper at the projecting point. This is the method used by Ramey and Nabor and which permits the hydroxyl ions or colored front to reach the anode. As shown in Fig. 2, the electrical voltage used is 220-v DC and a shunt is placed across the terminals to step down the voltage as required. Further adjustment can be made as necessary using a lamp board in series with the shunt to obtain the

Jan 1, 1958

By Jr. F. M. Perkins.

Capillary forces play a controlling role in water-drive displacement processes both in laboratory experiments and in actual reservoirs, but their quantitative importance may be quite different in the two cases. Because of the importance of conducting laboratory experiments which are representative of field conditions, it is necessary to understand exactly the role of capillary forces in the displacement process. Though a number of experimental investigations related to this subject are contained in the literature, there appears to be a lack of information pertaining to unsteady-state experiments in water-wet media. This experimental study was conducted to obtain additional laboratory data to clarify further the role of capillary forces in both the macroscopic and microscopic flow of oil and water in porous materials. THEORETICAL CONSlDERATlONS The capillary pressure is defined as the difference in pressure between a continuous oil phase and a continuous water phase in a porous material.' The magnitude of this pressure difference depends on the interfacial curvature and the interfacial tension. The interfacial curvature is determined by the geometry of the pore spaces, the wettability of the rock surfaces, and the quantity of cach phase present. Capillary forces are involved in a water-drive displacement process in that they exert a controlling influence on the microscopic fluid distribution which in turn is reflected in the saturation or macroscopic flow behavior. Microscopic Fluid Distribution Because of the microscopic nature of the displacement of oil by water, it is necessary to consider the flow and the fluid distribution in individual pores. On this microscopic scale the capillary Forces, which act over a distance of one or two sand grain diameters, control the distribution of oil and water under static equilibrium conditions. When an external force is applied to the fluids, such as in a water-injection experiment, the applied forces tend to distort the oil-water interfaces. However, in most fine-grained, water-wet sands, the applied pressure difference across one or two grain diameters is usually several orders of magnitude less than the capillary pressure difference. These con-siderations lead to the theory' that even during flow the capillary forces continue to control the microscopic distribution of oil and water within the pores of a porous material for all practical reservoir and laboratory flow rates. This concept of capillary forces controlling the microscopic distribution of fluids has been substantially verified by other investigators3-7 who have found a lack of dependence of relative permeability and residual oil saturation on rate of fluid injection. Macroscopic Distribution The microscopic influence of capillary forces cannot be observed easily and only the effect on the macroscopic or average saturation can be detected. The saturation, of course, is really the point of interest. During a water flood, large differences in saturation at the flood front cause large capillary pressure gradients. This, in turn, causes water to advance ahead of the flood front thereby reducing the capillary pressure gradient in this region. The result is that in homogeneous porous media capillary pressure gradients tend to cause a diffuse displacement front. At low rates in laboratory columns, the front may extend over the entire column length. When the advancing water first reaches the outflow face of a core, the water, which is the wetting phase, cannot be produced because the pressure in the water just inside the core is lower than the pressure in the oil-filled space around the outflow face. This difference in pressure is equal to the capillary pressure for the water saturation existing at the outflow face. Water, therefore, accumulates at the outflow end of the core which causes a reduction in the capillary pressure. Because the capillary pressure does not vanish except at the residual oil saturation,7,8,9 water will not be produced until the residual oil saturation exists at the outflow face. This entire effect,"' which is called the "boundary effect", results in a region of relatively high water saturation near the outflow face. At low rates of injection in a short column, this region of high water saturation may extend over a considerable portion of the column. The influence of capillary forces on the macroscopic flow of oil and water have been described by Leverett.10 For unidirectional, viscous flow in the absence of gravity segregation, the expression in dimensionless form for the fraction of water in the flowing stream, f, is

Jan 1, 1958

By F. W. Jessen, John C. Miller

In many areas where carbonate rocks form important parts of the stratigraphic sequence, stratigraphers have experienced varying degrees of difficulty in differentiating and correlating limestone and dolomite units in both surface and subsurface work. With early Paleozoic rocks of the Mid-Continent, insoluble residues yield a remarkable amount of strati-graphic data and relatively good correlations may be carried over broad distances.' Unfortunately, neither such information nor electric logs and radioactive logs have been particularly helpful in interpreting the limestone sections of the Permian Basin of West Texas. This is because: (1) the variations in the sections may be very slight; (2) no completely satisfactory method of interpretation has been developed; and (3) the measurements themselves are not sensitive enough for small variations. Also, such logs are influenced by the fluid content. Paleontology and micro-paleontology remain the ultimate arbiters. As a routine tool, however, paleontol-ogical examination is slow and tedious. Chemical analysis may be used, but this, too, is extremely slow. Although rocks are not classified according to chemical composition, there is considerable variation with rock types. Correlation by chemical composition has two advantages, first, the characteristics determined are subject to minimum human error and interpretation, and secondly, the lithologic changes are not masked by fluid content as in the case of electric and radioactive logs. Some fossils concentrate certain elements which tentatively might be used to date rock units.' Rapid chemical analysis by spec-trographic means could be used as an adjunct to other means employed in correlation work, or might, in itself, present a suitable method. PURPOSE OF THIS INVESTIGATION Sloss and Cooke' have published data concerning spectrographic analysis of limestone rocks specifically for purposes of direct correlation of a single formation. These authors found satisfactory evidence that differences in percentage of four elements (Mg, Fe, Al, and Sr) in the Mississippian limestones of northern Montana were useful in carrying out correlation of this formation over a distance of approximately 50 miles. It was concluded from the preliminary work that the spectrochemical method offered possibilities of solution of some problems of correlation heretofore not possible. Since the work of Sloss and Cooke' was confined to one particular limestone zone, extension of the use of the method to examine two or more geologic formations would aid materially in the over-all problem of correlation of such rocks. Equipment is now available commercially with which very rapid spectrographic analyses may be made, and hence the problem was to determine whether the variations existing in the minor constituents of limestones were sufficient for use in possible correlation. Qualitative and semi-quantitative investigations were made to determine whether significant changes in the chemical condition occurred. It was a further purpose to investigate the geologic time-boundaries to see whether significant chemical variation could be found corresponding to the paleontological breaks. It was desirable to attempt correlation of a thick section of limestone or dolomite rock and to have as much information as possible on the section. Furthermore, it was felt that examination of formations more difficult to correlate by other means would enhance the value of the method should definite points of correlation be found. Samples were chosen from the Chapman-McFarlin Cogdell No. 25 well in the Cogdell field, Kent County, Tex., and from the General Crude Oil Co., Coleman No. 193-2 well in the Salt Creek field, Kent County, Tex. These fields belong to the famous series of "Canyon" reef fields of West Texas. Cores from the above wells were available from the United States Geological Survey, Austin, Tex. THE SPECTROGRAPHIC METHOD The choice of procedure to be followed in this investigation was based on the anticipated requirements peculiar to the problem. Since the problem was primarily to investigate the possibilities of applying the spec-trograph to problems of correlation in thick carbonate sections, a precise quantitative analysis did not appear necessary. A qualitative analysis to show the possible absence of presence of any element, or a semi-quantitative analysis of the elements present to show the relative changes in magnitude of selected elements was required. Both types of analysis were employed. The two most widely applied methods of semi-quantitative estimates are those of Harvey and of Slavin4,5 though various other procedures have been described.6 while the Harvey method has been modified by Addink,7 this refinement did not seem necessary to the present problem. Essentially, the procedure employed is a variation of the total energy method of Slavin with two exceptions: (1) stressing matrix effect, and (2) using densitometer measurements. As measured by a densito-

Jan 1, 1956

By Robert Maddin

crystal prior to, polishing in order to eliminate coring. This treatment may be accomplished by wrapping the single crystal tightly in very thin, dead soft, brass foil and annealing in the presence of air for 20 hr at 800°C. Since the wrapping encircles the sptcimen three to four times, only a very slight amount of oxidation occurs on the specimen surface. On unwrapping one of these cylindrical single crystals. in. in diam by ro in. long (72.75 pct cu, 27.23 pct Zn, 0.01 pct P11, 0.01 pct re), mall light-gray depnrrits in the form of circular arcs werenoted on the part nf the foil which had been in contact with the single crystal, Fig r. (By superim- approximatetl). These deposits, which, from their color, suggest the appearance of sublimated zinc, were found to coincide roughly with a set of octahedral planes nearly perpendicular to the rod axis. The pattern shorn in the figure held no relation to the profle of the sample since the markin~s on the crystal More annealing werc attributed to traces of cube planes. It seems very likely that the deposits were formed by sutllimation of zinc diffusing from octahrdral planes since diffusian would Eogically take place along planes of maximum atomic spacing. However, it is difficult to understand why a continuous sublimation of zinc should occur from a single crystat in contact with a wrapping roil OF the same composition, and why diffusion would take place along specific octahedral planes and in a regular pattern.

Jan 1, 1949

By H. I. Meyer, D. F. Searcy

INTRODUCTION The analysls of our previous paper' on the behavior at two immiscible fluids separated by gravity into two dlstinct saturated zones in the porous medium was shown to be theoretically valid only if one of the two fluids was immobile. The practical problems associated with flow of both phases have so far been impossible of solution by these analytic methods. We, therefore, decided to resort to a simulator study to answer the following pertinent questions: 1. If the lighter fluid is produced from a point above the fluid-fluid interface, how long will it take for the heavier fluid to come up to the point where production of both fluids is taking place? 2. After steady-state two-phase production is established, what is the relative production rate of each phase, on what physical variables does this depend, and what are the boundary conditions at the outflow face? 3. A third question was at least partially answered in the course of this investigation: that of the shape of the interface under flow conditions. These questions are of fundamental importance in the fields of hydrology and the reservoir mechanics of oil and gas production. In order to simplify equipment used and still retain a fair physical representation of these phenomena, it was decided to use a Hele-Shaw type of analogy in which the flow took place between two vertically mounted pieces of plate glass. The advantage of this system is that it eliminates any surface effects between the matrix of the porous medium (e.g. packed sand) and also allows equilibrium conditions to be established more quickly. The principle disadvantage (apart from the obvious one of being one more step removed from the prototype) is that our equipment limited us to two dimensional flow studies. In spite of these limitations answers to the questions were obtained which seem adequate for our purposes. We would like to see more work of this nature done to verify and to improve our conclusions. DESCRIPTION OF EQUIPMENT AND PROCEDURE A drawing of the equipment used in this study is shown in Fig. 1. Fluid flow takes place between the two 36 in. x 12 in. pieces of plate glass held apart at the long edges by two spacers of cellulose acetate sheet (Kodapac IV) which is available in several thicknesses. This sandwich was clamped together by small c-clamps whose stress was distributed by long pieces of 3/8-in. keystock. Accurate spacing was obtained by tightening these clamps as indicated by micrometer measurements on the outside of the glass. At the upstream end of the plates a piece of 6-in. diameter pipe simulated an infinite reservoir, while at the downstream end a 2-in. Lucite cylinder with a small hole near the top of the flow region served to drain the fluid. Sealing was achieved by O-rings, the whole system being tightened by pressure on the Lucite tube provided by set screws (not shown in the drawing). The total head

Jan 1, 1957

By Bernard Greifer, Walter Rose

The purpose of this note is to call attention to a source of difficulty which can be responsible for inaccurate estimates of wetting liquid pressure gradients in mixture flow experiments of the Hassler1 type. It has been our experience occasionally to observe what were indicated to be negative pressure gradients, and these were regarded as anomalous in the sense that physically they seemed to contradict the requirement that the flux be in the direction of the potential field. At first it was thought that our scheme of assembling barriers and core sample led to such asymmetry in the distribution of isobars that the manometric leads at each end of the core were responding to internal pressures (within the core sample) which could be either positive or negative with respect to each other, and which in fact might tend to reflect on different effective core lengths in an unpredictable fashion as the wetting liquid saturation was changed. However, no compelling evidence of this possibility has been established. In addition, we were cognizant of the requirements to be satisfied in selecting manometric instrumentation to minimize the delay in response of the manometer to the differential pressures being measured, and were thus assured that our observations of anomalous pressure gradients could not be explained by faulty instrumentation. What we suggest is that if a leak sink occurs in the fluid lines connecting the core to either side of the differential manometer, errors exceeding 100 per cent may result in the estimation of wetting liquid pressure gradient, even though the leak is of such small magnitude that its existence would tend to be obscured by evaporation effects. This is because in a system with leaks at the specified places, the manometer rec- ords at steady state the pressure drop across the manometer barrier elements in addition to the pressure drop across the core sample. This possibility will be illustrated below analytically and by numerical example for the special case where the leak occurs on the high presure side of the core, since we are especially desirous to explain the significance of our observations of the so-called negative pressure gradients. It will be indicated, however, that leak sinks on the low pressure side of the core can account for observations of anomalously high values of pressure gradient, and that multiple leaks on both sides of the core can provide for some compensation so that the errors in pressure estimation are reduced. However, the major point to be emphasized is the fact that the impractical-ity of detecting the small leak sinks which give rise to the difficulties makes it a complicated task for the experimenter in a particular case to know with certainty that his estimation of pressure gradient lies within the limits of error which can be tolerated. Fig. 1 shows the electrical analog of the flow system we have employed in our studies. The inflow and outflow barriers. Rbl and Rb2, the manometer barriers, Rm1, and Rm2, and the core sample, Rc— for a particular fluid saturation and distribution— are all designated as resistance elements; the flowmeter is designated by an ammeter, A; the pressure source is designated by E; and the manometric device is designated by the voltmeter, V. Included in the circuit are the variable resistances, Rx and Ry, which may be regarded as the leak sinks, and which, in general, can vary in magnitude from zero (i.e., a large hole or shunt in the system) to infinity (i.e., no

Jan 1, 1950

By S. C. Sun

Most previous work on sedimentation of coal 1 and mineral 2-3 suspensions has been conducted in graduated 1-liter glass cylinders of 6-cm diam. With this type of large container it is often difficult to see through the suspension and tedious to perform a large number of tests. Furthermore, the heavy glass walls and the graduation lines of glass cylinders cause internal and stray reflections, respectively. To obviate these difficulties, an Atlab Emulsion Viewer from Arthur H. Thomas Co. was adopted as an alternative apparatus. Equipment: The viewer," shown in Fig. 1, consists of: 1) a stainless steel frame rack holding 21 flat-bottom Nessler tubes or an ungraduated replica 1.64 cm ID and 1.80 cm OD, 2) a movable masked 150-w lumaline lamp behind the tubes, and 3) a scaled glass panel with 100 vertical divisions in front of the tubes. The tubes are snugly held by springs in slots formed by spacer bars, which also serve as shields to eliminate stray light. The lumaline lamp is mounted behind a slit in a movable housing so that it can be positioned behind the suspension to be examined. The lowest or 100-divi-sion line on the front glass plate is leveled with the upper side of the bottom of all tubes. The scaled portion of each tube, roughly 19 cm high and 40 ml in volume, is used to study coal and mineral suspensions. Procedure: The following procedure was used in many tests. A 1.6-gm sample of dry coal was mixed with 16 ml of distilled water in an ordinary test tube and allowed to stand for three days, with occasional shaking to insure thorough wetting of all particles. The slurry was transferred to a Nessler tube and diluted to 32 ml. The pH regulator and flocculating reagent were added, and the slurry was diluted to reach the uppermost or zero-division line. The tube was immediately stoppered and inverted downward and up again ten times during a period of 35 to 40 sec. The lumaline lamp was turned on during the inversion period. After inversion the tube was quickly returned to the viewer rack. The time elapsed for each 10-division drop of the demarcation line between solid and liquid was recorded by stopwatch until the 80-division line was reached in the zone of compression. Additional readings were taken at 15, 30, and 60 min after settling began. The clarity of the supernatent liquid was observed also. As the settling rate became considerably slower at the 75-division line, it was convenient at this time to start the next test in a separate Nessler tube. This was continued until the suspensions in any number of the 21 tubes were tested. An attempt was made to correlate the experimental results between the Nessler tube and a 1-liter glass cylinder. Table I shows that coal particles settle much faster in the cylinder than in the tube, which has a large wall effect.' The correction factor for the tube impedance is 1.662 2 0.145 at the 40-division line in the hindered settling zone, and 1.614 & 0.139 at the 75-division line in the compression zone. This rough correlation was established by dividing the pulp height of each container into 100 divisions and comparing the settling rates of the two containers at the same divisions. Tests were also performed to determine the accuracy of the viewer. The results, not presented, showed that error was within 10 pct.

Jan 1, 1960

By Paul B. Crawford, Melvin B. Burton

A procedure is given which describes how the gelatin model may be-used to study the effect of mobility ratio on areas swept before and after breakthrough in fluid injection programs. Differences in mobility ratio are achieved through the proper selection of electrolytes for the invading and displaced fluids. The progress of the front is followed visually and photographed or traced onto plates (it desirrd positions before and after breakthrough. Example applications to standard flooding pattrrrls, vertically and horizontally fractured reservoirs and the in-situ combustion recovery process ore presentrtl. INTRODUCTION In water flooding, gas cycling and other fluid injection programs, the sweep efficiencies and swept areas after breakthrough are known to depend on the mobility ratio. Previous investigators have described the application of the X-ray technique, stepwise use of the poten-tiometric model and numerical procedures for studying these problems.1,3,4,6 Others have described the application of the electrolytic and gelatin models for studying sweep efficiencies at a mobility ratio near one.2,5,7,8,9 It is a purpose of this paper to describe a procedure for using the gelatin model to study swept areas at mobility ratios other than one. PROCEDURE The technique developed for gelatin model studies is composed of four phases: the construction of the model, the selection and preparation of electrolytes, the running procedure, and the recording of the swept areas. Each phase is discussed independently in order that the over-all procedure will not be confused. Construction of the Model Since some of the advantages of the gelatin model are its economy, and speed, it is desirable to have as small a model as is possihle without creating error through the inability to follow visually the progress of the colored front. For this work, it was found that a distance of 4 to 6 cm between salt bridges is convenient to use. Since the size is relatively small, it follows that the gelatin layer must be thin. For this study, 1/8 in. was used as the gelatin thickness in each case. The model was constructed on a flat 1/2-in. plastic (Lucite) base with boundaries constructed from 1/8-in. plastic strips. The well pattern to be studied was outlined with the 1/8-in. plastic strips on the base with narrow apertures (- - 2 mm) in the boundary to represent the wells. Behind each well opening, a rectangular area of some 8 to 12 sq cm was outlined by additional plastic strips. The plastic strips were fastened to the base by any suitable non-conducting cement so that the boundary system was liquid tight. The electrodes were constructed from sheet copper in a fashion that would allow easy removal. In this work, it was found that by simply forming a large U-shaped clip from a strip of the copper that would slip over the boundary was satisfactory and easily removed. The electrodes should be as wide as one of the sides of the rectangular area behind the well opening. If a fractured pattern is studied, fractures inside the well pattern may be represented by strips of copper of the desired shape mounted in some easily removable fashion. The reason that apertures (or salt bridges) were used for wells instead of metallic electrodes is that the plating of the electroactive ion at the cathode and the introduction of an electroactive ion at the anode has a detrimental effect on the swept area outline if these operations \rere permitted to be carried on within the well pattern itself. The anode may be used within the well pattern

Jan 1, 1957

By A. K. Schellinger, R. D. Lalkaka

IF the ball mill is considered only from an energy standpoint, it can be thought of as a converter of kinetic energy into heat energy and surface energy. The law of the conservation of energy must apply to the ball mill as it does to any machine or process in nature. The heat energy output of the ball mill is apparent to any casual observer of the operating mill since the outflow pulp will be appreciably warmer than the inflow water and rock. The rock in the ball mill is crushed by shearing of its ionic bonding caused by some impact-induced stresses beyond the elastic limit. As the bonds holding the mineral crystal lattices together are ruptured, new surface area is created on each unit of which a definite number of unsaturated bonds exist. Such unsaturated energy of bonding may be termed the "surface energy," and is a potential energy figure. This created energy was withdrawn from the ball mill system and represents an absorption, or disappearance of heat. To reduce the size of the rock, surface area must be created and with it the at- tendant characteristic surface energies of the minerals concerned. Thus the creation of surface energy, from an energy viewpoint, is the creation of useful work by the ball mill. Because of the controversial nature of the energy efficiency figures for modern operating ball mills, it seemed worthwhile to approximate the ordinary magnitude of such efficiencies from the above viewpoint. This was done by an energy balance of the three aforementioned forms of energy, kinetic, heat, and surface energy, for two 9Y2x10-ft grate-type ball mills grinding cement raw materials. Kinetic energy input to the balls was approximated as closely as possible while the heat energy output was measured by means of a thermometer and water and rock flow rates. The assumption was made

Jan 1, 1952

By Robert L. Slobod

In much of the work reported in the literature on long cores. true connate water value, probably have not been obtained because of insufficient flow of 011 to attain equilibrium. A -.satisfactory method for establishing connate water in long cores has been developed in which oil flow is maintained until no additiona1 water is displaced. INTRODUCTION Long cores have been used by sev-erals investigators in an effort to evaluate the efficiency of oil recovery for various producing schemes. The effects of many variables such as rate of displacement. pressure drop, volume of displacing medium, gas-oil ratio, inter-facial tension, and others have been investigated, and the merits of gas drive have been compared with water drive. In the older experiments no connate water was used. but in the more recent stndies the philosophy of the experiment calls for a core containing oil and connate water (irreducible water) as the starting point of the experiment. The method generally used to establish this condition in long cores involves dynamic' displacement wherein one or more phases are forced through the core. flow being maintained at a constant rate or at a constant pressure until a steady state is reached wherein there is no change of saturation with time. It is one purpose of this paper to point out that in much of the work reported in the literature true connate water values probably have not been obtained. The reason for this failure is pointed out. and a method for obtaining more reliable connate water values on long cores is presented. It is impossible at this time to completely evaluate the effect on the conclusions in the earlier papers resulting from the failure to obtain true connate water in the long cores, but some data are presented which indicate that serious errors may he present in many cases. MATERIALS AND APPARATUS Cores cut front outcrop sandstones (Strawn. Torpedo, and Elgin sandstones) with permeabilities of the order of 300 md were used. The major experiments were made with a core 18-in. long and 2-in. in diameter. Cores of the same diameter but only 12-in. long were used in a few tests? and in some work a core I-in. in diameter and 11-in. long was used. These materials were all somewhat bentonitic. 'To reduce the effect of such constituents, one of the cores (Torpedo No. 10) on which the most work was performed was acid extracted at the start of the experiment. Brine containing 50,000 ppm chloride and naphtha (Stoddard's Solvent) were used as the water and oil phases, respectively. The core was mounted in a rubber sleeve which forms the inner lining of a brass cylinder. In this arrangement2 the rubber sleeve is forced against the core by applying pressure to water in the annular space between the rubber sleeve and the brass cylinder wall. The core is therefore sealed in rubber so that all fluids introduced at the input end of the core flow through the core. With this equipment the core may be easily removed for inspection and analysis. Also, other cores may be introduced for study with no extra time for preparation such as is required when plastic mounting is used. When pressure or conductivity measurements are desired at intermediate points along tile length of the core, the brass cylinder comprising the outer jacket of the core holder is cut into section, of the desired length. Each section is then made up as an individual unit with its own rubber sleeve (see Fig. 1). The individual units are then butted up against a ring of plastic or other insulating material which carries an electrical contact for resistivity measurements and an opening which can be used for the measurements of fluid pressures. The individual units are forced tightly against the plastic ring separators and held in place with several tie rods. Inlet and outlet end butts of the same diameter as the core and several inches in length are provided to control the introduction and withdrawal of fluids and to complete the arrangement for sealing the core within the rubber sleeve. Fluid flow is maintained either by applying pressure to the liquid confined in a reservoir or by the use of a gear pump. The latter is preferable where continuous flow at a moderate rate over a long time interval is desired since a small volume of liquid can be readily recirculated using filters to prevent plugging of the core. EXPERIMENTAL The oven-dried core is weighed and is then completely saturated with brine

Jan 1, 1950

By H. Krueger, H. N. Hersh

USE of autoradiography in diffusion studies offers the advantage that no repeated sectioning is necessary and that the analyses are performed in a simple manner over the continuous range of penetration depths. As part of a program of solid-state physics, it was desired to develop the autoradio-graphic method' quantitatively for use in diffusion studies. Results are reported here for the self-diffusion of silver. Silver was chosen because the existing data are good enough to evaluate the technique." The silver used in this investigation was obtained in the form of ¼ in. diam rods of polycrystalline material, 99.99 pct purity. The radioactive silver, Ag110 (ß, y), was obtained as the nitrate and converted to the chloride for use in a standard cyanide plating bath. The diffusion specimens were 1/2 in. lengths of the rod. They were mounted in bake-lite and the exposed circular face carefully ground and polished. Prior to electrodepositing radioactive

Jan 1, 1956

By R. Greenwood

The advent of the space age and its promise of interplanetary flight has prompted new ideas for propulsion systems that will allow maximum energy with minimum fuel weight. The use of cesium as the source of energy for such rocket flights has been found desirable. Theoretical efficiency of a rocket fuel is measured in terms of specific impulse, defined as the number of pounds of thrust per pound of propellant consumed per second. Specific impulse is usually expressed in seconds (the number of seconds for which one pound of fuel would produce one pound of thrust) although it is really a measure of total energy, not of power. The most sophisticated chemical fuels have a specific impulse of 300 to 400 sec; liquid hydrogen heated by nuclear reactor has a specific impulse of 1000 to 1200 sec. Specific impulses as high as 20,000 sec, however, are theoretically attainable with the ion rocket, in which free cesium ions are accelerated across a voltage drop and ejected at high velocity.' Characteristics of the system have been sketched by Boden.2 The desirable properties of an ion propellant are: 1) low ionization potential, 2) low boiling point, and 3) high atomic weight. Alkali metals best fulfill these requirements, and Table I indicates the superiority of cesium. The use of heavy complex ions such as UCl3 is ruled out by their instability and other disadvantages.' Despite its enormous superiority in specific impulse, the ion rocket is inherently low-powered, capable of very small acceleration. Application of ion propulsion will be limited to large rockets and spaceships on missions requiring powered flight for weeks or months and employing a separate chemical propulsion system for escape from the earth's atmosphere where power requirements are large but of brief duration. For example, Kraemer and Larson3 considered the case of an unmanned 25,000-lb pay-load placed in a 300-mile orbit by chemical rockets, proceeding thence by ion propulsion to the vicinity of Mars, where it would go into orbit once again. Calculations provide for 8500 lb of cesium for such a voyage. The question of whether such quantities of cesium will be readily available to the space program does not appear to have been considered by geologists and mining engineers. Present Production and Uses Literature on industrial applications of cesium is scanty. The metal is used in scintillation counters, photocells, infra-red detection devices, and as a "getter" in low-voltage vacuum tubes. Production is sporadic and total figures are not published, but the annual consumption is measured in pounds rather than in tons. The few pollucite deposits known, small as they are, can easily supply the present limited demand for gram or pound lots of cesium. Until recently the price of cesium was $2 to $4 per gram, but according to Chemical Engineering, cesium salts are now available at $13 to $27.50 per lb. Geochemical Distribution As a large alkali ion, the cesium ion accompanies potassium in geological processes and tends to be concentrated in the latest crystallizing fractions of potassium minerals in much the same manner as rubidium. Most of the cesium in igneous rocks, therefore, is in the micas and potash feldspars of granites, and especially in granitic pegmatites. The cesium content rises markedly in the micas of the late by-drothermal replacement stage in complex pegmatite~.' Typically, cesium is only 0.5 to 0.01 times as abundant as rubidium in potassium minerals. Rb', with a radius of 1.47 A, is close enough in size to K' (1.33 A) so that rubidium forms no minerals of its own. Cs+ is so large (1.67 A) that only small concentrations can be taken up in potassium minerals; when cesium is present in solution in larger concentration it forms the mineral pollucite, Cs3-Na2A17Si17O48.3H2O, which is known only in pegmatites. In the weathering of igneous rocks, cesium is dissolved, carried to the ocean, and apparently in-

Jan 1, 1961

By H. I. Aaronson, C. Wells

THIS is a preliminary report on a detailed metal- lographic investigation of the bainite reaction in a plain carbon hypoeutectoid steel. In view of the current interest in the bainite reaction and of the controversies which still exist about even the basic phenomenology of this mode of transformation, it was considered desirable to present a summary of the more important results obtained to date prior to the completion of this investigation. The steel used contained 0.29 pct C, 0.76 pct Mn, 0.25 pct Si, 0.005 pct P, and 0.007 pct S. The alloy was homogenized for 48 hr at 1250°C. Individual specimens were then austenitized for 30 min at 1300°C and isothermally transformed for various times at temperatures above and within the bainite region, ranging from 775" through 500°C at intervals of 25°C. These specimens were carefully examined on a research metallograph; a few specimens of especial interest were also studied electron microscopically.' Bainite may be defined as the aggregate structure resulting from the precipitation of carbides from supersaturated ferrite which formed by nucleation and diffusion-limited growth. Two groups of experimental observations made during the present study provide support for this mechanism of the bainite reaction: 1—at 625°C, partial conversion of pro-eutectoid ferrite to bainite began after more than 99 pct of the austenite had decomposed and 2—the precipitation of bainitic carbides occurred only within the ferrite phase. The proeutectoid ferrite and the bainite reactions in the steel studied were found to be morphologically continuous. Following the classification scheme of Mehl and Dube,2 three principal morphologies of proeutectoid ferrite were identified in the temperature region (625" to 550°C) in which the two reactions blend—grain boundary allotriomorphs," * Grain boundary allotriomorphs are crystals which nucleate at and grow preferentially along matrix grain boundaries. Widmanstaetten side plates, and intragranular plates. Carbide precipitation converted these morphologies into their bainitic equivalents with increasing isothermal reaction time. Conversion took place more rapidly as the reaction temperature was reduced. The replacement of supersaturated ferrite by bainite, however, did not occur uniformly even within individual austenite grains and was noticeably incomplete at higher transformation temperatures, e.g., 625° to 575°C. The ferritic and bainitic forms of a given morphology thus were frequently found to coexist, often inextricably intermixed, in a given specimen. At 625" and 600°C, the conversion of ferrite to bainite was clearly seen to have occurred entirely by the nucleation of carbides at ferrite/ferrite boundaries, as shown in Fig. 1. The nature of the loci at which carbides formed at lower temperatures was often difficult to ascertain with a light microscope, although the alignment in rows of many of the carbides, illustrated in Fig. 2, suggested that nucleation had again occurred at grain boundaries or subboundaries within the ferrite. Application of the electron microscope confirmed this deduction for bainitic structures formed at these temperatures, as shown in Fig. 3. The dense black appearance of bainite formed at very low reaction temperatures in higher carbon steels3 indicates, however, that isolated lattice defects within ferrite crystals prob-

Jan 1, 1956

By William Loblowitz

A simplified system of flotation testing has been developed recently at the Bureau of Mineral Research of Rutgers University. The technique involves the known principle of skin flotation and can be used with minute quantities of sample and reagents in a beaker. A vessel containing the conditioned sample with added water and flotation reagents is held inclined and rotated slowly. Water-repellent particles come in contact with air and float on the surface of the liquid, while wettable particles are submerged. The float is poured off and filtered whereas the nonfloat remains in the beaker. The filtrate may be returned to repeat the process. This procedure can be made quantitative. Separations are obtained and are remarkably complete and repeatable. The effect of different reagents, optimum quantities, pH and other variables can be determined in a fraction of the time required for conventional testing. However, the method gives no information on the effect of frothers and the quality of froth to be expected in a cell, and it is not practical for particles finer than 200-mesh. Unlike other preliminary tests, separate float and nonfloat products are obtained, and their contents can be determined quantitatively by chemical analysis or grain counts. After the optimum reagent combination has been determined, the effect of fines and frothing may be verified in the conventional flotation cell. On the other hand, agglomeration-tabling can be directly duplicated from beaker tests. Procedure: Five to ten grams of sample are weighed into a 100-ml beaker. Flotation reagents and a small initial quantity of water are stirred together; additional water is then added to produce the proper water-solids ratio. The beaker is then tilted to 45" and rotated slowly. After three to five rotations, liquid and float are poured off and filtered; the filtrate may be recycled until the separation is completed. One test generally requires less than 10 min. Reagent concentration and pH remain quite constant because of the recycling of the filtrate. Two to four tests may be made simultaneously, and the effect of varied conditions may be observed by comparison. Considerable time is saved in preparation and handling since small quantities of sample suffice for a series of systematic tests. Repeatability One test was repeated four times under constant conditions. The sample used was a quartz sand containing approximately 24 pct feldspar and some clay aggregates. The +28-mesh grains had been screened out, and most of those finer than 100-mesh had been removed by hydraulic classification. The results are presented in Table I. For comparison, 500 g of the sample were separated by agglomeration-tabling using the same reagent combination and quantities as given in Table I. The weight percent float was 18.3 pct, composed almost entirely of feldspar and with only traces of quartz. Most of the remaining feldspar was recovered in a middling product with 2.2 pct by weight.

Jan 1, 1952