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By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey' have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel'perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,' and Fletcher and Wilson' have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a' phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a' platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a' phase in titanium binary alloys.' In the Ti-Mo system,' two modes of a' decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a', and the other involves diffusion across the a'-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a' along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a' phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a' over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a' structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a' are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a' peaks broadened during the initial stages of tem-

Jan 1, 1965

By H. C. H. Darley

The influence of particle size and concentration on the development of chip hold-down pressure (CHDP) was studied in an apparatus designed to measure the change of filtration rate during the first second of the filtration process. CHDP is controlled by the "bridging" particles (i.e., particles in the 50 to 0.2 micron range), whereas filter loss is controlled by the colloid fraction. The results indicated that a fast drilling fluid with a low filter loss could be obtained if the concentration of bridging solids and the viscosity were kept very low. A novel group of drilling fluids, which we have named colloid emulsions, was developed to meet the above requirements. These colloid emulsions are made by dispersing art oleophilic colloid in oil and emulsifying about 5 per cent of this dispersion in water or a dense brine. Good results have been obtained in field trials with emulsions which use asphalt as the oleophilic colloid. INTRODUCTION In recent years it has been found that fast rates of penetration can be maintained in hard formations by using "clear" water as a drilling fluid. In some cases, however, water cannot be used because the very high down-hole filter loss creates various difficulties in drilling, in logging, or in producing the well. It then becomes necessary to "mud up", which results in a decrease in drilling rate. The reason that mud decreases drilling rates is a complex subject which has been well covered by such authors as Garnier and van Lingen, Cunningham and Eenink,' and van Lingen.3 One of the principal factors involved is the tendency of the drilling fluid to develop a filter cake on the bottom of the hole. The pressure differential which develops across this filter cake opposes the action of the bit in dislodging chips from the rock. This pressure differential is referred to by Garnier and van Lingen' as the chip hold-down pressure, which is denoted by the initials CHDP in this paper. The work described in this paper was undertaken to develop a drilling fluid which would minimize CHDP but which would still have a low filter loss—in other words, a fluid which would deposit a filter cake on the sides but would lay little or no filter cake on the bottom of the hole. EVALUATION OF CHDP EXPERIMENTAL Conditions governing the growth of filter cake on the sides of the hole are obviously different from those on the bottom of the hole. On the sides of the hole, cake will form continuously but at a decreasing rate, until eventually the rate of growth will equal the rate of cake erosion by the mud stream.' On the bottom of the hole, each time a bit tooth dislodges a chip the cake is removed, a fresh rock surface is exposed, and the filtration process must start over again. Thus the CHDP is determined by the amount of cake which can form in the interval between successive tooth strikes at a particular spot, normally a fraction of a second. Our first step therefore was to study filtration rates over the first second or so of the filtration process. These tests were conducted in the simple type of dynamic filter cell shown in Figs. 1 and 2. In this cell the mud was filtered through a train of rock cores while rotating blades kept the mud flowing over the surface of the core. The procedure was to evacuate the cores to 0.05 mm of mercury, saturate with brine, and assemble in the holder under brine. The permeability of the core train was then determined. A plastic seal was placed on the face of the core train, and a rip cord was attached from the seal to one of the blades. At the start of the test, 500 psi was applied to the mud, and the meniscus in the capillary measuring tube was adjusted to zero. When the blades were started, t,he seal was ripped from the face of the core, and filtration began. The filtration rate was at first measured by photographing the advance of the meniscus in the capillary tube. Using

Jan 1, 1966

By V. Koump, T. F. Perzak, R. G. Olsson

The rate of dissolution of recrystallized alumina in molten iron oxide in equilibrium with iron at 1450°C was studied by rotating alumina disks in the melt. The samples were rotated from 1 to 12 min at speeds from 54 to 3270 rpm. It is concluded from the experimental results that the process is limited by diffusion in the liquid boundary layer. The interdiffusion coefficient for the dissolution of alumina disks in pure molten iron oxide was estimated to be about 3 xl0-5= sq cm per sec. THE erosion of refractory materials is of considerable importance in iron- and steelmaking processes. Since many refractories contain alumina, this investigation was undertaken to develop a further understanding of the erosion mechanism. Shurygin et al.1-3 have investigated the rate of dissolution of alumina in molten silicates and molten fluorides by rotating alumina disks in various melts. The rates were reported to be limited by diffusion in the liquid boundary layer. In the present investigation the rate of dissolution of alumina in molten iron oxide in equilibrium with iron was studied in a similar manner; alumina disks were rotated at different speeds in molten iron oxide at 1450°C. The relationship between the rate of dissolution of the flat surface of the disk and the speed of rotation was used to determine whether the process is limited by diffusion in the liquid boundary layer or by some chemical reaction mechanism. APPARATUS AND EXPERIMENTAL PROCEDURE A schematic diagram of the experimental apparatus is shown in Fig. 1. The iron oxide melts were contained in 2-in.-diam high-purity iron crucibles that were centered in a cylindrical graphite susceptor. Prior to each sequence of experiments, sufficient reagent-grade ferric oxide was added to a crucible to form approximately 350 g of molten iron oxide; the depth of the melt was about 11/2 in. To prevent excessive erosion of the crucible, about 70 pct of the required iron was added to the crucible in the form of iron powder. The mixture was melted in an atmosphere of purified argon by induction heating with a 250-kc generator. After the oxide was molten, a Pt/Pt-10 pct Rh thermocouple at the exterior of the crucible was calibrated against an iron-sheathed thermocouple immersed in the melt and was thereafter used to regulate the melt temperature. All experiments were conducted at 1450°C with a probable error of 10°C. The alumina disks were constructed from pure re-crystallized alumina having a density of 3.7 g per cu cm (porosity approximately 6 pct). For each disk sample a 1-cm-diam alumina cylinder of known length (0.9 to 1.0 cm) was cemented into a ground seat at the end of a 1.27-cm-OD centerless ground alumina tube. The ends of the tube and cylinder were flush and served as the disk surface. When mounted in the apparatus the alumina tube was guided by tungsten carbide bearings and rotated by a variable-speed motor. The bearing and drive assembly could be raised and lowered in order to allow the sample to be quickly moved in and out of the melt. At the start of an experiment, a sample was preheated for several minutes directly above the melt, and then immersed in the middle of the melt to a depth of a in. and rotated for 1 to 12 min at speeds of 64 to 3270 rpm. The speed of rotation was measured by a hand tachometer. At the start and completion of each experiment, a melt sample was withdrawn with a cold copper rod and the alumina content was determined by chemical analysis. During individual experiments the alumina concentration of the melt changed by the order of 0.25 wt pct. Average melt compositions for individual experiments were used in the subsequent computations and were in the range between 0.12 and 4.3 wt pct alumina. The extent of dissolution was determined by sectioning the end of the sample and measuring the final length of the alumina cylinder with a microscope. Since the exposed end of the cylinder, i.e., the disk surface, was etched in a manner characteristic of this geometry, a number of measurements were made on

Jan 1, 1969

By E. T. Turkdogan, L. E. Leake

A number of measurements have been made on the vapor pressure of pure iron at 1600°C. Experiments were carried out by the transportation method in which a sample of iron is exposed in a furnace to a stream of pure argon, metered at a predetermined flow rate for a specified period of time. The vapor pressure was obtained from the weight loss of the sample. A detailed diagram of the apparatus used for the experiments is given in Fig. 1. It consisted of a horizontal molybdenum-wire-wound furnace fitted with a recrystallized alumina tube 1 1/8 in. internal diam. The boats, 1 by 3/16 by 1/8 in., were fired in argon at 1600°C to constant weight before use. After this treatment, subsequent heating of the boats to 1600°C gave little or no further change in weight, e.g. ±0.05 mg in 24 hr. The furnace and reaction tube were separately fed with argon from two independent flowmeters. These were connected to a common supply source via an argon purification furnace containing metallic titanium sponge at 700°C, and an anhydrone drying-tower. A rotary displacement-type meter was included in the gas train to provide a direct means of measuring the total volume of gas passed through the reaction tube. The material used was vacuum melted high-purity iron in the form of wire 2mm in diam. The following impurities were present in the iron: 0.008 pct C, 0.002 pct Si, 0.005 pct Mn, 0.008 pct S, 0.001 pct P, 0.01 pct Ni, 0.001 pct Cr, 0.006 pct Cu, and 0.001 pct Al. Samples consisting of three small pieces of this wire were laid end to end in a recrystallized alumina-combustion boat, and were separated by small fragments of alumina. The wire samples were then melted in argon to form spherical beads 2 to 3 mm in diam. After weighing, the boat with its contents was placed on the boat carrier and introduced into the cool end of the reaction tube. The entire furnace system was then flushed with argon for 30 min. At the end of this period, the flow of argon to both furnace and reaction tubes was adjusted to the desired level; then the boat was slid rapidly into the hot-zone of the reaction tube. After a known volume of gas had passed through the reaction tube, the boat was withdrawn quickly to the cool end of the furnace. When quite cool, the boat was removed from the fur-mace and placed in a desiccator for subsequent re-weighing. The semi-micro balance used in these experiments had a sensitivity of 0.005 mg. The above procedure was repeated at several flow rates within the range of 25 to 300 ml per min. The flow of argon in the annular space between the two tubes was at a rate of 300 ml per min in all experiments. During all the experiments the furnace temperature was maintained at 1600° ± 5°C by means of a temperature controller. The temperature of the reaction zone was measured with a Tinsley high precision disappearing filament pyrometer which was initially calibrated against a Pt-13 pct Rh/Pt thermocouple; the errors due to temperature measurements were within * 5°C. RESULTS Assuming that the iron vapor is in the monatomic state, the vapor pressure can be calculated from the weight loss of the sample and the volume of the carrier gas. The results obtained are plotted in Fig. 2 against the rate of flow of argon through the chamber containing liquid iron beads. At low flow rates, the thermal diffusion of iron gives an apparent high vapor pressure, but at high gas flow rates, the carrier gas is not saturated with the vapor, and therefore, low vapor-pressure values are obtained. This is now a well-known phenomenon. There is a distinct inflexion of the curve at about 120 to 160 ml per min rate of argon flow and the vapor pressure of iron within this

Jan 1, 1961

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By L. E. Tanner

A study was made of the transformation kinetics of the commercial titanium-base alloys, Ti-2.5Al-16V and Ti-4A1-3Mo-1V, using two different heat treatment cycles: 1) step-quenching to aging temperatures from a ß solution anneal and 2) water-quenching from an a+ß solution anneal followed by reheating to aging temperatures. Metallographic examination and hardness testing provided the major portion of the data, while electrical resistivity, dynamic elastic modulus, and X-ray diffraction techniques were also used to obtain critical or confirnzatory data. TTT diagrams were constructed from these results. The sheet alloys, Ti-2.5Al-16V and Ti-4Al-3Mo-lV, are of current interest to the Department of Defense. As an aid to the planning of their respective heat treatments, a program was carried out to determine the transformation kinetics of these alloys using ß and a + ß reference states. This paper presents the TTT diagrams constructed from data obtained by metallographic examination and hardness testing, as well as by X-ray diffraction, electrical resistivity, and dynamic elastic modulus determinations. EXPERIMENTAL PROCEDURE Materials—Sheets of the alloys were obtained from the producers in the "mill anneal'' condition and were tested prior to shipment to assure their meeting mill specifications. Chemical analyses were also supplied and are presented in Table I. Heat Treatment—The majority of the data presented in this study were obtained from hardness testing and metallographic examination. Sample coupons were cut from the alloy sheets and heat treated on a mass scale. The annealing cycles were operated in the following manner: 1) The ß solution anneals were carried out in a horizontal tube furnace with the bare samples protected by a dynamic helium atmosphere. Following this treatment, the samples were quickly transferred to lead, solder, or oil-bath furnaces for aging. After prescribed times at the various reaction temperatures they were water-quenched. 2) The second cycle simulated commercial practice, which requires the alloys be quenched to room temperature following the a + ß sotution anneal. This anneal was carried out in a muffle furnace with a dynamic helium atmosphere. The specimens were then reheated from room temperature to the reaction temperatures in lead, solder, or oil-bath furnaces, followed by water-quenching after prescribed times at these temperatures. Information concerning the critical temperatures of the alloys was obtained from the literature and solution treatments were based on these values. A summary of the solution annealing treatments is found in Tables II and 111. The aging temperatures for the (a - ß alloys ranged in 50°C intervals from 200°C (392oF) to approximately 50°C below the ß/a + ß transus in the first cycle and approximately 50°C below the a + ß solution temperature in the second. The transformations in these alloys were known to be rather rapid, and thus aging times started at 0.5 min and went to a maximum of 7000 min. Hardness Testing and Metallographic Preparation— Heat-treated samples were sheared and mounted in Bakelite with their cut edges exposed. After a flat surface was ground, the hardness was determined in Vpn on an Armstrong-Vickers machine utilizing a 20-kg load. Three to four impressions were made on each specimen. After this procedure, the hardness impressions were removed and the edge surfaces of the specimens were prepared for metallographic examination in the usual manner. The etchant was 20 pct HF and 20 pct HNO3 in glycerine. Electrical Resistivity—It has been shown that the isothermal reactions in titanium-base alloys can be followed by measuring the changes in e1etrical resistivity attending these transformations. As mentioned earlier, the reaction kinetics of a-ß alloys are rather rapid; thus, it would be expected that resistivity data obtained from these alloys would be more significant if measurements were made continuously at the respective aging temperatures. To accomplish this end a special apparatus, based on the current-potential principle, was assembled. Its design was derived from earlier devices constructed by Colner and zmeska1 4 and Levinson.5 The set-up provided for the heat treatment zof machined specimens (approximately 2 x l0-4in. in cross section by 3 in. in length) and the determination of their relative

Jan 1, 1962

By H. J. Levinstein, H. J. Guggenheim, C. D. Capio

An optical incestigation of the phase transformations in RbFeF, has been conducted. Details of the ferromagwetic phase transition and the metamagnetic state are disczrssed. The three-dimensional magnetic domain structure existing in bulk crystals of RbFeF3 is described, as well as the effect of the magnitude and direction of the applied magnetic field on the domain struclure. The strong magnetoelastic interaction in RbFeF, is demonstrated. The results of the direct observation of the role of dislocation subboundaries and slip bands as nucleation sites and as pinning sites for magnetic domain walls are reported. THE perovskite compound RbFeF, has recently been shown to exhibit three magnetic states.''' Above 102°K it is paramagnetic, between 102" and 87°K it is antiferromagnetic. and below 87°K it is ferromagnetic (i.e., exhibiting remanence) with a modification of the magnetization occurring at 40°K. The changes in magnetic structure at 102o, 87°. and 40°K are accompanied by shear transformations to successively lower crystal symmetry classes.3 At 102°K a second-order phase transformation to a tetragonal crystal structure occurs. The c/o ratio increases with decreasing temperature to a value of 1.0034 at 87°K where the crystal undergoes another shear transformation to an ortho-rhombic crystal structure. The magnetic modification at 40 K is also accompanied by a shear transformation to a lower crystal symmetry. RbFeF3 is unique in that in the ferromagnetic state it is transparent in the bulk to visible light, has a low saturation magnetization, a large magnetic rotation. and has good optical properties.' All these features make it an ideal material for the investigation of magnetic domain structures in bulk crystals. In addition a dislocation etch has been developed which reveals the point of emergence of dislocations with the (100) surfaces of RbFeF3,5 making it possible to determine the dislocation arrays in the material. As a result domain wall dislocation interactions can be observed in the bulk crystal. In this paper we report on 1) the crystallography of the phase transformations in RbFeF3. 2) the domain configurations as a function of magnetic field and crystal orientation. 3) the interaction of dislocations and magnetic domain walls in RbFeF,. EXPERIMENTAL PROCEDURE Since the temperature range of interest is below room temperature the dewar shown in Fig. 1 was employed. It was designed to fit on the stage of a Leitz panphot metallograph, and permitted examination of the sample at a magnification up to 150 times. The dewar consists of a double-walled glass cylinder bent into an L shape. The space between the walls is evacuated. The viewing wirldows were made of four optically flat quartz discs aligned parallel to each other and sealed to the sides of the concentric cylinders. The specimens were mounted in a holder attached to a flexible plastic shaft. Various holder designs were employed depending upon the type of observations to be made. For studies of the phase transformation between the antiferromagnetic and ferromagnetic state the holder shown in Fig. 2(d) was employed. This holder permitted accurate temperature control at 82" to 88°K by balancing the heat input from the carbon resistance heater against the heat loss to a heat sink immersed in liquid N2. Magnetic field studies were conducted by employing the holders shown in Figs. 2(a) and (b). The holder shown in Fig. 2(n) has a solenoid imbedded in it. such that the magnetic field direction is in the same direction as the incident light. The magnetic field provided by the holder in Fig. 2(b) is perpendicular to the incident light direction. The holder in Fig. 2(r) was employed when observations of the specimen were desired while an elastic bending stress was applied to the sample. The stress was applied to the sample by pulling a wire from outside of the dewar. The wire was attached to a lever pivoted on the holder. which caused the knife edge of the lever to push against the sample. The crystal growth and the sample preparation were described previously.' PHASE TRANSFORMATIONS The first phase transformation in this system is from the cubic perovskite structure to n tetragonal

Jan 1, 1970

By P. Majani, F. P. Kokesh, M. Grosmangin

Determination of the quality of cementation of casing in oil wells in the past has involved inflow and circulation tests to insure that the producing zones were adequately sealed off from the adjacent zones. Existing logging methods, such as temperature and radioactivity surveys, may detect the presence of cement behind the casing. However, the qualities of the cement (i.e., its hardness and particularly its bond to the casing) are not indicated. The new logging method described in this paper operates on the principle that the attenuation of a sonic pulse transmitted by a casing is greatly increased when that casing is bonded to an outer annulus of hard material (such as set cement) which has an appreciably smaller sonic-wave velocity than that of the casing. The down-hole tool contains a source of recurrent sound pulses which are detected by a receiver spaced a few feet from the source The amplitude of the detected casing-borne pulse is measured, and the resulting signal is transmitted to the surface where it is recorded vs depth. Since amplitude is a function of attenuation, the log is readily interpreted. Laboratory studies have shown straightforward relationship between attenuation and such variables as source-detector spacing and per cent of circumference bonded. It is shown that cement not set or not bonded to the casing has compara- tively little attenuating effect. Field examples show not only the cement top, but also the variation in cementation quality below the top. Further, the increase of bonding with time and after squeeze cementation is depicted. The detection of poor cement jobs is confirmed by production tests and by formation-test results. It is anticipated that the method will have wide application in evaluating cementation quality prior to formation testing in completions and recompletions. The analysis it affords may aid in further improving cementation techniques. INTRODUCTION The main purpose of oilwell cementing is to isolate a production zone from other undesirable zones. To investigate whether this purpose has been accomplished, several logging methods have been used such as temperature logs, radioactive tracer logs, etc. While these logs all respond to the presence of cement behind the casing, they do not indicate the degree of bonding of the cement to the casing. Early in the application of sonic logging, it was noticed that considerable attenuation of sound signals takes place in cemented pipe and is often made evident on the standard Sonic log by cycle skipping.' The development of a circuit capable of continuously recording the amplitude of the casing-borne sound signal has made possible an extensive series of laboratory and field tests, which gave the following results. The amplitude of a sound signal after it has traveled in a firmly cemented pipe is only a small fraction of that recorded by the same device in free pipe. This provides a wide spectrum of energy levels; for given local conditions, empirical values of the amplitude can be correlated with the quality of cementation. Interpretations made in this manner generally have been confirmed by production tests, circulation tests and squeeze cementation. The purposes of this paper are to give a general description of the new logging method and to present some laboratory and field results. CYCLE SKIPPING Early attempts to study the quality of the cement behind the casing were performed with a standard Sonic log, which measures the transit time At, and were based on the well known phenomenon of cycle skipping.' Cycle skipping normally is interpreted as being a manifestation of weak signals at the receivers. The log of Fig. 1 was run with the recording instrumentation adjusted to enhance cycle skipping. A mirror-image presentation was used for better visual interpretation. The transit time of sound in steel is about 58 microseconds/ft (corresponding to a velocity of 17,000 ft/ sec), and the portions of the log where this value is recorded are interpreted as zones with no cement bond. Where cycle skipping produces a higher value of At, weak signals (or a high rate of attenuation) are indicated, and a good cement bond may be present. The occurrence of cycle skipping, however, depends too much on instrument adjustment to give a uni-

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

By J. E. Burke, A. M. Turkalo

IN 1923 Desch¹ pointed out that the grains in a metal which is anisotropic with respect to its thermal coefficient of expansion would contract differently upon cooling, and that the stresses developed might approximate the plastic strength of the metal. More recently Boas and Honeycombe2-5 studied the behavior of several metals upon thermal cycling and observed that the stresses developed in arlisotropic metals are great enough to produce slip lines in individual grains and a roughening of the specimen surface. This phenomenon they have named "thermal fatigue." The mechanism they propose involves essentially a kneading of the grains, the deformation being alternately in compression and tension in a given grain as the temperature is changed in one direction and then the other. The present work was undertaken to investigate the possibility that an additional mechanism might operate to produce plastic deformation during thermal cycling—a "thermal ratchet" that depends upon a combination of grain boundary flow to relax the stress that develops between differently oriented grains upon raising the temperature and transcrys-talline slip to relax the oppositely directed stress which develops on lowering the temperature. Thus, thermal cycling should produce a nonreversible distortion such that certain grains will change shape differently from their neighbors with a simultaneous displacement being produced at the grain boundary. Temperature Dependence of Grain Boundary and Grain Strength The critical resolved stress for the initiation of slip in metal grains is only mildly affected by temperature." For example, in cadmium it decreases from 0.15 to about 0.05 kg per sq mm when the temperature is increased from 20° to 458°K and further temperature increase causes little further decrease. On the other hand, the work of KG1 indicates that the grain boundaries behave in a viscous fashion that can be described8 by the expression: t = BVexp(Q/RT) [1] t is the shearing stress on the boundary; B, a constant; V, the flow rate at the boundary; Q, the activation energy for grain boundary flow; R, the gas law's constant; and T, the absolute temperature. Eq 1 indicates that the stress necessary to cause a given grain boundary flow rate, V, decreases rapidly with increasing temperature. The value of the constant B is such that at sufficiently low temperature and ordinary strain rates deformation will occur preferentially by slip rather than by grain boundary flow. There is considerable evidence to indicate Consider the bicrystal shown in Fig. 1. In grain 1 the slip plane lies 45 " to the boundary while in grain 2 the slip plane is 90" to the boundary. The coefficients of expansion of the grains in a direction parallel to the length of the crystal are a1 and a, with a, > a2 for the orientations shown. The sequence of events that can occur upon heating and cooling this specimen is illustrated schematically in Fig. 2. Initially there is assumed to be no stress in the specimen (A). Upon heating, grain 1 attempts to become longer than grain 2, but is constrained by grain 2. Thus grain 1 is loaded in compression and grain 2 is loaded in tension, and a shearing stress is present across the boundary (B). As the temperature is increased, the stress will build up, and finally grain 1 will be plastically deformed by slip, since the greater stress is resolved on its slip planes. Any further heating will result in more slip and the stress will remain constant until some temperature T* is reached where the stress can be relaxed by grain boundary flow.† At this relaxation temperature (C) a step will appear between grain 1 and grain 2. Further heating above T* will cause grain 1 to become relatively longer, but no stress will appear because the grain boundary is too weak to support the stress (D). Upon cooling again, at T* (E), the grain boundary will again be able to support a shearing stress, and upon cooling further, grain 1 will be loaded in tension and grain 2 in compression (F). When the decrease in temperature below T* is sufficient to impose the critical shear stress upon the slip plane of grain 1, it will be stretched by slip.

Jan 1, 1953

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By A. Lubinski, J. L. Logan, W. S. Althouse

A4ost gas twells and flowing oil wells are completed and treated through a string of tubing and a packer. Changes in temperature and in pressure inside or outside the tubing will: (I) if free motion of the tubing inside the packer is permitted, increase or decrease the length of the rubing; or (2) if free motion is prevented, induce forces in the tubing and on the packer. If pressure inside the tubing is greater than outside, the tubing may buckle helically even in the presence of a packer-to-tubing tension. The tubing will always buckle, and much more severely, if free motion is permitted. The buckling may be prevented by pulling the tubing in sufficient tension. The prediction of these forces and tubing movement has here to fore been based upon calculations that did not inciude helical buckling. This paper preseitts means with which these length or force changes can be calculated while taking into account the effect of helical buckling. To avoid damaging formations, failure of remedial operations, or damage to the tubing or packer, application is made to practical problems involving calculations of the required length of seals, amount of sluckoff or tension, and prevention of permanent corkscrewing. INTRODUCTION Leakage of a packer may result in costly failures of such operations as squeeze cementing, hydraulic fracturing, etc. To avoid such failures, the authors are often asked questions pertaining to the length of necessary seals, the amount of necessary slackoff, etc. Published work' does not take into account helical buckling of tubing. Investigation of helical buckling was prompted by the fact that allowance must be made for this phenomenon in order to provide relevant answers. In the past, theoretical work on helical buckling was confined to conditions for which such buckling does not The mathematical treatment of behavior in a buckled condition, given in the Appendix, is novel. Assumptions upon which this investigation is based are listed and discussed in a special section. The following are a few of the many kinds of problems which may be solved with this paper. 1. Consider a packer in which tubing may move. Such movement will occur after pressures and temperature are changed. The paper provides means for: (a) calculating the amount of such movement and, therefore. the required length of seals; and (b) calculating the necessary amount of initial slackoff, for which there is no danger of unsealing the packer, if the length of seals is given. Such calculations, as well as those which follow, tully take into account the fact that part of the movement ib due to elastic helical buckling of the lower part of the string. This buckling may occur even in tubing under tension. Insufficient initial slackoff for a given length of seals, or insufficient length of seals for a given slackoff, may result in costly failures. A field case of such a failure will be given further in this paper. 2. In the case in which tubing cannot move in the packer, changes of pressure and temperature result in tubing-to-packer forces and forces in the tubing above the packer, both of which may be calculated. This knowledge is important because, if these forces are too large, the) could damage the packer or the tubing. 3. For wells in which wireline tools are to be run through the tubing, the paper provides means to keep the tubing from buckling, thereby permitting free passage of tools. 4. In deep wells, mainly in the presence of large casing, tubing may become "corkscrewed", i.e., take a permanent helical set. A field case is described further in the text. Using this paper, one may calculate in advance conditions under which permanent corkscrewing would occur, and then take preventive steps. HELICAL BUCKLING Consider a string of tubing, freely suspended in the absence of any fluid inside casing, as shown in Fig. I(a). Now consider an upward force F applied at the lower end of this tubing. This force compresses the string; and if the compression is large enough (which is always the case in actual problems), the lower portion of the string will buckle into a helix, as shown in Fig. 1 (b). The lower end of the tubing is subjected to a compression F. This compression decreases with the distance from the bottom and becomes nil (neither compression nor ten-

By M. F. Williams, L. G. Hendrickson

IN classification of pulps bearing magnetized ferromagnetic particles, depolarizing is of great importance. If size separation is to be effective, particles must be individual rather than in floes. Depolarizing is also practiced in heavy medium separations in which ferrosilicon or magnetite is the medium. When particles of ferromagnetic material have been removed from a magnetic field, residual magnetism causes agglomeration. The term depolarizing refers to the operation of reducing or eliminating this residual magnetism and may thus be considered magnetic deflocculation. The terms demagnetizing and randomizing are also used. At the Research Laboratory of Oliver Iron Mining Div. in Duluth a method was developed for measuring depolarization of the pulp of ferromagnetic material. Experiments were made with Mesabi taconite,' a natural magnetite of low coercive force. Ferromagnetic materials of higher coercive force, such as lodestone or the artificial magnetite produced by reduction roasting of hematite, present a more difficult problem, which was not within the scope of this investigation. It is possible, however, that some of the techniques evolved for measuring and calculating electrical characteristics of alternating current coils would be of use in depolarizing high coercive force material, particularly in conjunction with high-frequency alternating current, as proposed by Hartig and others.'," Properties of Ferromagnetic Materials:'7 Experimental work, described below, has shown that if a sample in the magnetized state is heated above the Curie point and cooled, much of the preferred orientation is destroyed and the sample is substantially depolarized. It has been thought that when the sample cools below the Curie point the domains cancel each other, leaving a zero net moment. However, such particles still exhibit a tendency to cohere, and undoubtedly this is caused by the forces of residual magnetism. -AS measured by the percent depolarization, this tendency is reproducible for any sample upon repeated heating above the Curie point and subsequent cooling and is independent of the initial state of magnetization. It is postulated, therefore, that as the material is cooled below the Curie point the domains in any particle do not completely cancel each other, but rather are preferentially oriented to some extent. Mechanism of Depolarizing with Alternating Current Magnetic Fields: It is believed that when ferromagnetic material is passed through an alternating magnetic field, depolarizing occurs in the decaying portion of the field. As the particles pass through the portion of highest intensity they become magne- tized. If the particles are not free to move, the polarities of the particles will be reversed (by a mechanism similar to that described above for magnetism) at a frequency equal to that of the applied field. As the material moves through the decaying field, intensity levels become such that a domain does not completely reverse, but stops on an axis of easy magnetization. By the time the material reaches the point of zero field intensity, a state of fairly random orientation of domains is achieved. If conditions are such as to give a completely random orientation, the particle will have little or no external magnetic field, and a pulp of such particles will be depolarized. Previous Work In 1918 E. W. Davis was granted a patent for demagnetization of magnetite pulps.' His method consisted of passing the pulp through a tapered coil, activated by alternating current of normal frequency (60 cycle). This method, with minor modifications, has been used almost universally in all pilot plants and commercial installations in which depolarization of low coercive force materials has been required. Hartig, Onstad and Foot2,3 avd made a detailed study of the factors involved in depolarizing both low (below 100 oersteds) and high (above 100 oersteds) coercive force material. They developed a method for evaluating the relative degree of depolarization of any pulp based on the settling characteristics of the pulp. Their standard of comparison was a sample heated to above the Curie point and cooled in a zero field, all in a neutral atmosphere.* For low coercive force material they found treatment.Thisprocedure is subsequently called, in this report,theCurie that results equivalent to Curie treatment could be

Jan 1, 1957

By Leendert de Witte

Conventional resistivity logs consisting of a short normal, a long normal, and one or more long lateral curves do not give data that allow a complete quantitative interpretation in beds thinner than 20 ft. Reservoir rocks usually exhibit zones of continuous homogeneity of quite limited thickness where the long lateral curves become useless because of adjacent bed effects and boundary phenomena. If the beds are 12 ft or thicker, the short and long normals may be used for qualitative interpretation, which can be streamlined by the application of simplified departure curves. For beds of a thickness less than twice the long normal spacing, this procedure breaks down. The combination of the limestone curve, the later-olog or guard electrode log, and the microlaterolog permit quantitative interpretation for beds that are at least 10 ft thick, provided the mud resistivity and the hole diameter are known with sufficient accuracy. For beds thinner than 10 ft, combinations of the microlaterolog with short spaced laterologs and pseudo laterologs appear to be promising. Interpretation of these curves again requires the application of simplified departure curves. Resolution of various possible combinations was analyzed using departure curve data calculated on the Whirlwind I computer at the Massachusetts Institute of Technology. A field example is shown using the microlaterolog-microlog combination, and the combination of a 6-in. modified laterolog plus a 6-in. pseudo laterolog. INTRODUCTION For the purpose of quantitative interpretation of resistivity logs in porous formations, we want to obtain two essential quantities from the logs, namely, the true resistivity of the undisturbed formation, Rt, and the resistivity of the part of the formation invaded by mud filtrate, Rt. The apparent resistivities of all conventional logging devices are functions of these two parameters and are also influenced by a third unknown parameter, the diameter of the invaded zone, d. It has been shown' that from the normal curves alone it is impossible to arrive at a unique solution for the three unknowns, Rt, R1, and d1. In very thick homogeneous beds, if invasion is not too deep, we can obtain a fair approximation to Rt from the long lateral curves and then use the two normal curves to find Rt and d1 Even under the most favorable conditions, the resolution of this system is not very good. The short normal does not give a reasonable approximation to R1 unless invasion is very deep (dl>16 hole diameters). For very deep invasion, however, the long laterals no longer approximate Rt. For bed thickness between 20 and 40 ft, the long laterals are affected appreciably by the adjacent beds; and the curves are distorted by boundary anomalies to the extent that they lose their quantitative usefulness in most cases. For the same bed thicknesses, the normal curves still function reasonably well. Although it is impossible to find unique solutions Lor R1 and Rt using the normal curves alone, we can obtain a reasonable approximation for the ratio R1/Rt through the use of simplified departure curves. This fact was brought to our attention by A. J. de Witte, geologist with Continental Oil Co. As the magnitude of Rl/Rt is a major clue to the presence of oil in formations, this method can be used to good advantage for qualitative analysis and will be discussed in somewhat greater detail. With the aid of suitable bed thickness corrections, the analysis of the normal curves may be used for bed thicknesses larger than 12 ft. For thinner beds, the method rapidly loses its resolution; and we have to resort to different types of resistivity logs if we want to attempt to analyze the curves quantitatively. The inadequacy of conventional resistivity curves in thin beds is far more serious than generally realized. Fig. 1 shows a conventional E. S. with a 16-in. and 64-in. normal and a 16-ft lateral through a section of Lansing-Kansas City lime, in comparison to a guard electrode survey through the same section in a neighboring well. The porous zones, which show up as low resistivity breaks on the guard electrode log, are completely masked by adjacent bed effects and boundary anomalies on the conventional curves. Even the short normal shows most of the porous Zones only as Vague deflections and in many cases fails to register Their

Jan 1, 1955

By J. L. Huitt, J. L. Pekarek, D. K. Lowe

In a theoretical study of hydraulic jetting, the velocity of the abrasive material relative to the velocity of the fluid in the jet stream is analyzed as the jet stream moves through the convergent and straight sections of the nozzle and the region between the nozzle exit and target. The results revealed that the abrasive material exits from the jet nozzle at a lower velocity than the fluid. The exit pmticle velocity can be increased by increasing either the density of the fluid or the length of the nozzle, and/ or decreasing either the particle density or particle diameter. In the divergent jet stream, there exists a point after which the particle velocity exceeds that of the fluid. The relative velocities were considered in the derivation of an equation to predict cutting rate of a circumferential notch and maximum notch depth. Data of a general nature and data which substantiate the theoretical results were obtained experimentally. INTRODUCTION The use of a fluid containing an abrasive material has been an established technique for cleaning and cutting for many years. In the petroleum industry, the early effort to use this technique1 to perforate and/or to overcome wellbore damage met with only limited acceptance because of the short life of the jet nozzle. With the introduction of improved perforating techniques, and later, hydraulic fracturing, the use of hydraulic jetting as a well completion technique became even less appreciated. It was only in recent years that interest in hydraulic jetting was revived. Once this interest was revived, the results of surface tests stimulated the interest of the industry even more than the state of the technology probably warranted because many of the tests were not appropriate for down-hole conditions. However, because of the stimulated interest, the development of the jet nozzle progressed very rapidly to the point where the nozzle life was no longer a prob- lem. With this accomplished, the use of hydraulic jetting in well completion became an accepted practice in a short time. The purpose of this paper is to present a theoretical analysis of the hydraulic jet stream as it passes through the nozzle and travels to its target. With a better understanding of the jet stream and the effects of various parameters, the performance of the process can be predicted more accurately. Equations are presented for cutting rate as applied to circumferential wellbore notching that relate the jet stream make-up, notch configuration and formation material. Also, experimental data are presented on some factors pertinent to hydraulic notching that are not theoretically analyzed. RELATED STUDIES Most of the studiesl-5 reported in the recent literature have pertained to the more practical aspects of hydraulic jetting; i.e., the effects of certain parameters as interpreted from experimental results, and the application of hydraulic jetting in well completion. In reviewing the effects of various parameters, it is interesting to note the reported depths of penetration obtained under various imposed conditions. In general, the depths vary from a few inches to several feet; however, a depth of penetration of less than 6 in., as reported by Thompson,4 seems more realistic for the usual field practice of hydraulic jetting with sand in water for a period of 20 to 30 minutes. In addition to the practical aspects, the study of Brown and Loper5 included a theoretical approach to hydraulic jetting. Their study resulted in the development of a theoretical expression for the maximum depth of penetration if jetting were continued for an infinite time. An analysis of the equations presented reveals that the initial cutting rate is infinite. The equation expressing centerline velocity is that of Forstall and Gaylord,6 which is applicable for a jet stream exiting in a large stationary medium. Since practically all of the fluid pumped into a perforation (or cut) must flow back through the perforation prior to re-entering the wellbore, a description of the medium as finite and non-stationary seems more reasonable. Thus, in this

By R. J. Lutton

Empirical data from 91 rock excavations have been used to construct a family of slope curves on a chart relating excavation height and inclination. The highest and steepest slopes from each excavation are plotted and connected by a line. The 31 1ines appear to establish one or two geometrical slope fields through which the curves are projected. The curves apparently represent a lumped eflect of many factors too complex to be considered individually. Important factors such as geological structure or ground-water conditions can dominate the picture, but where these factors do not overshadow others, the slope chart should be useful for estimating or checking optimum inclination. The U.S. Army Corps of Engineers (USAE) has been engaged since 1962 with the U.S. Atomic Energy Commission in a joint research program to develop nuclear excavation technology. The Corps is responsible for collecting the requisite data on engineering and construction problems associated with nuclear excavation. The ultimate objective is to develop a capability to use nuclear explosives as a construction tool on public works projects such as harbors and canals. The present study on empirical inclination-height curves for conventionally excavated slopes is an outgrowth of an investigation' sponsored by the USAE Nuclear Cratering Group on applicability of data from existing excavations in establishing guides for engineering judgment in crater excavation. Data were generously contributed by over 50 mining companies among other organizations. Inasmuch as several companies preferred that their contribution be anonymous, all data are treated so here. Some Factors Affecting Stability Many factors affect or are suspected of affecting the stability of excavated slopes, e.g., adverse structural orientation, degree of structural ordering, ground water, climatic conditions, mechanics of excavation, and plan-profile configuration. Such factors are lumped together in developing a slope chart. Obviously geological structure and ground water can overshadow all other factors. Where such is the case, the simplification of slope charts may give an erroneous picture (not conservative enough). A further complication results from the fact that the concept of stability may vary according to the use of the excavations. For example, slope adjustments that would be regarded as failure in a powerhouse excavation, might be tolerable in a mining operation. Mine slopes are continually being modified by further excavation, and instability that would develop in a similar permanent excavation slope over a period of years might not have time to develop in a mine. Inclination vs. Height Charts Charts of inclination vs. height for particular formations or conditions have been used in the past as an aid for designing excavation slopes. Some of these have been based upon empirical analyses of collections of data and experience. MacDonald" and Lane have presented slope tables and charts for excavated and natural slopes in relatively weak sandstone and shale. Coates' has shown an inclination-height chart for slopes in incompetent rock. Most organizations have developed slope design criteria which relate bench widths, heights, and inclinations to use in various rocks. Slope data collected in present studies can be similarly used to develop inclination-height charts; however, a plot of all slopes on such a chart shows very little because of the wide spread of the data. Reasons for the dispersion of points are: (1) many slopes are not carried at optimum inclination, particularly in mines where maintaining roadways and following irregularities of ore bodies are more important than achieving steep inclinations; (2) many engineers and geologists with varied backgrounds and viewpoints have been involved in designing these slopes; and (3) each slope is characterized by a unique combination of factors affecting stability and in turn optimum inclination. Significant curves can sometimes be constructed where the points can be grouped into related clusters from the same excavation. The essence of this approach appears when only two slopes from each excavation are considered—the highest slope and the steepest slope, connected by a line segment (Fig. 1). This reduces considerably the usable data because in many cases only one of these two slopes is available. Nevertheless, the concession seems justified. Construction of Slope Curves Ninety-one pairs of points and connecting line segments were assembled in this study. The line segments were assumed to approximate a geometrical slope field (Fig. 2), and a family of curves has been visually projected through to represent the slope field. It should be

Jan 1, 1971

By Lyman Johnson

Single crystals qf copper in "single slip" orientatiorzs have been deformed in compression. During defortnation all of the independent deformation parameters have been measured. These parameters consist of thefive strain components and three components descrihing the lattice rotation. By a finite strain analysis these pararmeters , forrming a deformation gradient martrix, are related to the amounts of slip on each of the twelve slip systems. The results show that the amount of secondary slip is about equal to the amount of primary slip. This is an order of magnitude larger than has been believed previoutsly. ACCORDING to early theory and experiments, when a single crystal of a fcc metal is deformed in tension or compression it should deform by slip on only one slip system until the stress axis reaches a symmetrical orientation.' However. the observation of a large increase in the secondary dislocation density during ..single slip" makes it clear that some slip does occur on secondary systems. Knowledge of the amount and distribution of this secondary slip is essential to a complete understanding of the mechanisms of single-crystal deformation. Ahlers and Haasen 2 and Mitchell and Thornton1 have tried to detect the amount of secondary slip in single crystals of silver and copper, respectively. Each simultaneously measured the angle A, between the tensile axis and the primary slip direction and the length 1 of a gage section of the specimen after incremental amounts of deformation in tension. The measured A, was then compared with the theoretical single slip angle hp. given by sin Ap = j sin . hO where ?o was the initial angle between the tensile axis and the primary slip direction and lo was the initial gage length. In both sets of experiments a small but systematic difference between ?e and ?p was found. This difference must be due to the occurrence of secondary slip. However, as Mitchell and Thornton1 pointed out. nothing quantitative can be said about the amount and distribution of this secondary slip from the measurements that they made. The reason that no quantitative conclusions could be made is because no unique solution for the distribution of slip on the twelve fcc slip systems can be determined from only two measured deformation parameters such as A and 1. There are, in fact, eight independent macroscopic deformation parameters that can be measured when a single crystal undergoes a homogeneous deformation. Physically these can be thought of as the five finite strain components and the three angles describing the crystal lattice rotation. All eight of these parameters were measured by Taylor4,5 for aluminum deformed in tension and compression. At that time the concern was to show that slip occurs on {111 (110) systems in fcc metals, and the mathematics were not available to determine what slip distributions were compatible with the measurements. In this paper the mathematics6,7 are developed that allow the slip distribution to be determined from these measurable macroscopic deformation parameters. The analysis is applied to the measurements of the strain and lattice rotation of copper single crystals deformed in compression. The results show that the amount of secondary slip is an order of magnitude larger than had previously been thought. CRYSTALLOGRAPHIC DESCRIPTION OF A HOMOGENEOUS DEFORMATION The deformation of a solid body can be represented by a transformation matrix F that transforms the un-deformed state into the deformed state. Consider a vector X connecting two material points in the unde-formed material and the vector x connecting the same two material points after deformation, where both vectors are referred to the same set of Cartesian axes. The final vector x is related to the initial vector X by the equation: X = FS. [2] Eq. [2] can be considered as the equation defining F, which is called the deformation gradient matrix. Its components are: If the deformation is homogeneous, the transformation is linear and the components of F are constants. Using subscript notation, if P is the unit vector in the initial direction of a material line, the components of the unit vector p in the direction of the same material line after deformation are given by:

Jan 1, 1970

By A. Stanley, J. C. Mead

The MacIntyre Development of the National Lead Co. is located at Tahawus, N. Y. The operations involve the mining and concentrating of a titaniferous iron ore to produce an ilmenite concentrate and a magnetite concentrate. Construction of the MacIntyre plant was commenced during the summer of 1941,when world conditions threatened to cut off the supply of Indian ilmenite. An open pit mining operation was developed and the crushing and milling equipment put in operation in July 1942. A general description of the operation was given in the Adirondack Issue of Mining and Metallurgy for November 1943. The metallurgy of the mill operation was described by Mr. Frank R. Milliken,* Plant Manager, National Lead Company, MacIntyre Development, and presented at the AIME New York Meeting, February 1948. The magnetite concentrate produced in the milling operation was too fine (minus 20 mesh) to be used directly in iron blast furnace operation, and most of the magnetite had to be stockpiled in 1942 and 1943. In 1943, the Defense Plant Corp. built a Greenawalt sintering plant at Tahawus, N. Y., to put the magnetite concentrate in a more suitable form for use in the iron blast furnace. The Greenawalt sintering plant consists of three 10 by 25 ft sintering pans designed to produce 1800 gross tons of sinter per 24 hr. The vacuum to each pan is produced by two Greenawalt fans in series, pulling approximately 30,000 cu ft of air per minute at 50 in. water gauge vacuum. The plant started operation in August 1944. The present plant production averages 25 tons per operating pan hour (approximately 224 lb per operating hour per square foot of grate area) of plus 1 in. sinter. Raw feed to the plant consists of 61 pct magnetite, 4 pct anthracite coal culm, and 35 pct minus 1 in. return fines which are conveyed to a pug mill where the materials are mixed thoroughly and water added to give the mixture 5.5 to 6 pct moisture. The mixed prepared feed is conveyed to two 4 by 10 ft vibrating screens where the minus 1 in. plus 5/8 in. return fines are screened out and discharged into a surge bin for use as a hearth layer. The minus % in. prepared feed is discharged into another surge bin for use as prepared feed. A charge car, electrically operated, having a capacity of one charge of prepared feed and several charges of hearth layer, lays a thin layer of plus 5/8 in. return fines and 9 1/2 in. depth of prepared feed into the pans. A fluffing roll and a vibrator on the car fluffs and spreads the prepared feed into the pans. An ignition car, electrically operated, ignites the top of the bed with a 30 sec flash burn. The 9 1/2 in. bed sinters in approximately 13 min. Dumping the pan, and recharging and igniting the bed requires 2 min. To improve the quality of the ilmenite concentrate produced in the mill and to reduce the amount of titanium dioxide lost in the mill tailings and in the magnetite product, extensive research work and pilot plant operations have been done on grinding the crude ore to minus 65 mesh size (rather than to minus 20 mesh) and concentrating it by a combination of magnetic separation (for magnetite recovery) and flotation (for ilmenite recovery). These tests have proved successful in increasing ilmenite recovery and grade. With the development of the ilmenite flotation process to a stage where a full scale flotation plant was in the design stage, the problem arose of handling the 65 mesh magnetite concentrate that would be produced. In order to study and solve the problems of handling and sintering the 65 mesh magnetite in the sinter plant, a pilot sinter plant was plus from John E. Greenawalt. The effect of using 65 mesh magnetite in the sintering operations was then studied on the 2.4 sq ft test pan, operating under conditions as similar to the large plant as could be set up in the laboratory. A series of tests were run in the test pan on present sinter plant feed that had been mixed in the plant pug mill. An average production and an average quality of sinter produced in this series

Jan 1, 1950

By C. E. Hottman, R. K. Johnson

Fluid pressure within the pore space of shales can be determined by using data obtained from both acoustic and resistivity logs. The method involves establishing relationships between the common logarithm of shale transit time or shale resistivity and depth for hydrostatic-pres-sure formations. On a plot of transit time vs depth, a linear relationship is generally observed, whereas on a plot of resistivity vs depth, a nonlinear trend exists. Divergence of observed transit time or resistivity values from those obtained from established normal compaction trends rinder hydrostatic pressure conditions is a measure of the pore fluid pressure in the shale and, thus, in adjacent isolated permeable formations. This relationship has been empirically established with actual pressure measurements in adjacent permeable formations. The use of these data and this method permits the interpretation of fluid pres.rure from acoustic and resistivity measurements with an accuracy of approximately 0.04 psilft, or about 400 psi at 10,000 ft. The standard deviation for the resistivity method is 0.022 psi/ft, and for the acoustic method 0.020 psi/ft. Knowledge of the first occurrence of overpressures, and of the precise pressure-depth relationship in a geologic province, enab1es improvements in drilling techniques, casing progroms, completion methods and reservoir evalzmtions. INTRODUCTION CENKRAL STATEMENT Operators engaged in the search for and production of hydrocarbon reserves in Tertiary basins are more and more frequently confronted with complications associated with over pressured (abnormally high fluid pressure) formations. This is particularly true in the Texas-Louisiana Gulf Coast area. The problems associated with these formations are of direct concern to the combined activities of all phases of operations, i.e., geophysical, drilling, geological and petroleum engineering.' - Knowledge of the pressure distribution of a given area of operations would greatly reduce the magnitude of many of these complexities and in some cases would completely eliminate specific problems. his pape; presents techniques developed for estimating formation pressures from interpretations of acoustic and electric log data. Specifically: the acoustical and electrical properties of shales, reflected by conventional acoustic and electrical surveys, can be used to infer certain reservoir properties, such as formation pressure, at any level in a well. It has been possible to develop these techniques because of a firm understanding of the basic principles that govern and apply to such overpressured provinces. NORMAL PRESSUKES Normal pressures refer to formation pressures which are approximately equal to the hydrostatic head of a column of water of equal depth. If the formations were opened to the atmosphere, a column of water from the ground surface to the subsurface formation depth would balance the formation pressure. On the Gulf Coast, the shallow, predominantly sand formations contain fluids which are under hydrostatic pressure. These formations are said to be normally pressured or to have a normal pressure gradient.* Experience has shown that the normal pressure gradient on the Gulf Coast is approximately 0.465 psi/ft of depth. OVERPRESSURES Formations with pressures higher than hydrostatic are encountered at varying depths in many areas. These formations are referred to as being abnormally pressured, abnormally high pressured, or overpressured. Formation pressures up to twice the hydrostatic pressure have been observed. These formations require extreme care and much expense to drill and to exploit. COMPACTION-FLUID PRESSURE RELATIONS THEORY The generation of overpressured formations in Tertiary sections of the Gulf Coast and several other Tertiary sedimentary basins is, in general terms, considered to be primarily the result of compaction phenomena.' This portion of the paper presents a brief review of the theory which associates compaction and fluid pressure relations, and should thus provide the necessary background for an understanding of the techniques presented. See Hubbert and Rubey' for a more comprehensive treatment of this subject. The theory of the consolidation of a water-saturated clay' has been well established by workers in soil mechanics. The concept is explained by a model with perforated metal plates separated by metal springs and water and enclosed in a cylindrical tube. Fig. 1 is a schematic representation of such a model (see Ref. 5, Fig. 27, page 74). The springs simulate communication between clay particles, and the plates simulate the clay particles. Mano-

Jan 1, 1966