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By R. F. Hehemann, R. H. Goodenow

Thermal arrest, hot-stage microscopy, and transtnission electron microscopy techniques have been employed to study the transformations in low-carbon iron and Fe-9 pct Ni alloys. In continuous cooling experiments, each alloy transforms at an essentially constant temperature for cooling rates below the critical rate required for martensite formation. However, high-tenzperature transformation in pure iron takes place by a different mechanism than that in the 9 pct Ni alloys. Pure iron exhibits an equi-a a structure with a low and random dislocation density while the 9 pct Ni alloy exhibits a cell or lathlike substructure analogous to that of low-carbon martensite. This same substructure characterizes upper bainite in higher-carbon inaterials. UNTIL relatively recently, diffusionless transformations have been considered to take place by the same mechanism and have been termed mar-tensitic transformations.l-3 The most characteristic feature2 of this mode of transformation is the shape change produced by a shear deformation and growth of the product phase frequently occurs at an extremely high velocity approaching that of an elastic wave.4'5 A different mechanism of diffusionless transformation was recognized first in Cu-Ga and other copper-base alloys.6,7 From the absence of surface tilting in these alloys, it has been concluded that transformation is not accomplished by the cooperative shear displacements that occur in mar-tensitic reactions. Transformation presumably takes place by the rapid movement of an incoherent interface which is capable of propagating across parent grain boundaries. Although the transformation is diffusionless in the macroscopic sense, advancement of these interfaces is accomplished by an atom by atom rearrangement. Transformations of this type therefore require thermal activation and are generally operative only at high temperature. Although requiring short-range diffusion at the interface, propagation still occurs so rapidly that the reaction cannot be suppressed with normal cooling rates.7 The resulting microstructures exhibit large, irregular-shaped regions of the product phase, which are essentially free of crystallographic features. Consequently, these reactions have been termed massive transformations. Transformation by the massive mechanism has been reported to occur in ferrous systems involving pure iron and binary alloys of iron with nickel, chromium, and silicon by Gilbert and owen.' The Fe-Ni system is of special interest in that the massive transformation was observed in alloys with less than 15 pct Ni while alloys having more than about 28 pct Ni transformed by the conventional mar-tensitic mechanism. By employing cooling rates substantially higher than those used by Gilbert and Owen, Swanson and Parr have been able to suppress the massive transformation in alloys with 0 to 10 pct Ni9 and produce martensite as revealed by surface relief. The massive transformation in the alloys having less than 15 pct Ni was identified by the lack of surface relief and an irregular rather than clearly acicular microstructure.' Speich and Swann, using thin-foil electron microscopy, identified three distinctly different structures10 in quenched binary Fe-Ni alloys. From 0 to 4 pct Ni the structure consisted of blocky grains of a with a low and random dislocation density. Alloys with 4 to 25 pct Ni exhibited a cell structure with a high dislocation density; and at greater than 25 pct Ni the structure consisted of internally twinned plates. The structural change at approximately 4 pct Ni suggests that alloys with low nickel content transform by a different mechanism than those with intermediate nickel contents and the transition from the cellular to the internally twinned structures at approximately 25 pct Ni is analogous to the transition from needles to internally twinned plates that occurs over a narrow range of carbon contents in Fe-C martensites.11,12 Conventional bainitic and martensitic modes of austenite decomposition operate in ternary Fe-C-Ni alloys having less than 10 pct Ni. This investigation was conducted in order to explore the conditions under which the massive, bainitic, and martensitic transformations occur and the relationships between these modes of decomposition.

Jan 1, 1965

By E. L. Claridge, K. S. Lee

Areal sweep efficiency of oil displacement by enhanced-viscosity water exhibiting pseudoplastic behavior was measured in a Hele-Shaw model representing one-quarter of a five-spot pattern. The pseudoplasticity of polymer solutions and the velocity distribution in the five-spot pattern produced a condition under which the mobility ratio between the displacing and the displaced fluid could not be assigned a single value. Instead, the movement of the displacement front is governed by local mobility ratios which are also time dependent. The areal sweep at breakthrough with polymer solutions was poorer than the sweep obtained with Newtonian fluids of comparable viscosity. However, the areal sweep at 1 PV throughput was greatly improved as compared to flood water without polymer. It was also demonstrated that, even after the oil-cut had declined to a low value during a regular waterflood, switching to polymer flood efficiently swept out the oil remaining in the model. INTRODUCTION The behavior of fluid displacements in isotropic porous media for various patterns of injection and production wells has been extensively investigated.1-7 These investigations all concerned Newtonian fluids, i.e., the viscosity of each fluid was constant regardless of flow rate. The generally unfavorable influence on areal sweep efficiency of higher mobility of the displacing fluid as compared to the mobility of the displaced fluid has been established for both miscible and immiscible fluids. The principle was also established that a close correspondence exists between miscible and immiscible flood front behavior,2, 3 although oil recovery in a waterflood at unfavorable mobility ratio may be less than that observed in a miscible displacement at the same mobility ratio. This is true even when oil recovery is expressed on the basis of movable oil. The reason is that oil saturation only slowly achieves its final value behind the water-flood front in accordance with the Buckley-Leverett8 simultaneous flow relations. It is convenient to use miscible displacements for laboratory simulation of waterflood frontal advance since the interfacial tension forces which are negligible in proportion to viscous forces on a reservoir scale9 are thus made nonoperative in the laboratory model. For miscible displacements, the Hele-Shaw type of model adequately represents a porous medium so long as the appropriate scaling rules5-10 are observed in its design and operation. During simulation of waterflood front behavior in the laboratory by using miscible displacements, the behavior of connate water may ordinarily be disregarded since it is usually indistinguishable from flood water in this process. However, when the flood water is deliberately thickened to improve the mobility ratio between water and oil. the effect on the sweep efficiency due to generation of a connate water bank during the process must be considered. In a uniform porous medium, such a bank is generated11 and efficiently displaced by injection of thickened water.l2 The oil originally in-place at the start of the waterflood is then displaced by connate water followed by thickened water. If the flood water must be thickened to obtain a favorable mobility ratio, the mobility of the oil phase is appreciably less than that of the connate water. Hence, the oil phase is inefficiently displaced by the connate water bank, and a considerable proportion of the oil comes in contact with and is displaced by the thickened waterflood front' A recent study 12 of five-spot displacements using miscible Newtonian fluids in which connate water banks of various sizes were simulated shows that, for connate water banks as large as 40 percent of 1 PV, major improvements in sweep efficiency resulted from use of a thickened

Jan 1, 1969

By L. F. Mondolfo, B. E. Sundquist

The crystallographic orientation relationships resulting when lead is nucleated from the liquid by Ni, Cu, Ag, and Ge were determined. For each nucleating agent several definite orientatioz relationships were found. These relationships seemed to be controlled by good symmetry relations and low crystallographic disregistry between mating planes. For any given nucleating agent the under colling for nucleation was found fairly constant and independent of the orientation relationship and consequent disregistry. It was also found that, upon re melting and refreezing the Pb, the orientation relationship was changed. These findings prove that crystallographic disregistry is not the controlling factor in heterogeneous nucleation from the liquid. The results of this investigation tend to confirm the theory presented in a preceding paper that heterogeneous nucleation starts with the formation of an adsorbed layer of nucleated metal on the nucleat-ing impurity. Evidence is given that cavities in the nucleating agent act as centers of nucleation. IT has long been known' that solid extraneous particles are active in catalyzing phase transformations that occur in a system, particularly condensation and crystallization. It is well established that these heterogeneities act as catalysts by providing surfaces upon which nuclei of the precipitating phase can form with activation energies smaller than those required for homogeneous nucleation. Numerous investigations have shown that in this process of heterogeneous nucleation: a) the nucleus forms with one, or several, definite crystallographic orientation relationships with the nucleating phase2-4 and b) that there is a small range of undercoolings or super saturations characteristic of the nucleation of a given solid on a given Substrate.5-10 Turnbull and vonnegut11 have developed a theory based on theories developed by Volmer12 and Turn-bull and Fisher1= for heterogeneous nucleation from gases and liquids, that relates the super saturation or undercooling required for nucleation to the dis-registry between the lattices of the nucleus and the nucleating agent. This theory predicts that nucleation should occur with the orientation relationship between the nucleus and nucleating agent that minimizes the disregistry. Further, it predicts that the undercooling or super saturation necessary for nucleation should be a function of the disregistry. Numerous investigations have dealt with the orientation relationships resulting from the condensation of vapors onto crystalline solid substrates2,3 and a few with the nucleation of one phase by a second phase in solidification4,14. Others have dealt with the supersaturation8-10 and undercooling5-7 associated with nucleation in condensation and solidification respectively. However, there is virtually no report that gives both of these factors for the same system. In this investigation a study was made of the undercoolings and orientation relationships resulting when Pb is nucleated from the liquid by Ni, Cu, Ag, and Ge. It was the purpose of this investigation to check the Turnbull-Vonnegut theory, i.e., the importance of crystallographic disregistry between nucleating catalyst and nucleated metal. The results indicate that disregistry is not an important factor in nucleation and that the nucleation process is probably somewhat more complex than current theories suggest. EXPERMENTAL PROCEDURE Small single crystals of nickel, copper, silver, and germanium were prepared from materials of four to five nines purity, and the Pb used was also 99.999+ pet pure. Cu and Ag single crystals were prepared by sealing small chips of Cu or Ag in an evacuated quartz capsule and heating the capsule at 2000°F for 1 hr before cooling. Nickel crystals of 200 diam were also prepared in evacuated quartz capsules, but melting was done by heating the capsules in an oxy-acetylene flame for a few minutes. These spheres were invariably polycrystalline so

Jan 1, 1962

By K. E. Gray, G. M. Myers

In previous publications,5 results of single-blow bit tooth impacts on saturated rocks at various stress states were reported. This paper extends these earlier works to include study of bit impact tests on salt water-saturated Berea and Bandera sandstone samples under conditions of elevated confining and pore pressure. During the tests dynamic filtration and deposition of a mud cake were occurring due to the presence of drilling mud in the borehole and a borebole-to-formation pressure differential. Results indicate that saturation of these sandstones with salt water tends to make them weaker than when saturated with nonreactive fluids. Plastic failure often occurs even when extremely high fluid-loss muds are present in the borehole. The failure mode tends toward plasticity with decreasing fluid loss. Brittle failure of sandstones in mud-filled holes is apparently relatively rare. Depending on the stress level, and the associated failure mode, withdrawal of the bit tooth induces a tensile force that seems rather important relative to the quantity of rock removed by vertical tooth impact. INTRODUCTION A vast majority of the oil wells drilled today involve the use of colloidal muds having a measurable mud filtrate loss. It is known from field experience that reduction of the water loss of a mud generally results in a reduction of the penetration rate. This paper describes an investigation of crater formation at simulated bottom-hole pressure conditions for drilling fluids having different water losses. The literature on single bit tooth impact (cratering) at atmospheric conditions is extensive, but only a limited amount of work has been performed at the stress conditions similar to that found in oil wells. Spherical penetrator cratering tests on rocks at hydrostatic pressure were performed by Payne and Chippenda1e.1 Chisel impact studies on limestone with independently varying overburden and borehole pressure and atmospheric pore pressure were reported by Garner, et al.2 Gnirk and Cheatham3 performed "static" penetrator tests on dry rocks at equal overburden and borehole pressures. Podio and Gray4 studied the effect of pore fluid viscosity at atmospheric pore and borehole pressures and varying overburden pressures. Their results illustrated the importance of fluid saturation of the rock. Yang and Gray5 reported single tooth impact tests on saturated rocks at elevated borehole, pore and confining pressures, but with equal pore and borehole pressures. For the work reported in Refs. 4 and 5, filtration across the hole bottom purposely was avoided. Maurer6 has investigated the effect of independently varying pore and borehole pressures at elevated overburden pressures by using a zero water-loss mud in the borehole. His tests were carried out under conditions that allowed independent control of overburden, pore and borehole pressures, but without control of filtration at the hole bottom. EXPERIMENTAL APPARATUS AND PROCEDURE APPARATUS The single blow chisel impact apparatus used by Garner,2 as modified for this study, is shown in Fig. 1. A cross section of the pressure vessel is shown in Fig. 2. Several pieces of auxiliary equipment were added to the original apparatus in order that the borehole and pore pressure could be applied in a manner analogous to the actual bottom-hole situation. The pore-pressure system included a filtrate volume-measuring transducer and had sufficient surge capacity to allow filtrate to be injected into the sample without significant changes in pore pressure at points remote to the borehole. The borehole-pressure system contained a cross connection to the pore-pressure system so that both systems could be pressured simultaneously. The borehole-pore pressure differential was applied rapidly by the use of a quick and full-opening valve. The operation of this valve triggered two industrial

Jan 1, 1969

By A. E. Jenkins, L. A. Baker, N. A. Warner

The electromagnetic levitation technique has been successfully applied to rate studies of the de-carburization of liquid Fe-C alloys from 5.5 to zero pct C at 1660°C using gas mixtures containing 1 to 100 pct CO2 with CO or helium as diluents. The rate was shown to be independent of carbon concen -tration in the melt and only slightly affected by total pressure. The results were shown to be consistent with control either wholly or predominantly by gaseous diffusion. As well as avoiding side reactions with the crucible, levitation allowed precise calculation of reaction rates since the geometry of the system was accurately known. It also enabled interpretation using the established mass-transfer correlations for a gas flowing past a single sphere, The existence of gaseous-diffusion control and the extremely high rates of reaction reported for gas flowing past small spheres are of great practical significance in relation to current investigations into the use of spray-refining techniques in continzcous steelmaking. PREVIOUS work on the kinetics of carbon removal from liquid iron has generally involved the use of oxygen as the gaseous oxidant. Investigations have been made on commercial steelmaking furnaces and in addition laboratory-scale experiments have been attempted with a slag phase present. The general lack of agreement and the obvious difficulty in interpreting the results is at least partly due to the complexity of the systems used. This work has been reviewed by carter1 and more recently by Bods-worth2 and ward.3 The gas-liquid metal reactions have also been studied with slag-free melts by the conventional technique of blowing oxygen onto the melt contained in a crucible. The reaction between the oxidant and carbon could be followed by sampling either the melt or the gas phase. Side reactions with the crucible material have precluded direct interpretation of the results. Fujii, 5-7 using O-A mixtures, attempted to correct for the crucible reaction and reported that the reaction between carban and oxygen occurred at the melt surface and was controlled by gaseous diffusion for carbon contents greater than a critical value and by carbon-diffusion control in the metal for carbon contents less than the critical. The critical value was given as approximately 0.15 pct C. However, whereas this was the case for oxygen contents in the gas stream up to 10 pct, between 10 and 20 pct the rate was found to be approximately independent of oxygen content, and Fujii attempted to explain this observation by postulating the presence of an oxide "film".7 Turkdogan et a1.' have studied iron fuming during decarburizing and suggested gaseous-diffusion control of the reaction above a critical carbon concentration, given as approximately 2 pct C. Filippov9-12 reports in a similar manner to Fujii but makes no mention of the crucible reaction with the carbon in the melt, even though this would be expected with the temperature, crucible material (MgO), and carbon contents used. Both CO2 and O2 were used as oxidant gases. In the present work the decarburization of liquid Fe-C alloys was studied using an adaptation of the electromagnetic levitation technique, and thus the complexities introduced by crucible side reactions were eliminated. In this technique a single sphere of the Fe-C alloy is freely suspended and heated by electromagnetic induction in a flowing stream containing the oxidant gas. The full range of carbon levels up to saturation was studied, the temperature of the melts in this instance being held constant at 1660°C. The oxidant was CO2 which was used either pure or in association with a diluent gas, the total gas pressure being maintained either at 1 atm or at a reduced pressure. Thus the reaction under study was:

Jan 1, 1964

By M. R. Tek, F. F. Craig, J. O. Wilkes, C. S. Goddin

The waterflood performance of a water-wet, stratified system with crossflow is computed by a finite difference procedure. The effects of five dimensionless parameters on tile oil displacement efficiency, water saturation con-tour.7 and crossflow rates are evaluated in the absence of gravity forces. Crossflow due to viscous and capillary forces is shown to exert a significant effect on oil recovery in a field-scale model of a two-layered. water-wet sandstone reservoir. The crossflow is at a maximum in the vicinity of the front advancing in the more permeable layer. Under favorable mobility ratio conditions, the comparted oil recovery with crossflow always is interrnerliate between that predicted for a uniform reservoir and that for a layered reservoir with no crossflow. INTRODUCTION The important erects of reservoir heterogeneity on waterflood performance are commanding increased attention in the technical literature. Much of this attention is centered on two categories of layered reservoirs: those in which layers are non-communicating and those in which crossflow of fluids occurs between the layers. In the first category, the reservoir is assumed to consist of discrete layers, each uniform within itself and differing from the others only in such properties as thickness, porosity and absolute permeability. The performance within each layer is calculated by one-dimensional flow theory, and the performance of the total reservoir is obtained by summing individual layer performances. Capillary and gravity effects usually are not considered. Representative publications dealing with thi5 type of reservoir are those of Stiles,' Dykstra and Parsons,' Hiatt,3 Warren and Cosgrove' and Higgins and Leighton." Prediction of performance for reservoirs in the second category is considerably more difficult since viscous, capillary and gravitational forces all play important roles in causing crossflow between layers. A number of authors have investigated the simpler problem of two-dimensional displacement flow in a stratified system with a mobility ratio of unity and negligible capillary and gravity effects.'; Others have considered two-dimensional, non-steady-state flow of a single, slightly compressible fluid in a stratified reservoir. A limited number of laboratory oil displacement tests in layered models with crossflow have been reported. Miscible floods (with resultant zero capillary forces) in layered five-spot models were conducted by Dyes and Braun," who studied the effect of mobility ratio with zero gravity forces, and by Craig et al. 12 who studied the effect of gravity forces at constant mobility ratio. Waterfloods in layered five-spot models (with cross-tlow due to capillary, viscous and gravity forces) were conducted by Gaucher and Lindley,"' who showed the effect of gravity forces in causing underrunning of the injected water and by Carpenter, Bail and Bobek, 14 who demonstrated the reliability of Rapoport's" dimension-less parameters for scaling layered systems. Waterfloods in rectangular layered models were conducted by Richardson and Perkins."' who investigated the effect of velocity at constant mobility ratio and with zero gravity forces, and by Hutchinson," who studied the effects of varying mobility, layer permeability and layer thickness ratios. The differential equations which rigorously describe waterflooding in a heterogenous porous medium are non-linear and do not facilitate analytical solution. By using finite difference approximations it is possible to obtain a solution to any desired degree of accuracy. Such a solution, using an alternating direction implicit procedure (ADJP), is described by Douglas, Peaceman and Rachford.18 In the present study, a computer program using ADJP explores systematically the effects of important parameters on waterflood performance of a two-dimensional, two-layered, field-scale model of a water-wet sandstone system. Particular attention is given to evaluation of the water saturation contours and crossflow rates at the interface between layers to gain improved understanding of the crossflow mechanism. PROCEDURE BASIC: FLOW EQUATIONS The basic flow equations for two-dimensional, two-phase, immiscible, incon~pressible flow in a porous medium are:

Jan 1, 1967

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By Wilfred Walker

With the advent of the New Global Tectonics a coherent pattern of geology is emerging. To the economic geologist this is of vital concern because the type of mineralization in particular environments is predictable. Developments in geological reasoning now take their place beside developments in geochemistry and geophysics. Much is known of the worldwide geography of the Alpine orogenic period because it is now ending its 200 million years of existence, starting with the Jurassic, and we can see the mid-ocean rises and the down flow zones, and between them the stable oceanic and continental platforms. The concepts of mantle cells, the spreading sea floor, and continental drift have gained general acceptance. The oceanographers have demonstrated the uprises like that in the mid-Atlantic. In this paper it is suggested that down flows in the oceans are marked by island arcs, like the West Indies; and down flows in the continents are marked by orogens like the American Cordillera. The number and position of mantle cells is controversial: a total of about 16 cells is suggested in this paper. Certain cells expand, and as they carry continents with them give rise to concepts of plate tectonics. Specific types of mineral deposits are associated with the uprises, oceanic and continental platforms, and down flows. The uprises are accompanied by the currently described Red Sea and Salton Sea deposits, the oceanic parts of the platform have the nodular deposits, and the continental platforms have the post-tectonic deposits. However, most economic metal deposits are associated with the down flow zones in which the stage of geosynclinal development controls the type of deposit: (1) In the initial development stage the simatic upper mantle may be tapped and give rise to the volcanogenic massive base metal sulfide deposits and to the ophiolite suite which characteristically carries nickel, chrome, and cupreous pyrite. (2) In the early geosynclinal stage sialic crust is driven down into the simatic magma of the upper mantle and basic to acidic differentiates give rise to stocks accompanied by skarn and hydrothermal deposits. (3) The intermediate stage of geosynclinal development gives rise to tin-tungsten, lithium, and beryllium deposits as the magma chamber rises above the level of the upper mantle and there is no simatic component. (4) The late stage is one of regenerated deposits. The porphyry deposits are not restricted to stages but only by the time of generation of acid magma. As the geosynclinal system dies, the mantle is again the source of magma, giving rise to gabbro and diabase dykes and sills: in this last, post-tectonic, continental platform environment are found the Mississippi Valley type lead-zinc deposits, the Blind River and Witwatersrand type of sedimentary uranium and gold deposits, and also Sudbury's nickel. The key relationship of major ore deposits generated by downflows is depicted herein on a framework of uprises, platforms, and downflows in the Alpine orogenic period. There is evidence for nine orogenic periods, of which the Alpine period is the latest, having taken place from 3500 million years ago to the present. Each period was characterized by its own worldwide mantle cell system and associated uprises, platforms, and down flows. The cycle of geosynclinal development, including corresponding cycles of mineralization, can be precisely defined in relation to each of these orogenic periods. The development of the Alpine orogenic period therefore can be used as a guide to the study of the earlier orogenic periods which comprise well known periods: Kenoran, Hudsonian, Grenville, and Paleozoic; and less well known: Konkian, Aulian, Belomorian, and Elsonian [(Table 1)]. Each name is used for the period as a whole, and not for the main orogenic event.

Jan 1, 1973

By S. K. Mitra

A refinement of the Seeger model for intersection process is investigated which is in better agreement with experimental observations than the original. It is shown that, in single crystals, the strain hardening in Stage II is mainly due to the short-mnge interactions when intersection is the rate-controlling process. It is also demonstrated that the creep curves, as predicted by this theory, are in good agreement with the experimental observations. MOTT: Cottrell? and Seeger have developed an approximate theory for plastic deformation of single crystals over the range of variables where the strain rate is controlled by the rate of intersection of dislocations. Although it is now generally agreed that the low temperature deformation of many pure metals is controlled by the intersection mechanism, various dictates of the over-simplified Seeger model are not in good agreement with all the experimental facts. It is the purpose of this paper to reveal that by appropriate extensions of the Seeger model, particularly those suggested by Basinski: a much more reliable theory results. The refined model to be presented here will be shown to account, in a satisfactory way, for the effect of stress, temperature, and strain on the creep rate under constant stress and for the effect of temperature and strain on the flow stress in constant strain-rate tests. EXPERIMENTAL METHOD To Check the theoretical deductions, both creep and tension tests were conducted on single crystals of high-purity Al (99.994 pct Al) so oriented that both the active slip plane and the Burger's vector of the operative dislocations on that plane made angles of about 45 deg to the tension axis. Single crystals of aluminum (5/8 in. by 1/10 in. by 8 in.) were grown in a graphite mold under an inert atmosphere using the Bridgman method. The chemical composition of the aluminum is given in Table I. A common seed was used for all crystals and their orientation is shown in Fig 3. The extensometry consisted of two differential transformers with matched outputs mounted so as to measure the extension in a 2 in. gage length. The amplified difference in output of the two transformers was recorded by a potentiometer. The amplification was calibrated before each run so that one chart division of the recording potentiometer indicated a 105 shear strain on the specimen. Stresses were measured to the nearest 1 x l04 dynes per sq cm. ACTIVATION VOLUME The concept of Basinski that the activation volume is not constant but is a function of the force that aids thermal fluctuation in effecting the cutting of dislocations will be adopted in this section. The force acting due to an applied shear stress on the dislocation being intersected is where L is the mean spacing between the forest dislocations, is the Burger's vector and T is the back stress. A detailed discussion about the origin of back stress will be taken up later in this report. As shown by Basinski, the activation energy, U, that must be supplied by a thermal fluctuation in order to effect intersection, is equal to where x is the distance through which the dislocation must be translated for complete intersection, and Fm is the maximum force encountered in intersection. When the applied stress is decreased abrupt ly F also decreases and the activation energy increases correspondingly as documented in Eqs. [ 1 ] and [2]. The Seeger equation for the strain rate when the deformation is controlled by rate of intersection of where the shear strain rate (per sec) N = the number of points per unit vol at which intersection can take place

Jan 1, 1962

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By O. D. Gonzalez, R. A. Oriani

A thermo-osmosis technique has been used to measure the heat of transport, Q* , of hydrogen and of deuterium dissolved in a iron and in nickel, and of hydrogen in Feo.6Nio.4 in the tempevature range 400° to 600°C. For all these systems, Q* is negative and has a large temperature coefficient; an isotope effect can be established for the solutes only in nickel. The magnitude of Q* is considerably larger than the activation energy, E , for migration in the case of these isotopes in a iron, so that all variants of the Wirtz model must be rejected. The phenomenological definition of Q* is developed to show that Q* is related to the mechanisms by which the activation energy is dissipated back into the lattice, and that Q*/E is a function of the ratios of the mean free paths of electrons and of phonons to the distance of jump of the diffusing atom. A correlation is shown to exist between the sign of Q* in thermal diffusion and that of the effective charge in electro migration, and may be understood as due to the large ratio of the mean free path of electrons to that of phonons. THE study of nonisothermal diffusion in the solid state is of interest because certain aspects of the mechanism of diffusion are made manifest which remain concealed though still present in the isothermal case. The thermodynamics of irreversible processes characterizes nonisothermal diffusion, known as thermal diffusion or as the Ludwig-Soret effect, by a quantity, Q*, called the heat of transport, which essentially measures the sign and the magnitude of the steady-state concentration gradient produced by the imposed temperature gradient. The problem then is to understand the quantity Q* at the atomistic level. There does not exist a theory for the atomistic interpretation of the heat of transport. There are, however, two classes of simple models which seem to afford some physical insight into Q*. Wirtz's model1, z and its subsequent generalizations partition the activation energy, E, for the migration of the atom spatially about the region of the migrating atom, so that Q* is the difference between the portion of the activation energy centered about the original site of the jumping atom and that portion about the arrival site. Clearly, the magnitude of Q* cannot on this model be larger than the activation energy for migration. The model of Oriani3 also considers the spatial distribution of E not only before but also after the atomic jump, and Q* is related to the variation of the spatial distribution of E that is produced by the jump. The simplest kind of system with which to compare the consequences of these ideas is the interstitial solid solution, since one may easily choose a temperature at which only the interstitial component moves, the solvent lattice serving as a completely satisfactory frame of reference. Thus, one avoids complications arising when both species in a binary system move. In addition, one avoids the necessity of knowing the energy for the formation of a vacancy, something which is needed for the analysis of thermal-diffusion data on metals which diffuse by the vacancy-exchange mechanism. However, the number of well-measured interstitial systems is extremely small, and, in particular, there are almost no data in the published literature for the temperature dependence of the heat of transport. If one works with solutes which are gases in the pure state at ordinary temperatures, one may use the technique of thermo-osmosis4 which permits thermal diffusion to be measured over a small temperature difference so that the temperature dependence of Q* can be more easily determined. The choice of dissolved hydrogen in iron and nickel was based on these considerations as well as on the desire to look for an isotope effect associated with localized

Jan 1, 1965

By C. Gatlin, M. E. Chenevert

The effects of bedding plane orientation on the elastic constants and the yield strengths of three laminated rocks (one sandstone and two shales) and one isotropic rock (a limestone) were studied. The directional dependence of the elastic properties of these rocks was experimentally evaluated using a triaxial compression cell and auxiliary stress-strain measuring equipment. Symmetry of Poisson's ratios within the bedding plane suggested that horizontal isotropy exists, but the bedding planes do give rise to an appreciable difference between properties in the horizontal and vertical directions. For the three bedded rocks studied, Young's modulus was lower normal to bedding than along bedding. Yield strengths were determined at confining pressures from 0 to 12,000 psi in a triaxial compression cell. The rocks studied showed strength reductions as high as 40 per cent when the test specimen was oriented at 20°-30° to the bedding planes. The mechanical behavior of these rocks suggested that the rock properties of shear strength and/or coefficient of internal friction can vary with direction, depending on the particular rock tested. Tensile strengths were also measured and found to be lowest when failure occurred along bedding. This work shows that bedded formations exhibit sizable directional variations in both their elastic constants and yield strengths. It is suggested that these variations may be accounted for by using the "elastic laminate" model and the "variable coefficients" failure model. INTRODUCTION The nature of rock deformation at elevated pressures has been studied by many workers; papers by Handin,l,2 and Robinson3 illustrate the present state of knowledge. Most investigators have either chosen rocks which were as isotropic as possible (in order to avoid complications of data interpretation and analysis) or they have oriented their samples so that the effects of anisotropies (such as bedding planes) have been avoided. Of the studies performed, few were concerned specifically with mechanical anisotrop-ies. Griggs4 has presented limited data for specimens cut parallel, normal, and 45° to the bedding plane; he relates the strength anisotropy observed to the fabric (bedding) anisotropy. His tests were primarily concerned with large deformations (20 per cent strain); thus, no directional values of the elastic constants were reported. Handin has reported the results of similar experiments. Bott5has discussed rock strength anisotropies due to faults, cleavage, or bedding. He was concerned primari ly with determining the shear stress on such planes and did not mention the effect of friction. Jaeger6 later generalized Bott's work by taking friction into account and presented a limited theory for the failure of rocks having a "single plane of weakness", and also for rocks having a constant coefficient of friction, and a shear strength which varies with bedding plane orientation. Donath and Cohen,7 and Donathg have evaluated rock strengths from shale and slate specimens cut normal and parallel to bedding. A dependence of cohesive strength (7,) on the specimen orientation was also shown. Adler9 has also studied this problem and lists similar results. He assumes that all bedded rocks behave according to Jaeger's single-plane-of-weakness theory. Kalinin and Belorussov10 list results for strength tests parallel and perpendicular to bedding and use this information as a basis for hole deviation analysis. From the literature it is apparent that sedimentary rocks have been tested under widely varying conditions of stress; however, the assumption of isotropy is generally, but not always, made. Since geologic sedimentation often deposits sediments in very definite lavers.,. it seems that more svstema tic attention should be given to the possible effects of this natural bedding. Bedding, as used here, refers to visible regularities of grain size or orientation resulting from depositional processes. The mechanical strength anisotropies, which bedding may present, is not the only anisotronic property to be considered, since the elastic

Jan 1, 1966

By A. N. Crownover, H. T. Kennedy, E. P. Miesch, C. H. Bowman

The paper presents correlations of (l) molar volume of gaseous hydrocarbon mixtures with pressure, temperature, composition and properties of the C,-plus fraction; (2) shrinkage of oils during flash and differential liberation of gas, including the calculation of formation volume factor under various conditions; and (3) bubble-point pressure with temperature, composition and characteristics of C, plus. The data on which the correlations are based comprise 1,615 measurements on 900 hydrocarbon systems, including numerous systems containing nitrogen, hydrogen sul-fide and carbon dioxide. In each correlation, the number of data points covered and the accuracy is substantially greater than in previously available work. Thus, the equation yielding molar volumes of gases has an average deviation of 2.04 per cent, applied to mixtures having temperatures up to 313F and pressures up to 9,800 psis, compared to 2.37 per cent for the Benedict-Webb-Rubin equation applied to the same data, and 4.53 per cent for the method based on the law of corresponding states. he equations resented are all explicit in the dependent variable, and require no iteration on the digital cow puter. INTRODUCTION The ease and accuracy of determining the composition of hydrocarbon mixtures, compared to the difficulty of measuring their properties under reservoir conditions, makes it desirable to utilize composition as the key to physical behavior to the greatest possible extent. As a result, there are available correlations between composition, or easily measured characteristics dependent on composition, and practically every important engineering property of reservoir fluids. The task confronting us is one of finding more exact relationships between important variables rather than extending correlations to new properties. This paper describes new correlations of molar volumes of gases, formation volume factors, and bubble-point pressures with composition, temperature and where possible, pressure. Each correlation is obtained by employing a sufficiently large amount of data so the calculated properties are probably as least as accurate as the measurement on which they are based. MOLAR VOLUME OF GASES Although many equations of state have been proposed for pure gases, only a few methods are applicable to hydrocarbons at conditions comparable to those in petroleum reservoirs. Still fewer arc useful in describing the behavior of mixtures, with which the petroleum engineer is largely concerned. The correlation presented here involves procedures similar to those of Alani and Kennedy The van der Waals equation is modified to make a and b functions of temperature instead of being constants for each material.This is a cubic equation, which may have either one or three real roots. The lowest root corresponds to liquid volume, while the highest applies to gas. When the procedure was applied to 703 pressure-temperature points of 164 gases of known composition and volume, the average deviation was 12.08 per cent, and the standard deviation 8.15. The above calculations were made using the constants derived for liquids by Alani and Kennedy and the mixture equation developed by them. A closer approximation to measured molar volumes is obtained by employing different sets of constants for different areas on the pressure-temperature chart, and by changing the relationship between a,,, and b,,, for mixtures and the a, and b, for individual hydrocarbons. The various sets are shown in Table 1, and the areas for which they are recommended are plotted in Figs. 1 through 7. In these figures, the area designated by zero is in the critical region for pure materials, and the values obtained for them may be unreliable. For normal mixtures, however, the area may be added to any of the bounding areas without substantial error. The new relationships employed are

Jan 1, 1966

By Robert Maes, Robert de Strycker

The Fe-Ni-As phase diagram has been established by the study of about a hundred alloys, by microscopic observation, and by thermal analysis, with arsenic contents up to 50 pct. The iron and nickel arsenides present extensive solid-solution fields, owing to the substitution of nickel by iron and vice versa; the extent of the solubility field of each compound has been determined with an accuracy of ±1 pct. In the investigated range of compositions, the solidification reactions were established, and the temperatures of the invariant reaclions detevmined with a preciston of iZ°C in the most favorable and ±5°C in the least favorable cases. The isothermal lines of the liquidus surface have also been drazum, with an accuracy estimated at i5°C. Reactions in the solid state, which take place for the formation or the decomposition of certain phases , were investigated in detail. ThE constitution diagram of the Fe-Ni-As system is fundamental for the understanding of the properties of nickel speiss; these by-products of the extraction of certain nonferrous metals indeed often contain the three elements iron, nickel, and arsenic as main constituents. The Fe-Ni-As system has already been the object of earlier investigations. In 1932, Guertler and Savels-berg' have presented some elements of the ternary phase diagram, for arsenic contents up to 55 pct (all percentages in this paper are given in weight percent), including the vertical section FezAs-Ni&s2. This investigation is, however, incomplete and certain anomalies suggested the necessity to verify the results published by these authors: the section Fe2As-Ni5AsZ, for example, is presented as quasi-binary, with a field of complete miscibility in the solid state, even though these compounds do not have the same structure. Recently, ~useck' established an isothermal section at 800°C in the Fe-Ni-As system by X-ray diffraction and microscopic examination of water-quenched alloys. These techniques are sometimes inaccurate for the determination of the fields where alloys are liquid at the investigated temperature, and they may lead to erroneous conclusions when a compound exists at the investigated temperature but is not stable at room temperature and cannot be maintained by quenching. LIMITING BINARY PHASE DIAGRAMS The Fe-As constitution diagram has been the object of several investigations which have been reviewed by Hansen and Anderko.3 For the Ni-As phase diagram, a recent study has been effected by Yund.4 In this system, Heyding and calvert5 have determined the existence of a compound of unidentified structure at arsenic contents slightly higher than those corresponding to Ni5As2 and at temperatures lower than about 200°C; by analogy with iron and cobalt arsenides, this compound could correspond to the formula Ni2As, as suggested by Kulle-rud; although this is not definitely established. In the region of arsenic contents from 35 to 55 pct, Fried-rich7 detected anomalies in the solidification reactions; an interpretation of these anomalies was given by Hansen ,8 which assumed that the solidification reactions in practice are not in equilibrium, but are meta-stable. The main features of the Fe-Ni constitution diagram are the existence of a complete miscibility field, at least at high temperatures, for the fcc phase (which will be designated by My in the remainder of this work) and of a limited solubility field for the bcc phase (designated by Ma). EXPERIMENTAL METHODS The fundamental technique used in this investigation was microscopic observation, which allowed the determination of the reactions occurring during solidification of the alloys, and possible reactions in the solid state.

Jan 1, 1968

By Z. F. Oszter

This paper discusses the materials handling problems encountered in cement plants in the areas of raw and finished product grinding and cement storage. It illustrates by examples taken from actual installations, how optimum feed rate is maintained in grinding circuits with properly applied bin dischargers (vibrating hoppers, Mexican feed boxes and aerated bin bottoms) for materials with high moisture content and/or difficult handling characteristics. Initial operating problems with the equipment will be discussed and maintenance requirements will be indicated for comparison purposes. In a modern cement plant, properly functioning bins and feeders are as essential as process control, for no process control system, however sophisticated, can perform efficiently if raw materials do not flow into the plant processing facilities at the required time and rate. Most materials used in the manufacture of portland cement - such as silica sand, iron ore fines, crushed limestone, gypsum, clinker or cement itself-have difficult handling characteristics under specific conditions. High moisture content or even dampness due to condensation may create bin hang-ups, arching and ratholing, all of which result in improper functioning of the feeders or proportioning equipment. The occurrence of these problems in existing cement plants spurred a search for the corrective devices discussed in this article. The equipment investigated included bin dischargers in the form of vibrating hoppers for moist raw materials, Mexican feed boxes for clinker and aerated bin bottoms for cement. Operating experience with different types of bin dischargers showed that the actual performance of some did not come up to the expected level under prevailing operating conditions. The aim of this paper is to record the results of this experience and there- by aid designers and/or operators in selecting the most suitable equipment for their requirements. BIN DISCHARGERS (GENERAL) A discharger is a device that causes stored solids to flow out of a hopper without metering the rate of flow as a feeder does. The investigation discussed here encompasses the following types of bin dischargers used in a cement plant: (1) vibrating hoppers (horizontal motion), (2) whirlpool hoppers (horizontal and vertical motion), (3) aerated bin bottoms (air fluidization), and (4) Mexican feed boxes. Most of the bins used in the cement industry are of the plug flow type. Raw materials with difficult handling characteristics such as high moisture content may cause flow problems when fed through small openings (12 x 18 in.), even if two walls of the bin are vertical.' The most appropriate solution to these flow problems would be the installation of separate mass flow bins for the different materials such as silica sand, iron ore fines, crushed limestone and gypsum, with each bin correctly designed from test data obtained by measuring the flow properties of representative samples. However, limited storage capacity and plant space usually preclude this approach. Quantitative design of bins for flow based on measured flow properties of representative samples of the bulk solid to be handled is no longer an "engineering art," thanks to the basic research done on the flow of bulk solids in bins during the last decade.2, Where space limitations exist, however, or where improvements are being sought for equipment already installed, bin dischargers offer a satisfactory solution to flow problems. They can be applied effectively under flat-bottom bins or mounted to existing plug-flow bins with very little modification to these facilities. In both the foregoing cases, plug flow will be maintained, but the flow channel will be considerably increased so that it is larger than the discharger's bin-side diameter, and material flow can be sustained if the discharger is correctly selected. The main purpose of a bin discharger is to draw the bulk solids across the whole area of the bin outlet, to make the opening fully effective. As long as the bin-side opening of the discharger is large enough

Jan 1, 1969

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,' Mc Quillan,' Van Thyne et dl.,' and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger' discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95' *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By W. B. Nelligam, J. Tittman

Refinements in radiation logging techniques during recent years have involved increasing usage of scintillation ditectors. These detectors produce voltage pulses whose heights are related to the energies of the gamma rays which initiate them. Analysis of the gamma-ray spectrum, as indicated by the pulse heights, yields information about the chemical elements composing the formations surveyed. Refined scintillation counter techniques can furnish chemical information concerning earth formations in situ, from a study of the gamma-ray spectra emitted by the formation either naturally or as a result of neutron bombardment."' Accompanying the rising interest in gamma-ray scintillation spectroscopy, there has been increased activity in the development of accelerator-type neutron sources (in contrast to encapsulated chemical-mixture sources). Such neutron generators are attractive for several reasons: (1) they greatly reduce radiation hazards to personnel; (2) there is a great reduction in contamination danger if they are lost in the hole; (3) they can produce larger neutron intensities than can conveniently available encapsulated sources; and (4) they are capable of being pulsed, thus permitting new techniques in logging. In the past, both accelerator and encapsulated neutron sources have been used by others in conjunction with scintillation-detector pulse-height analysis. The results have not been too encouraging, due to the interference among different gamma-ray spectral lines and to the fact that the gamma-ray peaks were not too clearly distinguishable above the large and ill-defined background "noise".'.' This paper is a status report on laboratory studies of a technique using a borehole accelerator as a neutron source, which gives an improved scintillation spectrum, thus permitting more accurate chemical analyses of the formations penetrated. The Schlumberger-accelerator neutron source' is presented; the origins of inelastic and of thermal-neutron, capture gamma rays are dis- cussed, and results are given for some laboratory measurements performed in borehole geometry. THE NEUTRON GENERATOR-TUBE ACCELERATOR In the attempt to develop an accelerator neutron source which would have the desirable properties outlined in the "Introduction" and which would operate satisfactorily under borehole logging conditions, a small-diameter, cylindrical, neutron generator tube has been developed. This tube utilizes the principle of accelerating deuterons (heavy hydrogen nuclei) by a high voltage so that they bombard a tritium (heavy, heavy hydrogen) target. The resulting reactions produce large numbers of neutrons of 14 Mev energy. Furthermore, the tube is permanently sealed and, thus, the use of pumping techniques in the sonde is avoided. The tube consists of a pressure control, an ion source in which the deuterons are stripped of their electrons, an accelerating gap down which the deuterons are sped by the high voltage, a secondary electron suppressor and a tritium-loaded target. Obviously, the tube requires auxiliary circuitry in a sonde for the control of the ion source, tube pressure, high voltage and other operating variables. Neutron yields, both continuous and pulsed, have been produced under simulated field conditions in the range between 1 and 10 times those conventionally used in neutron logging applications. For the experiments discussed in this paper, neutron-pulse repetition rates in the range between 500 and 5,000 pulses/sec are adequate. Furthermore, by making suitable adjustments in operating conditions, one can vary the pulse width from a minimum of several microseconds up to dc. As will be seen later, the present application to well logging does not require that one have available pulses of neutrons which are appreciably shorter than the time it takes for fast neutrons to slow down to thermal energy in water. As a consequence, much of our interest has been directed towards the operating characteristics of the tube with pulses longer than about 10 microseconds in duration. Our experience to date shows that tubes can be operated in this manner with reasonably constant, average neutron outputs.

By Wayne E. Glenn

The San Miguelito Field of Ventura County, California, lies along the coast approximately five miles northwest of the city of Ventura. The structure is one of several in the Ventura anticline, a series of anticlinal folds trending northwest-southeast through the San Miguelito Field. The Ventura Avenue Field lies to the southeast along the anticline, and Padre Canyon and Rin-con Fields lie to the northwest; the series then extends beneath the Pacific Ocean. Production is obtained from the Lower Pico and Repetto formations of Pliocene age, and oil accumulation is controlled by faulting, lithology and structure. The first well in the First Grubb Pool was completed in November, 1931, and to date 48 producing wells have been drilled on the 276 productive acres. Approximately 685 ft of net pay are contained in the eight sand bodies grossing 1,220 ft of section. Production of oil to date has been 15,-600,000 bbl. A gas injection project was instigated in April, 1940, but was discontinued in September, 1949. This paper is confined to a discussion of the development and performance history of the First Grubb Pool of the San Miguelito Field. LOCATION AND GEOLOGY The San Miguelito Oil Field is located in Ventura County about five miles northwest of the city of Ventura along the coastal highway to Santa Barbara. It is located within sections 23, 24, 25, and 30 of Township 3 North, Range 24 West, San Bernardino Base and Meridian. Surface elevation in the field ranges from sea level to plus 1,200 ft, and the terrain is extremely rugged. The structure is well defined on the surface and on the wall of the Amphitheatre Canyon where appears a so-called "text book" anticlinal section. The San Miguelito structure is an asymmetrical, elongated anticline about two miles long and three-fourths of a mile wide. The trend of the axis of the anticline is northwest-southeast. Fig. 9 illustrates the contours and major faults of this structure. Dips on the southwesterly flank average about 40 degrees, whereas the northeasterly flank ranges from 60 to 75 degrees. There are several faults striking generally east and west. These faults do not appear to affect materially the area of accumulation or performance behavior. It is believed that accumulation was affected by steeply dipping beds and extremely low permeability of the northeast flank of the structure. As shown by the typical log, Fig. 1. the San Miguelito Field is divided into two stratigraphic producing intervals. The First Grubb Pool comprises the interval from the "G" to "L" markers; the Second Grubb Pool from the "L" to "M" markers. The First Grubb Pool, ranging in thickness from 1,105 to 1,680 ft, with an average of 1,220 ft, includes approximately 685 ft of oil-bearing sands. The First Grubb zone consists of eight sand intervals separated by shales. The shale bodies separating the eight sand intervals within the First Grubb Pool are continuous throughout the major part of the structure and serve as an effective barrier. Many of the thin, irregular shale or siltstone streaks within these sand bodies are discontinuous and do not affect well performance appreciably. The productive horizons in the First Grubb Pool are siltstones and sandstones of the Lower Pico and Repetto formations of Pliocene age. It is apparent from inspection of the typical log that the "G" to "L" interval might have been separated into at least six producing zones and selectively pro. duced. Unfortunately the electric log and some of our modern tools were not available or were in their infancy dur. ing the period 1931 through 1937. Not until 1937 when eight wells had been completed were there sufficient geological data to permit definition of the sand bodies. Then the problem of reservoir control in this multiple-sand field, where all sands are open to a common

Jan 1, 1950

By E. H. Lee, F. J. Fayers

Problems in reservoir analysis can usually he cupressed in terms of a system of nonlinear partial difjerential equations. A rnethod for .setting physically reasonable boundary conditions for these systerrls by ayplication of the theory of characteristics is discussed. A short description i.c. given of the technique for finding chnmcteristics of general first order and second orrler equations. Specific examples are quoted jrorn eqrrations occurring in theoretical reservoir studies. The princip1e. ossocicred wit11 the use of chnracteristic to set physically realistic boundary conditions me developed, and thr method is discussed in terms of boundary condition for the noncupillary, compressible, two-phase flow problen: jor the cupillary, ir~cowlpressible, two-phase flow problems for the tlrtergent flooding prohlenl; as for the compressible. noncapillary, two-phase flow pro11letn. INTRODUCTION In most problcms in reservoir analysis the physical situation is described by a system of nonlinear partial differential equations. The general solution to the set of equations usually comprises a wide range of functions ancl a particular solution is normally selectetl by applying suitable boundary conditions to the problem. In some cases it is clear from the physical situation what form the boundary conditions should take, but it is usually desirable to have an independent mathematical check of the suitability of the chosen conditions. From the mathematical standpoint, a system of partial differential equations with boundary conditions is said to be properly set if the combination determines a unique solution which is continuously dependent on the equation and the boundary conditions. Such a solution is sometimes termed "reasonable". In investigating the properties of the mathematical representation, it is useful to determine the structure of the system by the application of the theory of characteristics. This theory determines in the space of the independent variables, lines or surfaces which play a special role in thc system's behavior. The characteristics determine the possibility and nature of the propagation of discontinuities in the derivatives of the dependent variables. Along the characteristics certain differential relations hold which for some problems allow a so- lution to be obtained analytically. In the case of hyperbolic equations the characteristics can bc used as 3 basis for a numerical solution. If a complicated nonlinear system is to be solved, a study of behavior of the characteristics will indicate what boundary conditions should be chosen. By using the method of characteristics, several advances have rccently been made in solving reservoir engineering problems. Sheldon, Zondek and Cardwell' have discussed how the the method may be used grap-phically to solve the incompressible two-phase displaccmerit problem when the gravity term is included in the equations. Fayers and Perrine' have applied the method to study the equations representing detergent flooding. When compressibility and solution-gas effects are introduced into the two-phase flow problem, the equations and their characteristics become more complicated. It will be seen that in this problem the characteristics are useful for indicating a reasonable set of boundary conditions but cannot readily be used to compute a numerical solution. This problem has been solved on the IBM 701 using normal finite difference methods hy West, Garvin and Sheldon." The material to be prcscntcd in this report is divided into three sections. The first discusses the determination of the characteristics of first and second order partial differential equations; the second describes the selection of suitable boundary conditions by the application of the principle that the future cannot affect the past; the third discusses the use of characteristics for setting the boundary conditions of the two-phase solution-gas flow problem. A useful introduction to the method of characteristics has been given by Hildebrand.' A summary of the method will be given in this section of the paper. The First Order Equation The quasi-linear equation of first order is It is linear in the partial derivations of z. The properly linear equation has the form The characteristics of are curves along which the

By W. A. Riggs

In a single year the total transportation cost equals nearly 30 pct of the value of mineral commodities, the largest single cost from the deposit to consumer. The magnitude of this economic factor calls for more complete understanding of cost and operational problems between producer and carrier than now exists. Details are given of the costs of providing transportation as well as freight rates for selling transportation. In 1958, transportation of mineral commodities in the United States required 600 billion ton-miles to move 1 3/4 billion tons of products of mines comprising solid fuels, crude oil, industrial minerals and rocks, and ores. Possibly 17 pct was handled by more than one mode of transport, since combinations of several modes of transport may, at times, achieve better service/cost results than any single mode. Total transportation cost of nearly $5 billion equaled roughly 30 pct of the value of the mineral commodities, the largest single cost from the mineral deposit to the consumer. The tremendous magnitude of this transportation undertaking demands much more complete understanding than now exists between mineral producers and carriers about the economic and operational problems of each other. A substantial portion of the daily work of the writer is spent in trying to act as a combination interpreter and catalyst between potential shippers and carriers, hoping to direct both to points of mutual understanding and advantage. For the purpose of this paper, it is necessary to ask mining people to accept some terminology and to try to appreciate the mental approach of the freight rate making people of the carriers. This paper will consider costs of providing transportation as well as freight rates for selling transportation—although these are fields of limited certainty. There are no accurate statistical breakdowns for all modes of transport and types of carriers indicating commodities, volume of traffic, distances, costs, and rates. Much information is available for railroads, and some for the regulated portions of air, motor, pipeline, and water transportation. Unregulated carriers, handling about half of the transportation of products of mines, are not required to report, and very little is known of their activities. Figures used herein are national in scope, unless otherwise indicated, and have generally been derived from Interstate Commerce Commission reports and files. Tonnage figures have been reduced to net tons of 2000 lb. The very generalized comparison of average mileage freight rate levels for various modes of transport provided by Fig. 1 affords advantageous perspective for the entire field of transportation costs. Dashed guide lines show cents per ton-mile, and dotted guide lines show percentage of first class railroad freight rate. While costs of other than railroad transportation more nearly follow constant cents per ton-mile functions, costs of railroad transportation show characteristic taper, or decrease in cents per-ton mile with increasing length of haul. This fundamental difference in cost is due largely to the fact that railroads and pipelines provide their own fully taxed roadway facilities while highway, waterway, and air carriers use government-provided tax-free roadway at no cost other than fuel, license, and certain excise taxes. Thus railroad and pipeline transportation might be said to carry heavy threshold costs in addition to those transportation costs which are directly variable with ton miles of transportation produced. The original basis of railroad freight rate structures lies in the classification of all articles of commerce into railroad class ralings ranging from 7 to 40 pct of first class (100 pct) rate level, dependent on value, hazard, loading characteristics, service requirements, and whether carload or less than carload. Classification tables and mileage-based (but arbitrarily grouped), rate scales are published as tariffs subject to approval by regulatory bodies. Used together, these determine class rates in cents per 100 lb between points in the U. S. Where local commercial or operating conditions render it advantageous for carriers to depart from

Jan 1, 1961