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By G. M. Gay, R. L. Perrine

This paper describes a method of numerical computation for three-dimensional, unstable, miscible displacement behavior useful for heterogeneous systems, as well as for more ideal conditions. In the method, flow equations are first linearized by a perturbation approach. The basic flow process is separated and a solution for its behavior readily obtained. The remaining problem of deviations from the basic flow caused by non-ideal conditions is then subjected to numerical analysis. Results obtained from use of the method are also presented. Although conditions assumed in the test cal-culations were severe, results show the type of dispersing flow expected and appear quite satisfactory. The method has eliminated or reduced in importance problems of oscillating values near steep fronts, excessive computer smoothing, etc. A unique advantage of the method is that the source of variations from ideal behavior can be observed. ,The one serious drawback results from the algebraic complexity of the perturbation approach, and the need for second-order terms to be retained in calculations of interest. Fewer array points are available and more computer time is required than would be desired. However, these difficulties are also experienced with other approaches to the solution of three-dimensional dispIacement problems. INTRODUCTION Prediction of behavior of the miscible displacement process within a porous medium for any system of engineering importance is plagued by a number of difficulties. With typical fluid properties the displacing fluid has the lower viscosity, and there is a natural tendency toward flow instability. The problem of predicting instability is compounded by the fact that every real system is heterogeneous. Permeability will vary from point to point — not entirely systematically, and yet not in a random fashion leading to a readily defined average. Furthermore, permeability is unlikely to be isotropic. These permeability properties, which are characteristic of any real porous medium, accentuate the effects of flow instability. Another factor to be considered is that flow dispersion accompanies the displacement process in a porous medium. Mechanistically, dispersion is due to the fact that flow between any two points in the medium follows multiple tortuous paths, each characterized by slightly different flow properties. The fact that the coefficient characterizing dispersive properties of the real medium JS a tensor with variable elements complicates matters. Further difficulties arise because the parabolic influence, while not negligible, is small. Thus, there is a tendency toward steep and uneven displacement fronts along which dispersion smoothing must be represented accurately. Yet frequently used numerical analysis schemes may tend toward either instability, oscillation or excessive smoothing, none of which gives the desired accurate picture of flow behavior. Thus, while many experimental and analytical studies of the process have been made, predictions of actual performance are still subject to considerable uncertainty and possible improvement. This paper reports on part of a study which attempts to develop improved methods for solution of the flow equations describing the miscible displacement process. Of necessity, the calculations were performed on a large digital computer. A three-dimensional system is represented, and the coefficients defining dispersion and permeability can be varied in a manner representative of a real system. Because the differential equations are nonlinear, a first step is to linearize them using a perturbation approach. Objective of this approach has been to separate the basic flow which would occur in an ideal system and for which predictions are readily made. Then the numerical analysis, which is necessarily complex, is directed toward solution of the perturbation equations. These equations state how the basic flow is modified

Jan 1, 1967

By H. J. Ramey

A general solution is presented for the transient temperature distribution caused by radial movement of a cylindrical heat source through a homogeneous medium of infinite extent. This problem represents a highly simplified model of the movement of a combustion front during the thermal recovery of oil. Numerical solutions are presented for a heat source moving at a constant velocity, and a velocity inversely proportional to the radial location of the heat source. Numerical solutions are presented for both finite and infinite vertical thickness of the heat source, i.e., with and without vertical heat losses. The numerical solutions are used to estimate the fuel concentration needed to maintain a combustion front during the thermal recovery of oil. The sensible heat carried to the combustion front by the injected gas stream is discussed in regard to the fuel concentration. Numerical solutions for a heat source (combustion front) of finite vertical thickness indicate the field conditions that may be necessary to sustain the temperature of a combustion front above the ignition temperature of the fuel over considerable distances from an injection well. The results also have implications in regard to the quantity of heat required during ignition. The results of this computation apply to a highly idealized model of a thermal recovery process. But the results may be used as a guide in engineering consideration of the thermal recovery process. INTRODUCTIO N The thermal recovery of crude oil has received considerable attention since the publication by Kuhn and Kochl of laboratory and field tests of this method of oil recovery. Other publications2,3,4,5,6, since that time have dealt with various features of the thermal recovery of oil and have illustrated the extremely complex nature of this process. Vogel and Krueger7 described an electric analog computer designed to solve a moving heat source problem which was analogous to movement of a combustion front during the thermal recovery of oil. The heat source was maintained at constant temperature and was a cylindrical source of infinite height (no vertical heat loss) moving radially at either constant velocity, or at a velocity inversely proportional to the radial location of the heat source. Jenkins and Ramey2 presented analytical solutions to a similar heat conduction problem and pointed out the possible importance of vertical heat losses. The following presents a general solution to the transient heat conduction problem introduced by Jenkins and Ramey4 as well as numerical solutions for a wide range of conditions possibly similar to those that might exist during field operation of the analogous thermal recovery process. DESCRIPTION OF PROBLEM The problem considered in this paper is determination of transient temperature distribution caused by a cylindrical heat source of infinite or finite vertical height, moving radially through an isotropic medium of infinite extent. It is further assumed that the heat flux generated at the surface of the moving heat source may be a function of time such that the fuel concentration required may be constant, or permitted to vary, and that heat is generated at the surface of the heat source only. In regard to the thermal recovery of oil the assumption that heat is generated at the surface of the front is equivalent to assuming that the thickness of the combustion zone is infinitely small, or that the reaction rate between fuel and oxidant gas is infinite. The last assumption does not appear stringent. See laboratory information published by Martin, et al3 Under these assumptions the temperature distribution throughout an infinite medium caused by a heat source moving radially with an arbitrary velocity may be described by The heat generation function or heat flux at the surface of the source, +(t), is Note that the fuel concentration may be defined as a function of time. Eq. 1 is derived in the Appendix.

By R. G. Aspden

Crystals with an (001) [loo] initial orientation of an iron-base alloy containing 3 pct Si were cold rolled with and without the use of constraints. A major difference in the rolling and annealing textures was observed between crystals rolled with and without constraints. These data show that the contribution of constraints at grain boundaries in a poly crystalline sheet should be considered in applying textural data on single crystals to grains in an aggregate. SILICON-iron alloys with a cube texture have been recently developed and their magnetic characteristics reported.1-4 Of interest in the development of this texture were the textural changes of single crystals accompanying rolling and annealing and the influence of constraints at grain boundaries in an aggregate on the behavior of individual grains. The present study was primarily concerned with the effect of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001)[100]. Barrett and Levenson5 were among the first to observe an influence of constraints at grain boundaries on the textural changes of individual grains during deformation. They tested Taylor's6 theory of plastic deformation of face-centered-cubic metals in which deformation textures were predicted. About one-third of the grains in poly crystalline aluminum did not rotate as predicted. Grains of the same initial orientation were observed to rotate in different directions under the influence of applied stress and anisotropic flow of neighboring grains. Recently, the various inhomogeneities of flow of crystals in an aggregate have been studied7'8 and reviewed.9-11 Barrett and Levenson" rolled (001) [loo] iron single crystals inserted in close-fitting holes in copper to limit lateral flow and to simulate rolling of grains in an aggregate. Deformation bands were formed after a 90 pct reduction in thickness, and the cold-rolling texture contained two components described by rotating the (001)[100] about 35 deg in both directions around the normal of the rolling plane. No annealing textures were reported. Chen and Maddin13 rolled molybdenum single crystals initially (001) [loo]. The crystals were mounted between two hardened silicon-iron plates and 96 pct reduced in thickness by rolling at a low rate of reduction, about 0.0001 in. per pass. The deformation texture had the mean orientation of (001) [loo], and the azimuthal spread included orientations described by rotating (001) [loo] about 35 deg in both directions about the pole of the rolling plane. The presence of deformation bands were not reported by Chen and Maddin or detected in subsequent work of Ujiiye and Maddin.14 The ideal orientation of the annealing texture was (001) [loo]. Recently, Walter and Hibbard 15 reported on the textures of 3 pct Si-Fe alloy crystals initially near (001) [loo]. Each crystal was in an aggregate cut from a columnar ingot. After 66 pct reduction by rolling, the texture consisted of two symmetrical components which had the orientations described by rotating (001) [loo] about 30 deg in both directions about the pole of the rolling plane. Annealing texture was near (001) [loo]. In the above work, the textures of body-centered-cubic crystals were studied after rolling under the influence of constraints. The deformation textures varied from (001) [loo] to near the (001) [110] type and appeared sensitive to the manner in which the crystals were rolled. No textural data were available on the effect of rolling (001) [loo] crystals with and without constraints. The purpose of the present work was to evaluate the influence of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001) [loo]. Rolling and annealing textures were studied for a) crystals rolled with no constraints at different rates of reduction, and b) crystals rolled with constraints imposed by neighboring grains and by plates between which a crystal was "sandwiched". PROCEDURES AND EXPERIMENTAL TECHNIQUES Data are presented on four crystals which are representative of several crystals studied. The orientation of each crystal prior to rolling was (001) [loo] as determined by the Laue X-ray back-reflection method," i.e., each crystal had an (001) within 3 deg of the rolling plane and [100] within 3 deg of the rolling direction. These crystals were obtained from two iron-base alloys containing 3 pct Si by weight which were prepared by vacuum melting electrolytic iron and a commercial grade of silicon. Crystals 1, 2, and S-1 were cut from a large single crystal grown from the melt of one alloy by the Bridgman technique17 in an apparatus described by

Jan 1, 1960

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 D. S. Rowley, F. C. Appl

Assuming that rock behavior, during cutting with a single diamond, may be approximated by that of a rigid, Coulomb, plastic material, a theory of single diamond cutting action has been developed. Using this theory, the stresses on the diamond cutting surface and the components of the cutting force have been determined. Theoretical results agree reasonably well with available experimental data. The theory of cutting of single diamonds may be used as the basis for subsequent study of the perfonnance of surface set diamond drill bits and other surface set diamond cutting tools. INTRODUCTION For more than twenty years, surface set diamond bits have been used successfully in the mining and petroleum industries to drill and core rock formations that range from medium hard to the hardest known formations. Most extremely hard rock formations cannot be economically drilled or cored by any other means. In view of the growing use and importance of surface set diamond drill bits, it is reasonable to study the way in which these tools cut, and the factors that influence wear of the diamonds. Such knowledge will contribute to better bit design and will improve operating procedures. To analyze the cutting performance of these tools it is appropriate to consider the way in which an individual diamond cuts. Once this is established, the over-all performance of the bits can be determined by considering the total effect of the individual diamonds. In recent years there has been a growing interest in rock mechanics and there now exist several publications dealing with the deformation and failure of rocks. Notable experimental work has been reported by Bredthauer,1 Handin and Hager,2, 3 and Gnirk and Cheatham.4 An extensive collection of data pertaining to rock properties at low confining pressures has been given by Wuerker.5 Cheatham and Gnirk have recently presented an excellent review of the state of knowledge regarding analytical and experimental rock deformation and failure.6 Generally rocks are extremely weak in uniaxial tension, and weak or only moderately strong in uniaxial compression. Both tensile failure and compressive failure are generally brittle in nature. This means that there is little or no deformation or "flow" of the material before shear or tensile fracture occurs. Thus, until fracture occurs, rock behaves very nearly like an elastic material in uniaxial stress. Significant changes in behavior of rock occur under conditions of triaxial compressive stress. There is generally a marked increase in compressive strength and in ductility. It has been demonstrated that the failure becomes plastic (in a macroscopic sense) at sufficiently high values of confining pressure. Sharp wedge chisel indentation studies conducted by Gnirk and Cheatham indicate that many rocks behave in a plastic manner at relatively low triaxial compressive stress states.4 If "failure" under triaxial compressive conditions is considered to be either complete rupture or macroscopic plastic flow, then the general failure characteristics of a rock can be reasonably well represented by the commonly known Mohr envelope. This certainly is not a perfect failure criterion (since the effect of the intermediate principal stress is neglected) but it has been found to be adequate for most engineering purposes. Mohr envelopes usually are constructed graphically using experimental triaxial test data. For purposes of analysis it is convenient to represent the envelope in equation form. Among the several approximate forms appearing in the literature, a parabolic form is suggested by Cheatham,7 and an exponential form is suggested by Paone and Tandanand.8 The exponential form has been adopted for this study, and based on published data, appropriate parameters have been established for 19 rock types. A typical plot of the data compared with the approximate envelope, and a summary of the rock properties and

Jan 1, 1969

By Oren C. Baptist, Carlon S. Land

Laboratory research has been conducted to evaluute the effect of clay hydration on the permeability to gas of water-sensitive reservoir sands. Samples of a .sandstone containing trace amounts of montmorillonite and a sample of montmorillonite were .studied in the laboratory to detertnine whether swelling or dispersion was the cause of permeability reduction in these samples. Heliuin, containing various amounts of water vapor, was used to hydrate the clay minerals and to determine the gas permeability at various stages of clay hydration. The amount of water adsorbed by the samples using this method is small. The nonwetting-phase permeability at higher water saturations war investigated by saturating the with water and measuring the permeability to humid helium while decreasing the water saturation, Relative-permeability curves obtained from results of these procedures were used to estimate the effect of the swelling of trace amounts of mont/tlorillonite on the permeability of the .samples. Most of the damage to the permeability when reservoir sands containing trace amounts of montmorillonite are exposed to fresh water is due to dispersion and movement of clays. Blockage of pores by the increased volume of expanded montmorillonite is believed to result in permeability damage that is small in comparison to the observed damage to the samples tested. INTRODUCTION Studies have shown that permeability is severely damaged when sands containing only small amounts of montmorillonite are contacted by fresh water.15 When samples of sands containing large amounts of montmorillonite are placed in fresh water in the laboratory, these samples may completely disintegrate, forming an unconsolidated mass of larger volume than that occupied by the dry sample." In this case, it is apparent that the swelling of montmoril-lonite has destroyed the pore structure of the sand. If only a trace of montmorillonite is present in a sand. samples may remain intact when saturated with water, although the permeability to water is a small fraction of the gas permeability of the dry sample. Many workers in the field of water sensitivity have attributed this reduction in permeability to the blocking of pores and reduction of pore size by the increased volume occupied by expanded mont- niorillonite. if the sand contains a detectable amount of montmorill'onite or mixed-layer clay containing rnontmorillonite. Logically3 the smaller amount of montmorillonite present in a sand, the smaller should he the effect of montnlorillonite swelling on permeability; however, the quantity of montmorillonite sufficient to cause severe damage by swelling is not known. Although hundreds of samples have been tested in our laboratory, no correlation has been established between the amount of montmorillonite in samples and the permeability reduction caused by fresh water. To many petroleum engineers, the phrase "clay swelling" is synonymous with "water sensitivity", or "permeability reduction" implying that any formation damage due to the hydration of clays is caused by swelling. Although all clays adsorb water on their surfaces, montmorillonite is the only clay mineral commonly found in reservoir rocks which adsorbs water between intercrystalline layers, resulting in expansion of the clay particle. As montmoril-lonite swells, the first few layers of water adsorbed between platelets are strongly held and well oriented, and the montmorillonite retains its crystalline structure, although expanded. As swelling of sodium montmorillonite continues, the platelets become farther apart and the forces orienting the platelets in the crystalline structure become weaker, resulting in a less orderly orientation of platelets. In an abundance of water, small groups of platelets may become detached from the original monl-rnorillonite particle and may be dispersed throughout the water phase. Because of its swelling properties, sodium montmorillonite is very easily dispersed in water. Particles of other clay minerals. such as illite and kaolinite may also be dispersed in water. causing water sensitivity of sands not containing montmorillonite. The presence of an immobile layer of water adsorbed on the surface of clays has been considered a possible cause of the low permeability to water of dirty sands. Grim states that the thickness of the layer of immobile water held by sodium montrnorillonite is three nlolecular layers or 7.5 A (angstroms), with some orientation of water extending to 100 A. Assuming a very thick, immobile water layer adsorbed on the surface of a pore represented by a capillary tube, the maximum effect of the water layer on permeability can be calculated. Using a pore radius of 10 ' cm and an immobile water layer of 50 A. the calculation shows the permeability to be reduced only 2 per cent. Similar calculations can be used to show that the effect of electro-osmotic counterflow is of the same order of magnitude as that of bound water. The reduction of the permeability to water by either an immobile water layer

Jan 1, 1966

By S. Shapiro, G. Krauss

The strutural and cr~stallo~aphic features of the plates of austenite produced by the martensite to aus-tenite or reverse martensitic tramformation have been determined in an Fe-33 wt pct Ni alloy. Micro-focus X-ray techniques and single-surface trace analysis 072 bulk samples yielded two distinct habit planes, (0.174, 0.309, 0.~35)~ and (0.375, 0.545, 0.749jM. The former plane uas the one predorninantly observed and its existence was verified by transn~ission electron microscopy. The orientation relation-ship between the reversed austenite and the parent martensite was approximately the same as the Nishiyamna and other relationships reported for the direct tramformation. Replica and thin-joil obser-vations show that both high densities of tangled dis-locations and occasional twins constitute the fine structure of the reversed austenite. Application of the phenomenological theory to a variant of the predominant habit plane defines an irrational plane and direction for the second shear in accordance with the comnplexity of the fine structure. The shear accompanying the reverse martensitic transformation is at least 0.51, the maximnum value of- the tangent oJ the tilt angle measured on surface replicas. A mechanism relating the fine transformation twins in martensite to the nucleation of reversed austenite of the predominant habit is proposed. The reversal of Fe-Ni martensite takes place both at the edges of martensite plates and in a piecewise fashion within them.' The shear-type nature of the reverse transformation is verified by the surface relief which accompanies both edge-type reversal2 and the fragmentation of plates of martensite' as a result of rapid heating above the A, (austenite start temperature). The orientation relationship between the edge-type reversal product and the parent martensite, as determined by transmission electron microscopy, is reported to be within 4 deg of either the Kurdyumov-Sachs or Nishiyama relationships,' but there is no work at present in the literature relating to the crystallography of the platelike reversed austenite. The fine structure of reversed austenite after heating to 50°C above the Af is reported4 to be composed primarily of tangled and jogged dislocations in concentrations up to 10" per sq cm. A replica investigation of partially reversed Fe-Ni martensites5 corroborates the increase in dislocation density following reversal and presents indications of other possible modes of fine structure. This paper reports on an investigation performed to examine in detail the morphology and crystallography of the plates of reversed austenite and the shear which accompanies their formation in a matrix of Fe-Ni martensite. EXPERIMENTAL PROCEDURE Discs of a high-purity Fe-32.9 wt pct Ni single crystal served as the starting material. The single crystal had been produced in the course of an earlier investigation6 and the carbon content was determined at the time to be 0.006 wt pct. The M,, and the A,, were respectively -120" and 300°C. Partial transformation to martensite was performed at -125°C and reversal of some of the martensite was accomplished by heating in the temperature range 340" to 355°C. Most samples were heated to the reversal temperature by immersion' in a salt bath for 2 min. For surface-relief studies some polished and etched Samples were heated in a tube furnace for ten min in a hydrogen atmosphere maintained over the samples throughout the heating and cooling cycles. Samples were prepared for metallographic examination by electropolishing and etching with an HC1-HNOs-H20 et~hant.~ On one of the surface-relief samples two sets of fiducial scratches were placed on the etched sample by drawing it over a slurry of 0.06 p alumina on a "microclothJ'. The orientations of individual plates of martensite were determined by X-ray analysis. A Rigaku-Denki microbeam X-ray generator in conjunction with a Micro-Laue camera with facility for precision location of the sample in front of the beam was employed for this purpose. The collimator size was 30 p and the specimen to film distance was 5 mm. The Laue photograms were enlarged to an equivalent 3-cm specimen to film distance for analysis. The orientation of each of the plates of martensite was compared to that of the parent austenite and the relationship be -tween the two phases was, in all cases, within a few degrees of those predicted for the direct transformation. The orientation relationship between one of the larger plates of reversed austenite and its parent martensite was determined in a similar manner. The habit plane of the islands of reversed austenite in the X-rayed plates of martensite was determined by a single-surface trace analysis. Each reversal island had with the parent phase one comparatively straight boundary which was presumed to represent the habit plane trace. The pole locus technique7 was applied to traces from six different plates of martensite to determine the indices of the habit plane. A 40-cm stereographic net was employed for this analysis The morphology and fine structure of the reversed austenite were studied by electron microscopy of pre-shadowed direct carbon replicas,5 and the macroscopic shear was evaluated by a two-stage replica technique similar to that employed in electron fractog-

Jan 1, 1968

By E. P. Polushkin, Henry L. Shuldener

This paper describes the results of microscopic examination of a series of brass pipes removed from apartment and office buildings in New York City, adjacent localities on Long Island, and Philadelphia. They were selected as typical of approximately four hundred pipe specimens obtained over a period of five years during an investigation of corrosion in hot-water installations. A part of the investigation is reported in this paper and includes a brief history of the pipes, a description of their inside surface and microstructure, and a study of the effects of corrosion, with particular reference to the structural aspects of local and selective dezincification. Although the bibliography on the corrosion of brass pipes is quite extensive, it refers almost entirely to corrosion in sea water. The authors believe that their examination of this series of pipes, which had been subjected to the corrosive action of fresh water for various lengths of time, may throw some additional light on the problem of corrosion. Pipes Examined The pipes were made by different manufacturers and their sizes range from 3/4 in. to 4 in. nominal inside diameter, the majority being within I to 2 in. They can be divided into two groups according to chemical composition: (I) with a copper content of 60 to 62 per cent and (2) with a copper content of 65 to 68 per cent. The first group (pipes made of Muntz metal) comprises 22 pipes and the second (pipes made of high brass) comprises 18 pipes. The pipes had been in service in various locations in the hot-water systems of the buildings involved. Some were taken from horizontal lines in the basement, some from overhead distributors and some from vertical risers. The distance, in terms of feet of pipe, of the specimens from the hot-water generator was no less than 75 ft. and often IOO to 300 ft. In the majority of cases the water-heating equipment was provided with a regulator to limit the temperature of the hot water supply. The normal range of temperature in pipe systems of this kind is Ioo° to 160°F. Water Supples The average chemical composition of the water supplies carried by the pipes is shown in Table I. In evaluating the corrosiveness of a natural water, four factors are considered of prime importance: namely, hardness, alkalinity, pH and silica content. The waters listed in Table 1 are characterized by relatively low hardness, 10, alkalinity, low pH and low silica content. The waters of lower pH and higher CO2 content are more corrosive. A characteristic of all of these waters is that they do not deposit a protective mineral coating as do waters with high bicarbonate of lime content, which would be reflected

Jan 1, 1945

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature microhardness of as-grown and annealed MoaC single crystals was measured on the (0001), {2110), and1012) planes using Knoop and Vickevs indenters at loads ranging front 25 to 1000 g. The orientatimz dependence of hardness with respect to crystal axes was also studied. The average random hardness of as-grown crystals was determined to be 1520 kg per sq nm. Annealing to 2000°C decreased. the average hardness by 150 units. An increase in hardness after annealing at 2200 ;C was noted. Optical and electron microscopy revealed slip and twin traces on all planes studied, as produced by mi-cvohavdness indentations. Basal (0001)(2i10) slip was determined to be the primary slip system and was substantiated by electron transmission microscopy. A secondary {1010)(2110) slip was produced by mi-crohardness indentations. The lattev also produced twinning- of the {10i2)[0001] type, as proven by electron diffraction. Electrical resistivity and elastic-modulus anisotropy were found and correlated with hardness anisotropy and Mo2C crystal structure. Elastic-modulus values were obtained by microhard-uess and ullrasonic methods. Bonding mechanism of Mo2C is discussed. ROOM-TEMPERATURE microhardness indentations are useful for studying hardness anisotropy, slip, and twinning in brittle materials. Slip has previously been produced in this manner in and WS~~.~ Recently, the authors5 reported slip of the {10i0)(11~0) type produced by high pressure and microhardness indentations on hexagonal TiBz (c/a = 1.066) single and polycrystals. This slip system was also reported by French and ~homas' and Taka-hashi and ~reise~ for hexagonal WC (c/a = 0.976) crystals. These results suggest that prismatic rather than basal slip is favored in hexagonal nonmetallic materials having a c/a ratio considerably less than the ideal (1.633). Buerger precession and cylindrical X-ray rotation patterns were previously' taken on cleaved sections of the Mo2C single crystals studied in this work. Th~y were found to be hexagonal MoaC with a. = 3.0233A, co = 4.7344A, and C/O = 1.5660. The latter ratio is close to that of the beryllium metal (c/a = 1.57), which slips primarily on the (0001) plane: but also slips on the (1010) planes.'0 ~irconium" (c/u = 1.59) and titanium12 (c/o = 1.59) deform mainly by slip on nonbasal planes which contain a close-packed direction. This is due to the fact that for these two metals the initial resolved shear stress for slip on the (10i0) prismatic planes is lower than that on the (0001) plane. The prominence of basal rather than prismatic slip in metals of high c/o ratios is shown by cadmium (c/a = 1.89), zinc (c/a = 1.86), and magnesium (c/a = 1.62) which deform mainly by basal slip. However, in case of the latter, by stressing magnesium crystals in tension or compression parallel to the basal plane, slip on (10i0) planes can also be produced.13 Several hardness values for polycrystalline Mo2C are reported in the literature: Biickle ' and Samsonov'~ give a value of 1800 and 1479 kg per sq mm, respectively, at a 100-g load; and Kieffer and Benesovsk~'~ report a value of 1950 kg per sq mm at a 50-g load. ~ott'~ reports a Vickers hardness value of 2000 kg per sq mm, with the load unspecified. A Rockwell A hardness value of RA = 88 has also been reported.'' In the present work, for comparison with single-crystal Mo2C hardness values, a Khnloo value of 1600 It 150 kg per sq mm was found on 99.6 pct pure and 99 pct dense hot-pressed Mo2C. This work was undertaken partly to explain the considerable differences in hardness values reported for polycrystalline Mo2C. EXPERIMENTAL The Mo2C single crystals investigated were prepared by a Verneuil-type process using an electric arc by the Linde Co. of the Union Carbide Corp.lg The largest specimens grown were boules 7 mm in diam by 40 mm in length. The crystals had an average density of 9.04 g per cu cm, with a Mo + C content of 99.8 wt pct. The major impurities were: 100 ppm each Na, Zr, and Ca; 85 ppm 0, 55 ppm Fe, and 10 ppm each Cr and Ta. The crystals were found to be carbon-poor, the average carbon content being 5.73 wt pct (stoichiometric value is 5.89 pct). The molybdenum content was found to be 94.08 pct, which is nearly stoichiometric. Electron-microprobe traverses of selected specimens were done with a Phillips-AMR microanalyzer. Thin-film and carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to optical and electron-optical studies, specimens were mounted in Lucite and polished on a vibratory polisher using diamond-paste grades ranging from 9-1 p and Linde A powder for up to 48 hr. Dilute nitric acid was used for thin-section polishing and chemical etching for 1-15 min. Electrical-resistivity measurements at room temperature were taken with a Rubicon bridge, using gold contacts. For hardness measurements, a Tukon Microhardness Tester Type FB with Knoop and Vickers indenters was used. Measurements were taken at loads ranging from 25 to 1000 g; however, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Indentations of cracking classes 1 and 2 only were considered for hardness determinations.20)21 (There are six cracking classes, ranging from "class 1" for a perfect inden-

Jan 1, 1967

By A. Bauer, P. Calder, N. H. Carr, G. R. Harris

Since both rotary and jet piercing drills are used by the Iron Ore Co. at Smallwood, it is often desirable in planning to know in which regions of the orebody or new orebodies a particular drill will be the most economic. This makes it necessary to establish a correlation between drillability and pierceability and some physical rock properties. For rotary drills a good correlation was found with penetration rate and grinding factor index. The jet piercers were found to have a reciprocal relationship in the sense that the best rotary ground was the worst jet ground and vice versa. It is also indicated how an economic comparison could be made using these penetration rate versus grinding factor index curves, the hole size distribution curves for single pass and chambered holes and the mine distribution curve for grinding factor index. A discussion is presented on the fuel oxygen ratios to be used in jet piercing and on the site gas sampling and analysis which has been used to set up the drills. The fuel has been cut back so that stoichio-metric conditions exist, carbon monoxide is drastically reduced and pop-up or exploding holes eliminated. No decrease in penetration rate has been observed contrary to the published results of previous workers. The blasting procedure and results at Smallwood are discussed and the operation of Iron Ore Co.'s slurry pump-mix truck is also described briefly. Smallwood mine is part of the Iron Ore Co.'s Carol Lake operation and is situated in Labrador, 240 miles north of Sept-Iles, Quebec. Last year 15 million tons of crude ore were crushed to yield 6.3 million tons of concentrate and pellets. This year the figures will be 17 million tons of crude and 7% million tons of concentrate and pellets which is the full plant capacity. Carol Lake ores consist primarily of specularite and magnetite mixed with quartz. For convenience the ore has been split-into the following classifications depending on the percentage of magnetics in the sample, shown in brackets: specularite (0 to 10%), specularite-magnetite (10 to 20%), magnetite- specularite (20 to 30%), magnetite (>30%). The order of classification also represents the order of increasing grinding difficulty - the specularite generally being the easiest and the magnetite the hardest. The orebody also contains a small percentage of waste materials consisting of limonite carbonate, quartz carbonate and quartz magnetite. The first two materials are among the softest in the mine, generally softer than the specularite, and the quartz magnetite is amongst the hardest. The bulk of the material in the mine is of the specularite-magnetite and magnetite-specularite classifications. As a result of test drilling at Smallwood in 1960 with rotary, jet and percussion drills, the Iron Ore Co. purchased four JPM-4 jet piercers for the bulk of production drilling and set up an oxygen plant to supply 20 tons of oxygen per day. This oxygen is sufficient for two machines operating full time and one part time. In addition, there are two 50-R, one 60-R and one 40-R machines in use. The benches are 45 ft high and 50 ft holes are generally drilled. JET DRILLING At the onset of jet drilling in the late fall of 1962, two major problems were encountered: 1) freezing due to winter operations; experience and the use of heat at more places, such as the rotary head, has eliminated this,'" and 2) exploding or "popping" drilled holes; this happened frequently (several holes "popping" each day) and was the cause of two lost time accidents. In one instance a hole was being measured with a tape which fell down the hole causing it to "pop." Safety glasses though pulverized saved the wearer's eyesight. Various methods were then employed to detonate the holes before measuring or loading (dropping lighted rags of fusees down, or sparking across a spark gap). These methods were time consuming and far from completely successful. Consideration was given to the fuel oxygen ratio on the machines and what this would produce in the way of product gases. A fuel oxygen weight ratio of 0.35 which was quite oxygen negative was being used. Theoretically appreciable carbon monoxide would be produced at this fuel oxygen ratio. On the close down procedure of the jet which calls for low oxygen after flame out, oxygen would be left in the hole along with this carbon monoxide. This is an explosive mixture. The fuel oxygen ratio was cut back to stoichiometric

Jan 1, 1967

By D. C. Seidel, E. F. Fitzhugh

The Colorado School of Mines Research Foundation has developed a hydrometallurgical process for recovering nickel from oxidized ores, including both the iron-rich laterites and magnesium-rich, soft silicates. Known as the HSO-HTCP (Hydrothermal Sulfidization Oxidation-High Temperature Cementation in Pulp) Process, the system consists of feed preparation, sulfidization, oxidation, precipitation (cementation), and calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Nickel sulfide ores lend themselves readily to concentration before smelting or pressure leaching, but neither of the major oxidized ore types — the iron-rich laterites and magnesium-rich, soft silicates-has been directly concentrated. Upgrading of crude ore in current practice is limited to cobbing lumps of the harder, lower grade rock (protore) from the softer, enriched silicate ore, because only a small percentage of the nickel in these ores occurs in discrete, contrasting mineral particles. There is no apparent mineralogical contrast in the superficial, iron-rich lateritic ores and, in fact, there is no firm assurance that the nickel atoms are within the lattices of the limonite minerals, or else irregularly adsorbed on the limonite. Within underlying, "rotten rock" silicates, occasional veinlets of gamierite and related nickeliferous silicates are found.' The gamierite veinlets, however, are only incidental, and the majority of the nickel atoms occur as erratic replacements of magnesium atoms in the micaceous chlorites of the ore mass. Pyrometallurgical processes account for nearly all the nickel currently being recovered from oxidized ores. Plants in New Caledonia, Oregon, Japan, Brazil and Greece smelt the ores to make ferronickels or a sulfide matte,2 and the ammoniacal leaching3 at Nicaro, Cuba, is preceded by a reducing roasL4 The only fully hydrometallurgical installation has been the politically ill-fated Freeport Nickel Co. enterprise, and this process was limited to lateritic ores.5p6 A hydrometallurgical technique which might handle both laterite and the typically richer silicate ores has been an enticing goal. The technique described here was developed at the Colorado School of Mines Research Foundation, Inc. on behalf of the Republic Steel Corp. It uses sulfur, heat, air and metallic iron to recover nickel from these ores. Inasmuch as the ores are treated as aqueous slurries, the cost of drying a plant feed that normally carried 30% or more moisture is eliminated, and there are no dust problems. Patent applications have been filed by Republic Steel Corp. on the procedures used for getting the metal into solution and on the subsequent recovery without liquids-so l ids separation of the slurry. It is referred to as the HSO-HTCP Process (Hydrothermal Sulfidization Oxidation — High Temperature Cementation in Pulp). THE PROCESS FLOWSHEET The results of various experimental studies have been combined to form the continuous flowsheet illustrated in Fig. 1. This flowsheet serves as a general pattern showing the sequence of the operations which include: (1) feed preparation; (2) sulfidization; (3) oxidation; (4) precipitation (cementation); and (5) calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Feed preparation: In general, the silicate ores can be considered as earthy rather than hard, and preparation might be carried out before the addition of water in a trommel, or with water in a scrubber or log washer. This breaks up the earthy particles, allowing the hard lumps to be separated by screening. The oversize material from most ores is relatively barren and may be discarded. If there is occasion to control the iron-magnesium ratio in the plant feed, laterite, which normally breaks up readily into fine sized particles, and silicates are mixed in suitable proportions. The fine product slurry from the initial steps is mixed with elemental sulfur and fed to a conventional ball mill, although the amount of actual grinding that takes place is relatively small. The object of milling is to complete the disintegration to natural particle size and to produce an intimate mixture of the ore and elemental sulfur. This pulp, which is almost entirely -200 mesh, has a pH of about 7.0 and normally can

Jan 1, 1969

By F. M. Smith, R. H. Moore, J. R. Morrey

Electrodiffusion in y cerium reported by Henrie has been confirmed and a Preliminary estimate made of the relative rates of electrodiffusion of iron, cobalt, and nickel. These diffuse to the anode at rates decreasing in that order. In addition, copper and manganese exhibit slow, but detectable, diffusion to the anode and molybdenum exhibits detectable diffusion to the cathode. The electrodiffusion of carbon, .zirconium, antimony, magnesium , and silicon in y cerium could not be detected. Iron and cobalt diffuse in y cerium at rates proportional to the current density and with no apparent dependence on temperature. Decreasing polarization of iron and cobalt with increasing temperature, which cancels the expected rate increase, would account for this behavior. The electrodiffusion rate of iron in y uranium and in E plutonium has been measured. Diffusion of iron is anode-directed. Tin was found to diffuse to the cathode, in y uranium, at an appreciable rate. In all of these solvent metals, negative ions diffuse to the anode and positive ions to the cathode. The potential field effect appears to account satisfactorily for these results. FROM early experimental work summarized by Jost1 and Seith,2 the driving force for electrodiffusion was attributed to the potential field acting on ions in a metal. More recently, Heuman,3 Wever,4 and Huntington5 have shown that momentum interchange between conduction electrons and mobile entities in the metal contributes to electrodiffusion. Electron momentum interchange is anodically directed and the direction of diffusion resulting from the field force is dependent upon the charge on the diffusing entity. These two effects may either reinforce or oppose each other. Glinchuk6 has pointed out that momentum transfer in defect conductors should be cathode-directed and this appears to be the case as demonstrated by wever's4 work on iron. Barnett's7 work, on the other hand, indicates that, even in defect conductors, electrons show a negative E/m ratio when accelerated with respect to the lattice and should lead to anode-directed momentum transfer. In discussing this problem, Wever and seith8 suggest that defect electrons interact preferentially with activated ions so as to allow a net movement toward the cathode while still maintaining an electron momentum transfer in the anode direction. Williams and Huffine9 and Henriel0 have demonstrated that electrodiffusion may be useful for purification of yttrium and cerium. In yttrium, Williams and Huffine note that movement of several metallic impurities toward the anode is in keeping with observations in most other metallic systems and indicates that yttrium remains a normal electronic conductor at least to 1230°C. Close inspection of their data shows, however, that oxygen, nitrogen, and the transition elements diffused toward the anode, while nontransition elements diffused toward the cathode. This suggests that potential field effects may have been appreciable. The present work was concerned with the applicability of electrodiffusion as a technique for purification of plutonium, but, because of the obvious hazard inherent in work with this metal, experiments to develop the technique were carried out using cerium and uranium. The results of electrodiffusion measurements on these metals and on plutonium are reported here. EXPERIMENTAL The metal specimens prepared for this work were 6 in. long, 1/4 to 1/2 in. wide, and 1/16 to 3/32 in. thick. The uranium specimens were machined from a bar which analyzed 310 ppm Fe and the electrodiffusion of iron was followed by spectrographic and by chemical analysis. Cerium and plutonium specimens were cut from sheet rolled from ingots obtained from molten salt-metal equilibrations during which radioactive tracers were introduced. The electrodiffusion of the tracers was subsequently determined by counting methods. The specimens were electrolyzed between nickel electrodes containing resistance heaters used to equalize the specimen and electrode temperatures, thereby reducing thermal gradients. The temperature of the electrodes adjacent to the ends of the specimen was measured with chromel-alumel thermocouples which were connected to the heater controls. The surface temperature of the specimen at a point midway between the electrodes was measured with a sapphire rod pyrometer, the output of which controlled the dc power supply. This assembly was enclosed within an evacuable chamber containing a quartz viewing window. The temperature of the specimen over its entire length could be scanned with a portable pyrometer through

Jan 1, 1965

By A. Lubinski

In drilling operations, attention generally is given to hole angles rather than to changes of angle, in spite of the fact that the latter are responsible for drilling and production troubles. The paper presents means for specifying maximum permissible changes of hole angle to insure a trouble-free hole, using a minimum amount of surveys. It is expected that the paper will result in a decrease of drilling costs, not only by avoiding troubles, but also by removing the fear of such troubles. SUMMARY, CONCLUSIONS AND RECOMMENDATIONS Excessive dog-legs result in such troubles as fatigue failures of drill pipe, fatigue failures of drill-collar connections, worn tool joints and drill pipe, key seats, grooved casing, etc. Most of these detrimental effects greatly increase with the amount of tension to which drill pipe is subjected in the dog-leg. Therefore, the closer a dog-leg is to the total anticipated depth, the greater becomes its acceptable severity. Very large collar-to-hole clearances will cause fatigue of drill-collar connections and shorten their life, even in very mild dog-legs. Another finding regarding fatiguing of collar connections in dog-legs is that rotating with the bit off bottom sometimes may be worse than drilling with the full weight of drill collars on the bit, mainly in highly inclined holes when the inclination decreases with depth in the dog-leg. Means are given for specifying maximum dog-legs compatible with trouble-free holes. An inexpensive technique proposed is to take inclinometer or directional surveys far apart; then, if an excessive dog-leg is detected in some interval, intermediate close-spaced surveys are run in this interval. The application of the findings should result in a decrease of drilling costs, not only by avoiding troubles, but mainly by removing the fear of such troubles. The result would be much more frequent drilling with heavy weights on bit, regardless of hole deviation. Because of errors inherent to their use, presently available surveys are not very suitable for detecting dog-legs. There is a need for instruments especially adapted to dog-leg surveys. Crooked hole drilling rules should fall into two distinct categories—(1) those whose purpose is to bottom the hole as desired, and (2) those whose purpose is to insure a trouble-free hole. Three kinds of first-category rules in usage today are as follows. 1. A means to bottom the hole as desired is to prevent the bottom of the hole from being horizontally too far from the surface location; this may be achieved by keeping the hole inclination below some maximum permissible value such as, for instance, 5. 2. Another means to achieve the same goal is to limit the rate at which the inclination is allowed to increase with depth. A frequently used rate is 1/1,000 ft. In other words, a maximum deviation of l° is allowed at 1,000 ft, 2 at 2,000 ft, 3 at 3,000 ft, etc. 3. Whenever application of the first two means precludes carrying the full weight on bit required for most economical drilling, then the best course is to take advantage of the natural tendency of the hole to drift updip, displace the surface location accordingly and impose a target area within which the hole should be bottomed. This method has already been successfully applied,'.' and its usage probably will become more frequent in the future. Means for calculating the amount of necessary surface location displacement are avail-able.3'5'6 If in high-dip formations the full weight on bit should result in unreasonably great deviations, the situation could be remedied by increasing the size of collars and (if needed) the size of both hole and collars,351 or in some cases by using several stabilizers. Rules which would fall into the second category (i.e., rules whose purpose is to insure a trouble-free hole) are seldom specified today. It is vaguely believed that following Rules 1 and 2 of the first category will automatically prevent troubles. Actually, this is not true. If at some depth the only specified rule is that the hole inclination must be less than 4", the hole may be lost if the deviation suddenly drops from 4 to 2, or if the direction of the drift changes, etc. Rule 3 of the first category is generally used in conjunction with a rule belonging to the second category, namely, that the hole curvature' (dog-leg severity) must not exceed the arbitrarily chosen value of 1½ /100 ft. Moreover, when using this rule, the industry is not clear over what depth intervals the hole curvature should be measured. All this results in a frequent fear

By A. N. Chirico

This paper reviews the three major distillation processes: multiple effect (LTV) evaporation, multi-stage flash distillation and vapor-compression forced circulation evaporation. Scale preventative measures are discussed for all saline water applications. Operational data is presented on the Freeport, Texas, demonstration plant, which is the first government facility to produce one million gallons per day of fresh water for a municipality. There has been much publicity concerning the water crisis that confronts many peoples today. There is little doubt that the arid regions - which include the Middle East, parts of Africa and the Caribbean — have suffered to no slight extent for the lack of this most precious commodity. But what about our own country? Government experts have extrapolated demands and flatly predict that by 1980 we will be faced with a shortage of 80 billion gal per day. The validity of this prediction has been disputed by others; however, it appears certain that there will always be a natural abundance in some areas, a shortage of supply in other areas. Distributing our total natural water resource equitably would be impossible. Transmission of water by means of aqueducts can be an expensive undertaking. The controversial Feather River Project in Calif. is an example. The estimated cost for this venture is a staggering three billion dollars. As our population continues to increase and our standard of living rises, agricultural and industrial requirements will be proportionate. What can be done to avoid a crisis? We can conserve and use our water for industrial and irrigation purposes more judiciously: we can attempt to eliminate pollution of our natural resources from sewage and industrial wastes; we can develop, while there is time, saline water conversion processes for the massive production of low cost fresh water. The scope of this paper will be limited to only the distillation type processes that are commercially feasible. The first step in making potable water is to find a source of raw material. An inexhaustible supply is provided by oceans in coastal regions, but the supply of water is more critical in the inland communities of our country. The source of raw material in these. regions is brackish well water and this must be utilized. There is a significant process difference when handling brackish water compared to seawater and this brings out an important fact: No single conversion method can be universally applied to solve all the water problems. Composition of the raw water and degree of distillate purity are factors which must be considered before a particular process is selected. Local conditions at the plant site, fuel costs, labor costs, disposal facilities, etc. are other equally important factors which must be evaluated. WATER CONVERSION PROCESSES Conversion processes commercially feasible today are: 1) multiple effect evaporation, 2) multiple flash distillation, 3) vapor compression distillation and 4) electrodialysis. The first three are distillation processes which take potable water out of the raw water, while the fourth is a membrane process which takes out the salt. In addition to the above there are a good number of other promising methods for production of potable water, many of them in the basic research stage. Freezing is another promising process with commercial potential. This process hinges upon the formation of ice crystals which are free of salt occulsions. Separation and washing of the crystals are problems that must be solved before this process can be considered commercially feasible. Freezing processes have several advantages mostly attributable to the low temperature of operation. This low temperature reduces the scaling and corrosion problems encountered in higher temperature operations. Several different freezing processes are being considered and will be tested in the pilot plant at Wrightsville Beach. One process is a flash freeze process, a second uses a secondary refrigerant such as butane for freezing, and a third process employs a secondary refrigerant particularly controlled to produce large ice crystals. Of the above processes, only the distillation processes are reliable when water of high purity is re-

Jan 1, 1963

By L. C. Michels, O. G. Ricketts

The disorientations between s?nall grains, whose growth has been arrested at an early stage of recrys-tallization, and the deformed matrix in cold-rolled aluminum single crystals were determined using transmission Kikuchi line and electron diffraction patterns. The orientations of the recrystallized grains were found to be random, and the disorientations of these grains with the matrix weve found to be intermediate to large. This leads to the conclusion that the observed vecrystallization began in small areas of large disorientation present in the cold-worked structure. heavily cold-worked thin sections of aluminunz single crystals and of polycrystalline aluminum and nickel were produced directly by a mechanical technique. The specinlens thus prepared were heated with the electron beam to bring about vecrystallization during observation in the electron microscope. Motion pictures taken du.ring heating and the electvon, microg.raphs taken both before and aftev heating allowed the recrystallization process to be traced to its ovigin. Re cvystallized grains originated in very s,mall regions of the cold-worked structure and developed through rapid migration of high-angle boundaries. The boundaries either were present as such in the matrix or were formed out of dense dislocation networks. SIGNIFICANT advances have been made in recent years in the study of nucleation of recrystallization using the technique of transmission electron microscopy of thin metal foils. Bollman1 in a study of heavily rolled polycrystalline nickel found support for the Cahn-Cottrell2,3 theory of nucleation. According to this theory nuclei form by the initially slow growth of subgrains formed through polygonization. During this initial period of slow growth (the incubation period) the migrating boundary of the subgrain increases its disorientation with the cold-worked matrix and thereby increases its mobility to become a rapidly migrating high-angle boundary. Bailey4,5 investigated the annealing behavior of several metals deformed both in tension and by rolling and concluded that recrystallization took place through the migration of high-angle boundaries. With low deformations these boundaries were present in the metal before deformation. With high deformation it was not possible to tell whether the boundaries were pieces of the original grain boundaries or were produced either during deformation or by polygonization during ameal- ing. Direct observation during heating of metal foils indicated that subgrains form by polygonization and grow at an uneven rate. The grain size obtained decreased with decreasing foil thickness indicating that the foil surface resists boundary motion. Votava,6 in heating stage experiments on rolled copper, observed nuclei to appear suddenly and grow in jumps of differing magnitude. However, he found no special dislocation configurations where the nuclei appeared. Fujita,7 as a result of a study of subgrain growth in heavily worked aluminum, concluded that the boundary of a recrystallized grain initially forms from the boundary of a group of subgrains. This occurred by a process of deposition of vacancies and dislocations in the group boundary as the boundaries within the group disappear. HU8,9 directly observed a similar process in heating stage experiments on 70 pct rolled Si-Fe single crystals. The growth of subgrains appeared to proceed by a coalescence mechanism. The observed fading away of the boundary between two subgrains was explained by the moving out of dislocations from the disappearing boundary into the connecting or intersecting boundaries around the subgrains. The subgrain size and degree of disorientation with the surrounding structure were thus increased. With the increase in disorientation occurred a corresponding increase in boundary mobility, which eventually allowed the boundary to migrate rapidly. This process was observed to occur within "microbands" consisting of parallel narrow segments disoriented by a few degrees present in the as-rolled structure. The conclusion of Rzepski and Montuelle10 that growth is preceded by the coalescence of blocks through disappearance of their common boundaries supports this view. In contrast to Hu's coalescence model for nucleation were the conclusions of Walter and ~och.""~ Working with the same material as Hu, of the same orientation and rolled to the same reduction, they concluded that nucleation occurred by the Cahn-Cottrell mechanism. They observed, in agreement with Hu, that recrystallization began in the "microband" regions which they referred to as "transition" bands. Bartuska13 studied subgrain growth in heavily rolled nickel using a beam heating method in the electron microscope. He concluded that nuclei for recrystallization form from the largest most perfect subgrains present in the cold-worked structure by rapid intermittent migration of parts of subboundaries. In rare instances he observed subgrain growth by coalescence. EXPERIMENTAL PROCEDURE The materials used in this study were 99.999 pct A1 supplied by A.I.A.G. Metals, Inc., and 99.999 pct Ni supplied by Johnson and Matthey and Co., Ltd. The Hitachi HU-11 electron microscope, with uniaxial

Jan 1, 1968

By Charles R. Stewart, William W. Owens

Reservoir performance predictions based on laboratory core test data assume that fluid flow is laminar for the laboratory test. A study has been made to determine the validity of this assumption for laboratory tests on various types of porosity found in producing limestone formation. Data are presented which show that turbulence and slippage can occur during laboratory tests on hetero-geneous-type porosity limestones, thus causing serious errors in measured single-phase permeabilities and two-phase relative permeability characteristics. In single-phase flow tests it is possible to eliminate turbulence and correct for slippage or to eliminate both factors by controlling test conditions. It is not always possible to control test conditions and thereby eliminate turbulence and slippage in two-phase .flow tests. A correction method is presented which can be used to calculate the true two-phase laminar flow relative permeability characteristic even though furbulence and slippage exist. .INTRODUCTION It is customary to make use of Darcy's law and modifications of this law, together with laboratory data on formation core samples to predict the performance of producing reservoirs. Such predictions are based on an assumption that fluid flow is in the laminar or streamline region for the laboratory test. It was the purpose of this inves- tigation to determine the extent to which turbulent flow may occur in laboratory fluid flow tests on hetero-geneous porosity limestones. Considering that turbulent flow conditions might exist in some laboratory fluid flow tests, additional emphasis was placed on the development of a method to correct for turbulence when laminar flow conditions could not be attained. FLUID FLOW CONCEPTS FOR POROUS MEDIA The Influence of Pore Geometry on Fluid Flow One of the more important factors influencing fluid flow in porous media is the geometry of the pore space which includes such characteristics of the pores as size, shape, distribution, roughness, uniformity, etc. In general, oil- and gas-producing formations can be divided into two broad types on the basis of pore geometry. One has been called sandstone-type porosity media, which is characterized by a small range in pore size, uniformity in shape of the pores, smooth pore surfaces and a regular and uniform distribution of pores. The other type has been called heterogeneous porosity media and is usually limited to the dolomites and limestones. This type is characterized by a wide variation in the size, shape, and distribution of the pores and rough, irregular pore surfaces. It is therefore apparent that conditions are much more favorable for turbulent flow* in heterogeneous-type porosity media than in sandstone-type porosity media. Interrelationship Between Turbulence and Gas Slippage In studying the problem of turbulent flow in laboratory tests on porous media, it is necessary to be aware of the interrelationship between slippage and turbulence for gas flow. As a result of slippage or the Klinken-berg effecta, apparent perrneabilities to gas are greater than the true value because there is no stationary layer of gas in contact with the walls of the flow channels. Gas slippage decreases as the mean free path of the gas molecules decreases. Since the mean free path of any gas decreases with increasing density, increases in static pressure result in lower apparent gas permeabilities. However, a reduction in gas permeability can also be due to turbulence. Therefore, in studying only turbulent flow in porous media, it is necessary to hold gas density, and slippage, constant or to reduce slippage to a negligible value by operating at high static pressures. Presentation of Laminar and Turbulent Flow Data A graphical relationship between permeability and a pseudo-Reynolds number, N,, will be used to show the two types of fluid flow, i.e., laminar and turbulent. The usual graphical method for such a description has been the use of friction factor-Reynolds number charts4. On such a logarithmic diagram, the laminar region appears as a straight line having a slope of 45 degrees. As the friction factor decreases and the Reynolds number increases, the turbulent region is reached and appears as a deviation from the 45-degree slope line. However, in petroleum engineering literature resistance of por-

By L. Valentik

Many attempts have been made during the last 40 years to evaluate the performance of gravity separation equipement, that is, the effectiveness with which light and heavy particles are separated. The most comprehensive treatment of the subject was made by Cerchar at the 1st International Conference on Coal Preparation held in Paris in 1950. The methods suggested by the Conference were accepted and very widely used in the last two decades. This paper discusses an improved method of evaluation in the light of the now-accepted standard presentation. The float-and-sink analysis of the product is presented on a Gaussian distribution curve, resulting in an easier visualization of the inherent difficulties of separation. The ogives of the distribution curve me then plotted, giving a quantitative measure of the deviation from perfect separation as an error distance instead of an error area. Illustrations of the new method are given both for gravel and for coal preparation, but the content is valid and applicable to other types of minerals which are separated by gravity methods. Many attempts had been made during the last forty years to evaluate the performance of heavy-media separation (HMS) equipment, that is, the effectiveness with which floats and sinks are separated.'-' The most comprehensive treatment of the subject was made by Cerchar at the 1st International Conference on Coal Preparation held in Paris. 6 The primary aim was the thorough understanding of the mechanism of separation and the unified presentation of data on gravity separation so that the evaluation and comparison of washery performance could be made from all over the world. No strict overall standardization has been achieved, but after the conference a more or less uniform presentation of performance was accepted, which, during the last two decades, has been very widely used. In this paper, illustration of the old methods and an improved method of evaluation will be given. HEAVY-MEDIA SEPARATION (HMS) PERFORMANCE CRITERIA In the ideal HMS process, all material lower in density than the specific gravity of separation (SGS) would be recovered as floats and all material of higher density would appear as sinks. In order to evaluate the misplaced material, the washery products are tested at the density at which the washing unit is operated. The original type of plot1,7, 8 is shown in Fig 1; this was developed primarily for coal cleaning units. The curve for raw coal represents the cumulative percentages of sink material. The refuse curve is also plotted as a cumulative sink, the percentages being expressed in terms of raw coal. This diagrammatic representation of the results of washing units has the merit of easy visual observance of the degree of separation obtained. The error areas (cross-hatched) are a measure of the amount of misplaced material and therefore they can be used to characterize the quality of separation. The ideal and actual separating performance between floats and sinks can be best seen from the partition curve developed by Tromp,2 where the ordinate is the percentage recovery of the sinks, and the abscissa is the specific gravity (Fig. 2). It can be seen from the shape of the curve that as the SGS is approached, the proportion of material reporting to the improper product increases rapidly. In fact, the SGS can be defined as the density of the material in the feed that is distributed equally between float-and-sink products. When the upper half of the curve is inverted, a shape similar to that of a Gaussian error distribution curve is obtained and therefore the analysis of gravity separation may be carried out by using the law of probability. The shape of the curve in Fig. 2 is determined partly by the density composition of the feed, and partly by the sharpness with which the unit separates floats from the sinks.9, l0

Jan 1, 1970

By Masatsugu Taniguchi

Onoda Cement Co., Tsukumi is one of the largest limestone producer in Japan. From mines called Suisho and Ganji, it supplies limestone for cement plant, lime manufacture, iron and steel industries and for many purposes. The Suisho mine is highly productive, though it's operations are governed by the utmost regard for its impact on the surrounding environment. However, it became difficult to meet additional expanding demand and to assure continuity of high rate production. Present production rate 1s 6 million tons per year. The Ganji mine, some 2 km south west of the Suisho mine, began first-stage development In mid- 1973 and in january I976 started production. The capacity of major facilities is 9 million tons per year. Full production is predicted in 1979. Mining and milling methods of these mines under strict environmental considerations are discussed.

Jan 1, 1976

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By J. Szekely, G. P. Martins

A formulation is given for describing the rate of expansion of spherical bubbles rising in liquids the freeboard of which is evacuated. The computer solution of the resultant differential equations has shown that, for low freeboard pressures (less than about 5 mm Hg), on approaching the free surface the bubbles expand much less rapidly than predictable from equilibrium considerations. In other words, in this region the pressure inside the bubbles will be significantly larger than the static pressure in the liquid corresponding to the position of the bubble. These theoretical predictions were confirmed by experimental work, using two-dimensional air bubbles rising in mercury. The important consequence of these findings is that the expansion of gas bubbles in vacuum degassing operations will be a great deal less than expected from hydrostatic considerations. This would lead to a significant reduction in the available interfacial area and may explain the apparent poor efficiency of many vacuum degassing units. VACUUM degassing as a treatment for liquid steel has gained widespread popularity in recent years; the number of known installations exceeds several hundred at the present time.' Although much information is available on both the thermodynamics of the system and the overall performance of various industrial units, much less is known about the fundamental aspects of the process kinetics.2-4 The basic physical situation common to virtually all vacuum degassing operations is the interaction between gas bubbles (swarms of bubbles) and the surrounding molten metal, held in a container, the freeborad of which is at a low absolute pressure. Once formed (or introduced from an external source) the bubbles will ascend, due to the buoyancy forces, and, during this ascent, a significant increase in their volume will occur. This progressive increase in the bubble volume is due to two factors: a) the continuous reduction in the static pressure acting on the bubble during its rise; and b) mass transfer into the bubble from the surrounding molten steel. In a recent paper Richardson and Bradshaw developed equations5 for describing mass transfer into gas bubbles from molten metals at reduced pressures. However, in deriving these expressions it was assumed that the pressure inside the bubble was identical to the static pressure in the adjacent liquid. In other words, the volume of the bubble was considered to be in equilibrium with the pressure of the fluid adjacent to it. This assumption, thus their analysis presented, was thought to be reasonably accurate for most of the bubble's ascent; however, it was unlikely to be valid in the immediate vicinity of the free surface, held at a low pressure. It was pointed out in the discussion6 that the region close to the surface may be of considerable importance as both the driving force and the interfacial area available for mass transfer are at their highest value here. The ' 'anomalous" behavior of gas bubbles when approaching a free surface at low pressures was recently confirmed in a preliminary investigation by Szekely and Martins. ?1 Here high-speed motion photography was used to study air bubbles rising in a column of n-tetradecane with a freeboard pressure of 0.1 mm Hg. It was found that significant distortion of the bubbles occurred on approaching the free surface; furthermore, the expansion observed was much less than what one could expect from hydrostatic considerations, i.e., factor a previously discussed. It follows from the foregoing that a detailed study of these phenomena would be justified both from fundamental considerations and because of their potential relevance to technology. The purpose of the paper is to present a more realistic formulation for the expansion of a gas bubble approaching a low-pressure region, together with a comparison of the theoretical prediction with experimental measurement. An inert bubble will be considered in the first instance; it is thought that the understanding of the fluid mechanics is an essential first step toward the realistic formulation of the mass transfer process. This latter problem will be the subject of a subsequent publication. FORMULATION The Physical Model. Consider a spherical bubble, of initial radius Ro, rising in a fluid, having a density pL. Initially let the bubble be at a distance H from the free surface, and at a pressure Pgo, as illustrated in Fig. 1. Pgo, the initial pressure in the bubble, is given by the following equation: pgo = Po = Ptp +pLgH [ la] where Po is the pressure in the liquid corresponding to the initial position of the bubble and Ptp is the pressure at the free surface. The fluid pressure at

Jan 1, 1970