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By William R. Patterson

ACCORDING to the phase diagram for the Mn-Ni system,' the high-temperature, fcc y-manganese solid solution is stabilized to below room temperature, in the range approximately 22 to 28 wt pct Ni. However, pearson2 cites evidence in the literature showing that for manganese contents greater than about 75 wt pct the quenched phase in Mn-Ni alloys is fct. This is in keeping with zener's3 suggestion that in manganese-rich alloys the fcc high-temperature phase undergoes a diffusionless or martensitic transformation to a fct structure upon quenching. Work by Basinski and christian4 on manganese-rich compositions in the similar alloy system Mn-Cu established that in alloys of greater than about 82 wt pct Mn the y-manganese phase underwent a fee fct martensitic transformation upon quenching to room temperature. Striking evidence for this martensitic transformation was the highly twinned or banded microstructure, an example of which is shown in Fig. 1. Similar microstructures have also been found in quenched Mn-Cr5 and Mn-Au6 alloys. In the present investigation, we attempted to obtain similar evidence of a fcc — fct martensitic transformation in manganese-rich Mn-Ni alloys. Manganese alloys in the range 10 to 30 wt pct Ni were prepared by arc-melting, under argon, at atmospheric pressure. The alloys all were 50 g in size, and negligible weight loss occurred during melting. The starting materials were electrolytic manganese and nickel, both of 99.9+ pct purity. The alloys were subsequently homogenized 48 hr at 1750°F, hot-rolled 50 pct at 1700°F, annealed 2 hr at 1700°F, and water-quenched to room temperature. All heat treatment was done in purified argon. Both X-ray and metallographic techniques were used to examine the structures of the quenched alloys. X-ray diffractometer studies were conducted on powder specimens obtained from filings rean-nealed 2 hr at 1700°F in argon and water-quenched. Identification of the intensity peaks from the diffractometer counter traces showed that below about 10 to 12 pct Ni the y phase decomposed partially upon quenching to give an a- + ?-manganese structure. In the range approximately 12 to 25 pct Ni, the structure was found to be fct ? manganese with a c/a ratio approaching 1.0 at 25 pct Ni. Beyond approximately 25 pct Ni, the structure remained fcc. These results, including lattice-parameter determinations, are given in Table I. Metallographic examination. was carried out on specimens polished and etched after quenching, and also on polished specimens reannealed and quenched. In the first case, the distinctive twinning or banding so prevalent in Mn-Cu alloys was sought, while in the second, the surface relief effect generally regarded as being truly characteristic of a martensitic transformation was sought. The microstructure of representative alloys in the range 12 to 25 pct Ni is shown in Fig. 2. The structure of the Mn-15 pct Ni

Jan 1, 1965

By Bagley A. S

The accuracy and precision of rutile analyses are discussed. Comparison is made between the wet chemical and X-ray fluorescence spectrographic methods of. estimating Ti02 in commercial rutile. Various allotropes of 'I'i02 are identified by diffractometry and a comparative analysis of the coloured varieties of rutile is given. For X-ray fiuorescence . analysis, specimen preparation is critical and sample grinding and pressures. for pellet making are discussed in detail.Cellulose bonded and backed pellets are shown to be subject to relaxation with increasing age.INTRODUCTIONTo date much of the analytical work on commercial samples has been done by wet chemical methods.This led to various discrepancies in results, which are of particular importance when certificates must be issued for overseas shipments. The present work reviews the nature of rutile and compares the results of Ti02 estimation by wet chemical methods and those obtained by X-ray fluorescence spectrographic analysis.In the rutile industry the results from different analysts and even those from the same analyst are not always consistent. To the analytical chemist this should not be surprising.Fairbairn (1951) showed the results obtained from 34 different analysts on a specially prepared sample of granitic rock. It is of some interest to note that the Ti02 content as determined by the 34 analysts using unspecified methods ranged from 0-17 per cent to 0·30 per cent. Fairbairn (1953) found that1. replicate analyses from the same analyst give a high order of precision,2. analyses by different analysts using the same procedures give reasonable precision, and...

Jan 1, 1965

By J E. Curfman

This paper deals with using track-type and rubber-tired machines in the ripping and handling of overburden and ores. The techniques and proper attachments pertaining to the ripping of materials are covered in some detail. Production and relative costs of ripping, as against other methods, are covered in cases pertaining to the mining industry. The use of the refraction seismograph in predetermining the rippability of materials, including a chart relat-ing velocity to rippability, is covered. This operates on the principle that sound waves travel through subsurface materials at different velocities, depending upon the degree of consolidation of the material. It is known that the same factors that affect consolidation also affect rippability. Proper equipping of the tractor to insure maximum efficiency is also covered in some detail. Introduction T HE idea of loosening consolidated materials prior to further handling and processing is probably as old as man. The purpose of ripping is to provide fragmentation of rock and loosening of consolidated materials.

Jan 1, 1965

By J. W. Faust, H. F. John

Generalized conditions for rod or ribbon growth by the twin plane re-entrant edge mechanism are given. It was shown that this mechanism can result in growth of twinned platelets from dilute metal solutions. The platelrts 01 the fee metals are faceted by (111) planes and contain two or more twin planes. Microsegregation traces were revealed in silver grown from a thallium solution. VOGEL has already set down conditions for dendritic growth;1 however, this was the normal single-crystal dendritic growth experienced during solidification. In this work it is desired to set down the crystallographic conditions that will lead to rod or ribbon growth with smooth facets. These are as follows. a) The growth must be crystallographically limited (i.e., faceted growth). b) In order to have directed growth, some mechanism must allow easier nucleation than two-dimensional nucleation. That mechanism is afforded by the re-entrant edges at twin planes.213 Thus there must be twin planes present in the rods or ribbons. c) The growth direction must lie in the twin plane. If not, the twin plane will grow to the face or side of the ribbon and the site of easy nucleation will be lost. d) The growth direction must be parallel to at least one plane of the faceting planes, and no set of the faceting planes can be perpendicular to the growth direction. A corollary to these conditions involves the number of twin planes necessary to maintain the indestructible re-entrant edge. The number depends on the crystal structure of the material. An analysis of the data available shows that a material whose faceting planes form an open figure requires at least one twin plane while materials whose faceting planes form a closed figure require at least two twin planes in order to form the indestructible re-entrant edges for extended growth. The conditions and an assessment of the possibility of rod or ribbon growth are given in Table I for several crystal systems. As can be seen the fee, diamond and zinc blende, or-thorhombic, rhombohedral, and one form of the hexagonal lattice systems can yield this type of growth, but not the bcc metals nor the hexagonal

Jan 1, 1965

By Robert M. Becker

Particle mixtures were sampled in the laboratory, using ordinary sampling procedures, to determine whether or not the compound-multinomial probability distribution and other developments of part 2 agreed with experimental results. The objective was accomplished by the Bureau of Mines by comparing the moments and moment relationships of the appropriate probability models with their corresponding experimental values over a fairly wide range. The overall agreement between the corresponding theoretical and experimental values is both good and complete. The results demonstrate that sampling to a constant amount, such as weight, of items per sample is not the same, in general, as sampling to some constant number of items per sample. The results seem to confirm all the developments of part 2 and the application of the compound-multinomial function to bulk sampling.

Jan 1, 1965

By E. R. Buchanan, R. E. Reed-Hill, F. W. Caldwell

Poly crystalline zirconium tensile specimens containing a sizable fraction of grains unfavorably oriented for slip were deformed at 77°K to strains as high as 9 pct. The contributions of the various twinning modes to the observed strain were deter~nlned quantitatively using measured twin volume fractions and Schrnid orientation factors. The results indicate that at very small strains twinning can account for almost all of the observed strain. At higher strains slip becomes the dominant means of deformation. The most significant form of twinning was {1121}. PLASTIC deformation in polycrystalline aggregates is poorly understood even today. This is primarily because slip cannot be easily observed or studied in the interior of a metal. On the other hand, twinning can be discerned inside a specimen after deformation. Twinning studies can therefore often yield quantitative information about polycrystalline deformation not otherwise obtainable. This investigation uses the above aspect of twinning in determining the contributions of twinning to the strain during tensile deformation at a cryogenic temperature (77°K). Polycrystalline zirconium was used as the object of study. There are several reasons why this information should be of value. In contrast to many metals, both the strength and ductility of zirconium increase with a corresponding decrease in temperature. This may be related to the fact that twinning becomes more profuse and complex with decreasing temperature. Secondly, it has been discovered that certain room-temperature properties of zirconium can be greatly improved by about 1 pct prestrain at 77°K. These include an increase in tensile elongation in critical directions by over 50 pctl and a large mechanical hysteresis effect.2 Both effects are believed to be related to twins formed by prestraining: plastic twin-boundary movements accounting for the increased ductility, and anelastic twin-boundary movements for the internal friction. Thirdly, hexagonal metals which twin primarily on only the (1012) mode (such as beryllium, zinc, and magnesium), unlike zirconium, are very limited in ductility at cryogenic temperatures. Therefore, the significance of the various types of twinning in zirconium at cryogenic temperatures is of more than academic interest. Three twinning mechanism-s have beenobserved in quantity at WOK, {1012), {1121), and {1122). Each must be considered as a unique deformation mechanism because of their markedly different twinning shears and basically different angles between twinning and basal planes, as shown in Table I. It is therefore necessary to separately consider the role of each of these twins during plastic deformation at 77°K. Fortunately, each twin possesses unique morphological features which makes its identification possible on a properly prepared metallographic section. The use of the polarized microscope3 can also greatly aid in identification of the various forms of twins. EXPERIMENTAL PROCEDURE Arc-melted sponge zirconium plate, previously describedY4 was machined into 1/8 by 1 1/4 in. threaded-end, round tensile test specimens. These specimens were deformed to the desired strains in a liquid-nitrogen cryostat mounted in an Instron testing machine. The tensile axis was the transverse plate direction. This specimen direction resulted in large numbers of grains in orientations unfavorable for deformation by prism or basal slip. Deformed specimens were sectioned, mounted in epoxy cold-mount resin, ground on metallographic papers, electropolished, and anodized to provide surfaces sensitive to polarized light. Standard quantitative metallographic procedures5

Jan 1, 1965

By S. E. Khalafalla

The Bureau of Mines investigated variations in the activation energy for the carbon monoxide reduction of magnetite and ferrous oxide with respect to the state of aggregation of the oxide material. Reduction phenomena can only be satisfactorily explained by including an adsorption step in the reduction process. Summation of the values of the exothermic heat of chemisorption and the variable apparent activation energy for reduction yields a nearly constant value of about 50 kcal for either ferrous oxide or magnetite regardless of whether they are aggregated in pelletized form or coarsely crystalline particles.

Jan 1, 1965

By Juel H. Stears

Research was done to determine if a hydraulically operated penetrometer developed by the Bureau of Mines could be used to estimate the roof-bolt anchorage capacity of mine roof rock. Tests were conducted both in the laboratory using cement cylinders and underground in shale rock. Hardness readings were measured by the penetrometer around the periphery of the bolt holes at the anchorage horizon. Roof bolts Nere then installed and subjected to an anchorage test. The results showed that the penetrometer readings could be used to determine the optimum stratum for roof-bolt anchorage but could not be used to make an accurate estimate of the anchorage capacity.

Jan 1, 1965

By T. Saburi, C. M. Wayman

The massive and martensitic transformations in ß Cu-Ga alloys were studied by optical microscopy and by transmission electron microscopy and diffraction. These types of transformation are distinct and do not merge into one another. An internal fine structure due to stacking faults was found in both the massive phase (m) and the martensite, but the origin of the faults is believed to be different in each case. The faults in the martensite are due to the lattice invariant or "second" shear of the phenom-enological theory, while those in the are probably growth faults and deformation faults arising from the transformation volume change. Evidence is presented for ordering in the ß phase prior to transformation into martensite, and the crystal structures of and ß' and ßi martensites are discussed. THE results from some previous investigations1,2 have led to the suggestion that martensitic and massive transformations have certain common characteristics. It presently seems established that massive transformations like martensitic transformations are essentially diffusionless,1,2 but unlike martensitic transformations, when a new phase forms massively there is no shape change or surface relief.= If the massive-type transformation is crystallographically similar to martensitic transformations, one would expect a fine structure as a result of the lattice invariant shear4 which is a part of the transformation mechanism. The existence of such a fine structure (i.e., slip, twinning, or faulting), if any, can be verified by transmission electron microscopy, and thus the present investigation was undertaken to compare the internal structure of massively and martensitically formed phases in Cu-Ga alloys which were derived from a parent of the same composition. The transformation characteristics of ß Cu-Ga alloys were also studied. The bcc ß phase in the Cu-Ga system, Fig. 1, is stable above 616oc.' Depending upon the cooling rate, ß Cu-Ga alloys can undergo three different types of phase transformations. The ß phase of eutectoid composition (23.7 at. pct Ga) decomposes into the ? phase (hcp) and the phase (complex cubic) by means of a eutectoid reaction. When the cooling rate is increased so that the decomposition of 0 into [ and ? is suppressed, the ß phase transforms into a nonequilibrium hcp phase, herein denoted ?m by a process of very rapid growth called a "massive" transformation. At even faster quenching rates the massive transformation can be suppressed and the ß transforms martensitically. Massive transformations, apparently similar to those in the Cu-Ga system, have also been studied in the Cu-Zn2,6-8 and Ag-Cd systems.9 Definitive characteristics if the Massive Transformations in 0 Cu-Ga Alloys1 1) The most remarkable feature of the massive transformation in Cu-Ga is that there is no bulk composition change on transformation. According to Massalski,1 the resulting [, phase is a supersaturated extension of the equilibrium [ phase. The lattice parameters continue the trend exhibited

Jan 1, 1965

Ilmenite production in Western Australia commenced in 1956. There are now five producers, all in the Bunbury-Capel district, and current total production capacity is about 450,000 t.p.a.The deposits occur near the surface and average between 10 and 50 per cent heavy mineral. About 70-85 per cent of the heavy mineral is ilmenite. Other heavy minerals present include leucoxene, zircon, rutile, monazite, and garnet. The ilmenite contains 52-60 per cent Ti02. and is very low in chromium (0·03-0·04 per cent CrS03)Mining is done by sluicing, drag line excavation, or dredging. Primary concentration of the heavy minerals is achieved by spirals, revolving cones, or Reichert cones. After drying and screening, ilmenite is separated from the heavy mineral concentrate by various types of magnetic separator.Separate leucoxene, zircon, rutile, and monazite concentrates are also produced. Each plant uses a different technique and the processes used include chemical attritioning, screen plate electrostatic separation, high tension rolls, air tables, and dry launders.INTRODUCTIONThe treatment of beach sands in the Bunbury/Capel area for the extraction of ilmenite is a very recent development in the mining industry in Western Australia. Nevertheless, since the commencement of production in 1956, ilmenite has become the sixth most important mineral produced (Table 1).The increasing world recognition of Western Australia as a major producer of ilmenite (Table 2) is due primarily to the low chromic bxide content of the mineral (0' 03-0' 04 per cent Cr203), combined with a medium to high titanium dioxide content (54-60 per cent Ti02), supported by large reserves, a stable government, and close access to good shipping facilities. Ilmenite is. produced from these deposits at low cost which enables the industry to compete on world markets despite high rates for sea freights because of the distance from major markets.

Jan 1, 1965

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.' Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts' Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg's method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By I. Hawke, K. Barron

I. Hawkes (Postgraduate School in Mining, University of Sheffield, Sheffield, England) — The photoelastic stressmeter is proving to be a very practical tool for 'in-situ' measurements in the fields of civil and mining engineering and Barron's article has therefore come at a very opportune time, supplementing as it does, the considerable amount of laboratory and field data which is being accumulated.1,2,3 There are however several points relating the application of Barron's conclusions to the practical use of the meter which require further elucidation. EASE OF READING If the photoelastic stressmeter is to have a wide application, the fringe orders must be easily measured. The system adopted by the writer and his colleagues at Sheffield for the uniaxial stress case is to read the fringe order at the 45 point, 0.20 in. from the center (11/4 in. diam meter). This procedure has been recommended because the fringes not at this point form a very distinct 'eye' which is obvious even to those who have had little experience with photoelastic fringe patterns. Barron points out that this point can also be used up to a stress ratio of 0.33 and in practice this is normally done. In biaxial fields above a ratio of 0.33 the 'eye' is no longer apparent and the fringe order must be ascertained at some other point. The writer and his colleagues experimented at various points and finally chose a point at a distance 0.175 in. (11/4 in. diam meter) on the minor stress axis and fixed this point on the meter by inserting a collar of this diameter. This procedure enables the 'eye' technique to be used for uniaxial stresses as the 'eye' falls outside the collar; any other technique for biaxial patterns would require lines to be engraved on the meter itself and reading difficulties would be experienced by all but the most highly trained. It is interesting to point out that in a great many field applications ranging from underground pillars to building foundation piles the stresses measured have been uniaxial. In such cases, reading the fringe order has been simple even for unskilled persons. SENSITIVITY The photoelastic stressmeter acts as an inclusion, and as such its theoretical behavior is as described by Barron's mathematical analysis. When considering its practical application, however, it must be remembered that rocks and concrete are not mathematically ideal substances. The theory relates the fringe order in the meter to the stresses and the E (Young's Modulus) and the µ (Poisson's Ratio) values of the surrounding material. There is of course no unique E or µ value for rocks or concrete. These values change both with stress level and time load application sometimes to the order of 300%. We at Sheffield have very accurately calibrated the photoelastic stressmeter in a wide range of materials and have also measured the average E values for these materials. The results prove that the meter sensitivity

Jan 1, 1965

By C. Wachmann

The theory presented ill this paper makes possible examination of the phenomenological aspect of secondary oil recovery by alcohol flooding. Limitutions of the theory are contingent on three primary assumptions: (1) chemical equilibrium, (2) no fingering, and (5) no dispersion. The second assumption implies one-dimensional flow. In a geometric sense the theory extends the Buckley-Leverett construction to systems of two slightly miscible fluids and to systems of three components. This is made possible by considering single-phase fluids to be made up two phases, namely of an excess of one phase and a negative amount of the other phase. The procedure is discussed in the paper. The theory also permits direct determination of the relationship between the aqueous phase saturation and the concentration of water in the aqueous phase in a zone of variable composition. The velocity of planes of constant water concentration and of constant saturation can be computted likewise and the existence of saturation discontinuities inferred. Consequently the behavior of such a Zone, which may exist at some time between a displaced and a displacing fluid, May be determined. mathematical details are given in Appendices. Problems of experimental verification are pointed out on the basis of a supporting experiment. Implications of the theory and effects of violations of primary assumptions are discussed briefly. The major conclusion is that, if the primary assumptions are met, with pure alcohol and alcohol-rich .slugs piston-like displacement of oil and water is possible. INTRODUCTION The recovery of oil from porous media by alcohol displacement has been studied for several years. Extensive experimental investigations into alcohol flooding have been carried out in the laboratory although little has been done in the field. A large amount of practical information is available, the extent being indicated by the first three papers cited 1-3 and their respecrive bibliographies. This has permitted the Formulation of inferential theories. A more analytical approach in which theories are developed primarily by reasoning from known physical principles and relationships has, however, lagged behind. In fact, an analytically derived theory of alcohol displacement has not been available. The theory presented in this paper on oil and water displacement by alcohol from a porous medium is a result of the analytical approach. The theory is idealized, as certain assumptions had to be made to make the mathematics tractable and reduce complexity of argument. In particular, major assuptions concerning conditions of equilibrium, interfacial stability, longitudinal mixing, etc., led to the exclusion of fingering, for example, from all considerations. In many laboratory experiments reported in the literature fingering could not be avoided. There is, therefore, disagreement between theories based on experimental evidence available and the analytically derived theory presented here. This theory presented is based on known physical data and makes use of the Buckley-Leverett construction and its suggested extension. The mathematical derivation of the theory is given in Appendices. Three examples relevant to alcohol displacement are discussed to explain the use of this theory: (1) system of two immiscible fluids (the Buckley-Leverett case); (2) system of two slightly miscible fluids involving an extension of the Buckley-Leverett construction; and (3) system of three components, including injection of pure alcohol or alcohol-rich fluid as a special case, which involves a more general extension of the Buckley-Leverett construction. In these discussions strict assumptions were made to impose equilibrium conditions and exclude mixing and fingering. Effects of relaxing these assumptions and consequent extensions of the theory are indicated. The complexity of the alcohol displacement process makes experimental verification of the theory essential. Some relevant evidence is offered in this paper.

Jan 1, 1965

By G. W. Thomas

A simplified mathematical model of underground conduction heating in a system of limited permeability is presented. The model applies to underground retorting of oil shale, or to reservoirs containing extremely heavy oils. We assume that heat is introduced at a constant rate into a horizontal fracture which communicates between wells. The radial temperature distribution along the fractured surface is approximated by a step-function. Heat transfer away from the fracture is assumed to be by vertical conduction, and all convection effects are neglected. The model also takes into account the possible temperature dependence of thermal conductivity. A general expression for calculating the growth of the step-function temperature distribution with time is derived. The use of this expression and solutions to the one-dimensional heat equation make it possible to construct isotherms. Expressions for calculating .oil recovery, well spacing and heat efficiency are also given. An example calculation is presented for the conduction heating process in oil shale. Finally, the effect of the heat transfer coefficient between the gas and the fracture boundaries is investigated. INTRODUCTION Thermal recovery processes of oil recovery fall into the four general areas of hot fluid injection, forward combustion, reverse combustion and conduction heating. The first three of* these processes have been rather extensively studied in the past decade from both the experimental and theoretical points of view. As a result, it is possible to make reasonable engineering predictions and analyses of these processes. Little attention has been devoted, however, to the conduction heating process other than to note its possible utility.I To a certain extent, conduction heating cannot be divorced from the other regimes cited above, insofar as these provide the source of heat energy. In the conduction heating process, heat is introduced (either by combustion in the forward or reverse mode or by hot fluid injection) into a small fraction of the total reservoir thickness. This fraction may be either a streak of high permeability or an interwell fracture. Heat penetrates by conduction into the adjacent, less permeable regions of the oil-bearing rock, where the direction of conduction is essentially perpendicular to the streak or fracture. The heated product then drains by gravity or is gas driven to production wells. Conduction heating is probably most applicable to systems containing immobile bitumens such as tar sands and oil shale deposits and perhaps to low-permeability reservoirs containing highly viscous crudes. The mechanism also acts in combination with other thermal processes where fingering or overriding of a bed occurs. It seems probable that in at least one field test, conduction heating of this type was very influential.2 In this presentation we give a first approximation to some of the quantitative aspects of conduction heating. Marx and Langenheim3 treated a similar problem where they focused attention upon the injection interval, which spanned the total reservoir thickness. In their model, conduction heat losses to the bounding media imposed a practical limit on the calculated heated area. In the present study, however, we shall confine the injection interval to a small fraction of the reservoir thickness and assume it has no heat capacity. We therefore direct our attention to regions outside the injection interval into which the conduction of heat is beneficial. In particular, we will endeavor to locate specific isotherms in the media bounding the injection interval. Furthermore, we will construct our model to allow the thermal conductivity to vary arbitrarily with temperature. Thus the model will be applicable to underground retorting of shale where variations in thermal conductivity may be important. THEORY We consider the rock matrix to have no or, at best, a very limited permeability; consequently a

Jan 1, 1965

By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By Robert M. Yonco, Irving Johnson, Martin G. Chasanov

The thermodynamics of the cadmium-rich portion of the Pu-Cd system has been studied with a high-temperature galvanic-cell method. The partial phase diagram of the Pu-Cd system was determined. The existence of the intermediate phases PuCd11 (cubic BaHg11 structure, ao= 9.282) and PuCd6 (cubic, CeCd6 structure, a, = 15.59) was established. The existence of at least one other intermediate phase richer in plutonium was indicated. PuCd11 was found to peritectically decompose into PuCd6 and liquid at 406" * 2°C. The solubility of plutonium in liquid cadmium may be represented by the equations: (355' to 399°C) log (at. pct Pu) = 6.223 -4282T-1 (399° to 632°C) log (al. pct Pu) - 5.148 - 5277T-1 > 1.156 x 106 T-2 The free energy of formation values (kcal per mole) of the two intermetallic phases are given by the equations: (PuCd11), ?Gf= -45.9 + 35.7 x 10-3 T (PuCd6), ?Gf0- -39.27 + 25.86 X 10-3T The excess free energy (kcal per mole) of plutonium in liquid cadmium may be represented by the equation: -(-16.72 * 29.54 NPu) 10-3T in which Npu and Ned are the atom fractions of plutonium and cadmium. The thermodyanamics of the U- Cd and Pu-Cd systems are compared. THERMODYNAMIC information on systems of the actinide metals with low-melting metals, such as zinc and cadmium, is useful in the design of pyro-metallurgical processes for the purification of nuclear reactor fuels. The thermodynamics of the Pu-Zn,1 Th-Zn.2,3 U-Zn,4-5 and U-Cd6 systems have been reported. The present report on the Pu-Cd system concerns the liquidus composition in the cadmium-rich region, the characterization of the two most cadmium-rich intermetallic phases, and the thermodynamic properties of these intermetallic phases and dilute liquid solutions of plutonium in cadmium. EXPERIMENTAL Phase Studies. The liquidus composition was determined by analysis of filtered samples of the liquid phase withdrawn at a series of temperatures. The apparatus and procedure were identical to that used in the previous study of the Pu-Zn system.' Briefly. a sample of the melt was withdrawn into a tantalum tube fitted with a porous tantalum filter (30-µ pore). the entire sample dissolved in hydrochloric acid (to avoid errors due to segregation

Jan 1, 1965

By Edward J. Harvey

Joplin, one of the most famous zinc mining camps of a bygone era, is today experiencing a healthy growth in manufacturing enterprises. Manufacturing requires water, and knowledge of its availability and quality often is the main factor in location of industry. For this reason in January 1964, on the suggestion of the former State Geologist, Dr. Thomas R. Beveridge, a study of the water resources of the Joplin District was undertaken as a cooperative effort of the Missouri Geological Survey and Water Resources now under the direction of Dr. William C. Hayes and the U. S. Geological Survey. The project area is in southwestern Missouri on the Springfield Plateau and is bordered on the west and north by the Osage Plains of Kansas and Western Missouri, (fig. l). Upland altitudes rise from 900 feet above sea level in the west to 1400 feet in the east. The countryside is rolling to moderately hilly and much is excellent farmland.

Jan 1, 1965

By H. H. Johnson, Eric W. Johnson

A newly developed ac technique was used to measure the electrical-resistivity changes associated with both cyclic stressing and subsequent annealing of high-purity and OFHC copper. The early stage of push-pull fatigue was explored at 293° and 4.2°K, with stresses chosen for an expected fatigue life of 2 to 8 X 105 cycles. For high-purity copper, fatigue at 293°K was accompanied by an initial increase in resistivity. After about 5000 stress cycles, no further increase was observed. Annealing studies showed that the resisticity increment could be accounted for solely in terms of an increased dislocation density, to about 2 x 1010 disl pev sq cm. Fov 42°K fatigue, however, the resistivity increased continually, with no evidence of saturation, as approximately (No. of stress cycles)1/4. This is intevpreted to result from both dislocation multiplication and vacancy production; estimated vacancy concentrations are 10-4 to 10-9. The continuous resistivity increase was inhibited by interspersed annealing treatments at 293°K, which also raised the level of the stress-strain curve. These effects are attributed to annealing of vacancies into dislocation loops. In contrast, OFHC copper fatigued at 4.2°K showed saturation of electrical vesistivity after only a few hundred cycles, and it appeared that vacancies annealed out completely between 77° and 293°K. MaNY observations suggest that both dislocation multiplication and point-defect production are important aspects of fatigue deformation. An increase in dislocation density with number of stress cycles has been demonstrated or implied by several experimental techniques, including optical metallography with lithium fluoride,' electron microscopy with copper,2 thermal conductivity of Cu-Zn alloys,3 and peak-stress measurements during cycling at constant plastic strain amplitude.4,5 At low amplitudes and/or stresses saturation of fatigue hardening and dislocation density occurs early in the expected fatigue life,4-6 frequently by a few hundred cycles. The evidence for point-defect production is somewhat less extensive, but it is nonetheless persuasive. Rosenberg7 reported briefly that, for equal stresses, copper fatigued at liquid-hydrogen temperature displays an increase in electrical resistance some ten times that which accompanies unidirectional stressing. Further, the extra resistance saturates after a few hundred stress cycles, and does not anneal significantly until a temperature of about 170°K is attained.' Point-defect production during fatigue is also suggested by 1) the softening during cyclic stressing of initially strain-hardened polycrystal-line copper9, 2) the strong temperature dependence of the yield strength of fatigue-hardened mono- and polycrystalline copper,579"0 and 3) the influence of intermediate annealing upon slip-band formation in copper fatigued at 90°K.8 It is evident that characterization of the fatigued state requires a knowledge of both point-defect and dislocation densities. For this purpose electrical-resistivity measurements are useful, but they are difficult to perform because of geometric limitations. Push-pull fatigue is necessary to obtain a macroscopic ally uniform deformation over the specimen cross section; however, the specimen must then have a low slenderness ratio to avoid plastic buckling, while the standard dc resistivity technique requires a very slender specimen for

Jan 1, 1965

This paper deals mainly with the modernization in the coal loading system at the loading piers of the Dominion Coal Company, Ltd., Sydney, Nova Scotia. The history of the operation is briefly outlined, and the construction of the Company's new pier is described in considerable de-tail. Particular attention is paid to the bins and conveyors, and to the loading tower. The paper concludes with a description of the S.S. Cape Breton Miner, built specifically for the coal trade, and the unloading facilities at Lakeview, Ontario. Coal Shipping at Sydney C OAL from the mines operated in Cape Breton by the Dominion Coal Company, Limited, has been shipped from the International Piers, situated on the east side of Sydney Harbour, for over sixty years. There were three piers, of which two were active-ly used in the shipping of coal until 1964. Nos. 2 and 3 were high piers about 600 feet long, of wooden construction throughout. They were founded on' rock-filled cribs and creosoted piles driven into the harbour bottom, and each had two decks which carried standard-gauge railway tracks.

Jan 1, 1965

The principal activities of the Bureau of Mines Explosives Research Center from July 1, 1963 to June 30, 1964 are described briefly in part 1. Part 2 gives short abstracts of publications that appeared during fiscal year 1964; in general; the research reported in these publications antedates the report period. Part 3 describes a short-term investigation into safety problems associated with shipping of molten sulfur; this investigation is not at present destined for publication elsewhere.

Jan 1, 1965