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By Shiou-Chuan Sun

THE fact that coals of different ranks and even of the same rank differ greatly in their amenability to iroth flotation is well known. In recognition of the need for an explanation of this phenomenon, two hypotheses have been suggested. Wilkinsl reported that the floatability of coals increased with an increase of the carbon content or rank. This postulate is handicapped by the fact that bituminous coals that possess moderate carbon contents are actually more floatable than anthracite coals that have high carbon contents, as shown in columns 6 and 9 of Table I. Taggart and his associates' implied that the difference of floatability between bituminous and anthracite coal was caused by the variation of carbon-hydrogen ratio. This is not applicable to the relative floatability of other coals and carbons. For example, column 11 of Table I shows that the carbon-hydrogen ratios of low-floating lignitic coal and non-floating animal charcoal are not only smaller than the moderate-floating anthracite coal, but are also similar to the high-floating bituminous coal. Furthermore, according to this hypothesis, high temperature coke-A (464), Ceylon graphite (1238), and lamp-black (357), all possessing extremely high carbon-hydrogen ratios, should be less floatable than other substances having much lower carbon-hydrogen ratios such as high volatile-B bituminous coal (11.9 to 22), anthracite coal (35.7 to 60.5), lignitic coal (15.6 to 33.6), and charcoal (13 to 26.2). However the former group is actually more floatable than the latter group. In this paper, a surface components hypothesis is Proposed to explain the different floatabilities of coals, carbons, and hydrocarbon minerals. The validity of the hypothesis is experimentally supported by the actual floatability, natural floatability, wettability, and adsorbability for neutral oils of coals, carbons, and hydrocarbon minerals tested. The combustible recovery of the flotation results, as used in this paper. was calculated from Eq. 1: P (100-Ep) 100 RWCP Rc= [1] F (100-E,) C, where R, is the percent combustible recovery; F and P are, respectively, the weight of feed and the weight of concentrate or product; E, and Ep are, respectively, the total percent of ash plus moisture in feed and in concentrate; Ru. is the percent weight recovery: and C, and C, are, respectively, the percent of combustible in feed and in concentrate. Except for ash and moisture content, all chemical components of a coal are assumed combustible. The experimental work included studies on flotation, ultimate and proximate analyses, contact angle tests, extractions of bitumen-A with benzene, adsorptions for liquid hydrocarbons, and wetting tests. Most of the flotation experiments were performed in a laboratory Fagergren machine; others were tested in a small Denver machine. The solid feed for the former was 300 g and for the latter was 30 g. The solid materials used for flotation were crushed to —48 mesh. After the mineral pulp in the flotation cell was agitated for 6 min and the pH was adjusted to 7.5 & 0.2 with sodium hydroxide or hydrochloric acid, a petroleum light oil having a viscosity of 5.73 centipoises at 77 °F was added and conditioned for 2 min. Finally, pine oil was introduced and the froth was collected for exactly 3 min. The weight ratio of petroleum light oil to pine oil was kept constant at 1.5 to 1. Tap water was used for all flotation tests. Contact angles were measured with a captive bubble machine. For each coal sample, three specimens were mounted in transoptic mounts and polished with levigated alumina, first on a sheet glass, then on a cloth-covered metal polishing wheel. The polished specimen was first washed with distilled water and wiped thoroughly on a cleaned linen pad, then transferred into the pyrex cell of the captive bubble machine and conditioned for 6 min., and finally measured for contact angles at three or more points. Except where otherwise stated, the induction time for each measurement was 1 min. The contact angle representing each material was obtained by averaging the measurements of three specimens. The linen pad was first washed with warm distilled water, then boiled 30 min in a 2N sodium hydroxide solution, and finally washed with distilled water until no trace of sodium hydroxide could be detected in the decanted solution. The cleaned linen pad was stored under distilled water. Immediately before using, the pad was rewashed and transferred into a clean pyrex petri dish partly filled with distilled water. The glassware and rubber gloves used were cleaned by soaking in sulphuric acid-potassium dichromate cleaning solution, followed by rinsing with distilled water. The polished specimens were handled only by glass forceps. The ultimate and proximate analyses were made in accordance with the ASTM standard procedures for coal and coke. The extractable bitumen-A was determined by weighing 1 g of —100 mesh sample and placing it in a desiccated and weighed ASTM aluminum-extraction thimble. The thimble was placed in condenser hooks and inserted into an extraction flask containing 100 cu cm of benzene. The flask was heated and the benzene vapor was condensed by water coils. At the end of 24 hr of percolation, the thimble was removed, desiccated, and weighed. Loss in weight of sample was taken as bitumen-A and calculated to dry and ash-free basis.

Jan 1, 1955

By M. L. Brashears

IN the last 15 years industrial use of ground water has more than doubled, and in 1951 amounted to 5 billion gallons per day. A similar sharp increase in the utilization of ground water for irrigation and public-water supply occurred in the same period. In many areas rapid increase in withdrawal from wells has taken place almost entirely unhampered by regulatory control and with little or no integration of effort. As might be expected, the chief interest in many regions has been maximum production rather than sustained perennial yield. As a result, widespread depletion of underground reservoirs and deterioration of the quality of the water stored in them has taken place in many areas, even though total pumpage in the United States is far below ultimate potential. Of even more concern is the fact that excessive withdrawal has drawn salt water into the reservoirs beneath many heavily populated centers along the Atlantic, Gulf, and Pacific coasts, causing costly abandonment of pumping plants.' Many hydrologists expect that consumption of water will rise rapidly in the near future, and some predict that industrial requirements will more than double in the next decade.2,3 Thus it appears likely that the draft on many already heavily pumped underground reservoirs will be greatly increased and the search for additional sources of usable ground water intensified in years to come. In view of this, industry as a whole will be forced more and more to recognize the potentialities and limitations of ground-water reservoirs and to utilize them more effectively to prevent costly water shortages and disruption of production. Through painful experience, some industries are already well aware of the need for effective water utilization, and have managed individually or through joint effort to check trends threatening to deplete underground reservoirs completely or to impair the quality of the water. Various remedial measures have been used to bring about successful management of local or regional ground-water resources. Of these, replen-ishment of aquifers by recharge wells or basins has played an important role in overcoming some ground water problems. Artificial recharge of underground reservoirs by water spreading has been practiced successfully in the United States for many years. In the West it has become an important method of salvaging flood run-off for irrigation of crops and maintenance of public water-supply reserves, and it is used to some extent in parts of the East. Artificial recharge by means of wells, on the other hand, is a relatively new development. Until recently it was employed in only a few areas, principally along the East coast. For the last few years, in the ever increasing search for additional water supplies, industry has had greater recourse to this method. Utilization of recharge wells to control the temperature and quality of underground water supplies is also being considered seriously. Operation of recharge wells, like water spreading, is governed largely by local conditions. It requires water relatively low in turbidity, whereas in some areas water spreading has been used successfully with water of high turbidity and silt content. However, water spreading must be employed in large areas and can be carried on effectively only where aquifers crop out at the surface. Recharge wells can be used in limited space. Recharge wells are similar to production wells except that the water flows in the opposite direction. Thus any water-bearing bed that will yield water to wells may be recharged by wells. Often, however, the water available for recharge is of a different character and temperature from that existing in the ground-water reservoir and if transmitted directly underground from a recharge well to a production well might require expensive or difficult treatment before it could be used. Fortunately the physical characteristics of reservoir beds, which control the movement and behavior of ground water, are generally not homogeneous. Moreover, the movement of ground water is very slow because of the frictional resistance of the reservoir beds. By taking full advantage of hydrologic and geologic conditions, it is therefore possible in many instances to bring about favorable changes of temperature and dilution as the water moves from the recharge wells underground to the production wells. Furthermore, if the natural quality or temperature of ground water is unfavorable for industrial purposes, recharge wells may be used to introduce water of more favorable quality or temperature into the ground-water reservoir. When water is discharged into a recharge well, the head in the well is increased. Because of this, a cone of elevation is produced on the water table or the artesian pressure surface in the area surrounding the well. The cone of elevation is similar to the cone of depression produced around a pumping well except that the apex of the cone is above the water table or artesian pressure surface. Thus if a recharge well and a production well tapping the same water-bearing bed are close together, as would be the case at many industrial plants, some of the water discharged from the recharge well would be drawn into the production well within a short time. Under such conditions it is apparent that water of unfavorable temperature and chemical characteristics should not be used for recharging. The more important ground-water reservoirs in the United States often consist of alternating layers of impermeable beds and porous material that will yield water readily to wells. Physical characteristics of individual beds in a ground-water reservoir may not persist over great distances, the impermeable layers grading into beds that will yield large quantities of water. Thus the water-yielding material in underground reservoirs, whether large or small,

Jan 1, 1954

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By J. W. Pugh, J. D. Nisbet

F. B. Foley—The use of data published by Wever and Jellinghaus in 1931 to fix boundaries of the sigma phase in the Fe-Cr system, in the face of the author's own references to the suggestions of Bradley and Goldschmidt, Aborn and Bain, and Hougardy that the phase is much more extensive, and the very much more accurate work, which weighs heavily in favor of these suggestions, of Cook and Jones, published in 1943 and evidently disregarded by the authors, makes their derived ternary diagram, especially fig. 15 for 400°C, quite inaccurate on the Fe-Cr side and affects the extent of phase boundaries in the most controversial and important part of this ternary system. In commercial Fe-Ni-Cr alloys the occurrence of sigma has been observed time and time again at lower chromium contents than that of the 24 pct Cr, 16 pct Ni, 60 pct Fe alloy which is the lowest permitted by fig. 15 of practically carbonless metal. Newel1 reports sigma in 27 pct Cr-Fe even with some carbon present to be one of the greatest detriments to its extensive application, whereas Pugh and Nisbet set a low limit of 36 pct Cr for sigma in the binary Fe-Cr system. J. J. Heger—The diagrams presented by the authors do not agree with observations made on commercial Fe-Cr and Fe-Cr-Ni alloys, nor do they agree with two recent investigations made on the Fe-Cr and the Fe-Cr-Fe systems. I refer first to the investigation made by Cook and Jones1' on the sigma region of the Fe-Cr system. On the basis of their results which were published in 1943, Cook and Jones established new boundary limits for the sigma and the alpha plus sigma regions. These new limits have been accepted and are incorporated in the Fe-Cr diagram that appears in the 1948 edition of the Metals Handbook. This diagram is shown here as fig. 34. As will be noted, the boundary limits of the alpha plus sigma region in this diagram extend to much lower chromium contents than do those in the diagram presented by the authors in fig. 2. These new limits indicate that sigma phase should form in an Fe-Cr alloy containing 26 pct Cr, and experience with commercial alloys confirms this finding. Indeed, recent studies on a commercial Fe-Cr alloy containing 17 pct Cr have shown sigma phase to be stable in this alloy at 550°C. I recognize that the authors' work did not include studies on the sigma region; however, I believe this is a serious omission because sigma phase may profoundly affect the physical properties of these alloys and should be evaluated in any investigation which attempts to relate physical properties to the equilibrium diagram. The second investigation to which I refer is that made on the Fe-Cr-Ni system by Rees, Burns, and Cook,'' who used pure alloys and employed heating 17 W. P. Rees, B. D. Burns, and A. 3. Cook: Journal Iron and Steel Institute. (July 1949) 162, Part 3. p. 325. times that extend to 200 days. These investigators published their results in July 1949 and from these results constructed isothermal sections at 800" and 650°C. The isothermal section at 650°C is shown here as fig. 35. This diagram indicates sigma phase should form in a pure 18 pct Cr-8 pct Ni alloy. Although sigma phase has not been observed after 10,000 hr at 1200°F in commercial 18-8 alloys containing carbon and nitrogen, it has been observed under the same conditions in 18-8 alloys modified with titanium and columbium, both of which serve to reduce the effect of carbon and nitrogen. This section and the one at 800°C suggest that the constant iron sections which are presented by the authors, should be considerably altered, if they are to represent an accurate picture of the system. A few of the suggested alterations are as follows: In fig. 9, the section at 50 pct Fe, the gamma plus sigma region should be widened, not narrowed at 800" and 650°C. In fig. 10, the section at 60 pct Fe, the gamma plus sigma region should be widened at 800° and 650°C. In fig. 11, the section at 70 pct Fe, an alpha plus sigma, an alpha plus gamma plus sigma, and a gamma plus sigma region should be added. In fig. 12, the section at 80 pct Fe, the alpha plus gamma region should be widened at 800°C. In fig. 13, the section at 90 pct Fe, the alpha plus gamma region should be widened at 650° and 800°C. Undoubtedly, the chief reason for the discrepancies between the authors' data and those of Rees, Burns, and Cook is that the authors did not employ long enough heating times to allow for transformation. In this connection, I wish to warn that transformations in these alloys, particularly transformations at temperatures below 800°C, are extremely sluggish and may require a year or more to approach completion. Therefore, unless extremely long heating times are employed or steps are taken to accelerate these transformations by such means as mechanical working, the results will not yield an accurate picture of the alloy system. Certainly, an accurate picture is needed for the development of better high-temperature materials. E. J. Dulis-The purpose of this work is not clear. If an improvement of the ternary equilibrium diagram of the Fe-Cr-Ni system was wanted, it seems logical that testing techniques superior to those previously used would be a prime requirement. To approach equilibrium in this system, long holding times are needed; a fact established long ago but apparently ignored by the present authors, who used the continuous heating and cooling tests in equilibrium studies. A publication on the same system by Bradley and Goldschmidt6 was criticized by Monypenny in a

Jan 1, 1951

By Fred D. DeVaney

DURING the past few years a radically new process for the magnetic roasting of iron ores has been investigated and developed by Pickands Mather & Co. and the Erie Mining Co. in the Erie laboratory at Hibbing, Minn. This process, originally devised by Dr. P. H. Royster of Washington, D. C., involves the use of a roasting technique quite different from older methods. It has now been demonstrated that iron-bearing materials can be roasted as effectively as by any previously known method, and at a much lower cost. The increasing shortage of highgrade iron ores in this country has accelerated the search for new methods that would permit low grade materials to be utilized. The concept of magnetically roasting low grade nonmagnetic ores such as the oxidized taconites and then separating such material magnetically has always had considerable appeal. The magnetic concentration idea is attractive because of the sharpness of the separations and cheapness of the method. Heretofore, however, the equipment and the processes available for the magnetizing-roasting -step have left much to be desired. The customary equipment available for reduction roasting has been: 1-multiple hearth furnaces, 2-rotary kilns, and 3-shaft type kilns. In addition, it is understood that some work has been done in magnetically roasting fine ores by a process using the FluoSolids principle, but little information on this process is available. The multiple hearth kiln has been used the most but first costs and operating costs have been high because of low capacity, high maintenance, and poor gas utilization. Magnetic roasting can be done in a rotary kiln, but the radiation losses are high and the conversion to magnetite is usually unsatisfactory because of poor contact between the gases and the solids. Of the shaft-type furnaces, probably the most efficient yet developed is that designed by E. W. Davis of the Minnesota Mines Experiment Station. This furnace was operated at Cooley, Minn., during 1934-1937 but was abandoned in 1937 because the operation was uneconomic. Heretofore the basic concept behind most magnetic roasting processes has been the idea of heating iron ore to a temperature of 800° to 1100 °F in a strong reducing atmosphere, preferably either carbon monoxide or hydrogen. Temperatures under 800°F were undesirable since excessive roasting time was required. Temperatures over 1100°F were avoided because of the danger of converting part of the iron to ferrous oxide which is nonmagnetic. In the new roasting process, the operation is carried on in a shaft furnace using a controlled atmosphere containing a low percentage of reducing gas. The temperature in the roasting zone is considerably higher than with the usual reducing gas and this speeds up the reduction time. Portions of the spent furnace gases are cooled and recirculated and this together with the good contact between ore and gas makes for high reducing gas utilization. High heat economy is secured by recuperating heat from the roasted ore by passing the cold reducing gases countercurrent to flow of ore. The heat transfer principle is similar to that employed in a pebble stove and to that used in the Erie Mining Co. furnace at Aurora, Minn., for pelletizing fine magnetite concentrates derived from taconite. The theory of controlled atmosphere during the roasting operation can best be appreciated by inspecting the equilibrium diagram of the Fe-C-O system shown in Fig. 1. An inspection of this diagram shows that in certain areas magnetite, Fe3O4, is the only stable form of iron. A further inspection of this table shows that if the proper ratio is maintained between carbon dioxide to carbon monoxide, such a gas will be reducing with respect to hematite, Fe2O3, and will be oxidizing with respect to both ferrous oxide, FeO, and iron, Fe. It should be kept in mind that the formation of ferrous oxide in a roasting operation is harmful, since this oxide is nonmagnetic; if it forms in any quantity, it will cause substantial loss of iron in the ensuing magnetic separation step. If a ratio of approximately three parts carbon dioxide to one of carbon monoxide is maintained, the resulting operation can be carried on at a relatively high temperature without fear of over-reduction. Specifically, most of the tests in the Erie furnace have been made at a temperature of 1500° to 1600°F, with an entrant gas containing approximately 5 pct carbon monoxide and 15 pct carbon dioxide, with the remainder largely nitrogen. It should be remembered that the ratios of carbon monoxide to carbon dioxide shown in Fig. 1 hold even though the bulk of the gas is an inert gas such as nitrogen. It may surprise many to learn that a gas containing as low as 3 pct carbon monoxide, and 12 pct carbon dioxide with the remainder nitrogen is an extremely effective reducing gas in the 1000° to 1600°F temperature range. The reducing gas is not limited to carbon monoxide, and mixtures of hydrogen and carbon monoxide may be used effectively, provided that a similar ratio is maintained between the reducing gases and carbon dioxide and water vapor. For a more detailed explanation of the theory involved, the reader is referred to U. S. patents 2,528,552 and 2,528,553. From a safety standpoint, the weak reducing gas used in the furnace offers an advantage. Its composition is such that it is well below the limits of explosion should air enter a hot furnace. This condition is not true with the usual reducing furnace, in which a gas rich in carbon monoxide or hydrogen is used. The general furnace design and method of operation may best be understood by an inspection of

Jan 1, 1952

By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf's remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By F. C. Frischknecht

Most early development and application of electromagnetic prospecting methods took place in Scandinavia, where geological conditions favor their use. In other parts of the world these methods have aroused cycles of interest, but in Scandinavia they have been used continuously and successfully since the 1920's. Electromagnetic methods may be classified into two general groups. One group includes methods in which the source of the electromagnetic field remains stationary while the receivers are moved about to explore the area. The other includes procedures in which the energizing and receiving systems are moved together. Other classifications could be based on the size of the energizing source, the particular components of the electromagnetic field which are measured, or the mode of transporting the equipment. The difference between fixed-source and moving-source methods, however, is of such great fundamental importance that it will be emphasized in this discussion. FIXED-SOURCE METHODS Essentially, a fixed-source method consists of the measurement of electromagnetic fields about the source. The mutual coupling between the source and the earth is constant, but the mutual coupling between the receiver and the earth (unless the earth is homogeneous) and also between the source and the receiver changes at each station. The results are usually normalized by relating the field data to the calculated free space or primary field. Turam and Radio Reference Signal Methods: The turam or two-frame* (see Fig. 1A) is probably * Turam means two-coil. the most common fixed-source method. The energizing source is an insulated cable grounded at both ends or formed into a large rectangular loop. Measurements are taken along a traverse at 5 to 50-meter intervals using two small receiving coils, the lagging coil being placed at the position previously occupied by the leading coil. The complex ratio (i.e., inphase and out-of-phase ratios) of the voltages induced in the two coils is measured. Operating frequency range is about 100 to 800 cps. In a typical turam survey a straight, grounded cable several kilometers long is laid out parallel to the probable strike of the ore deposits or conducting strata being sought. An area extending 1 or 2 km on each side of the cable, and within 1 or 2 km of the ends of the cable, is surveyed. Measurements are made at stations 5 to 25 m apart along traverses perpendicular to the cable. Measurements may be made along lines parallel to the cable to serve as base lines for the traverses or for other special purposes. Commonly the receiving coils are oriented with their planes horizontal so that only the vertical component of the field is measured. If additional information is required, one of the hori- zontal components may also be measured by orienting the coils with their planes vertical. In a modified turam technique developed recently for both ground and airborne measurements (Fig. 1B) the amplitude of the complex voltage induced in a single receiving coil is measured and its phase compared with that of a reference signal transmitted from the energizing system by a radio frequency carrier. Thus the un-normalized field is obtained directly, whereas with the turam method it is obtained by calculation from the ratios. The turam method and its modifications have a greater working depth than the other electromagnetic procedures used in ore prospecting. Under favorable conditions conductors have been located at depths of 200 to 300 m. A modified turam method with one of the electrodes grounded in the upper end of a plunging orebody was used to follow the extension of this body to a depth of 200 m beneath a layer of conducting schists. Straight grounded cables are usually preferred to insulated loops because they are easier to lay out and because they often make the method more sensitive. The greater sensitivity of a grounded cable is a result of ground return currents which may flow in the orebodies in addition to the eddy currents caused by induction from the current in the cable. Anomalies in the vertical field due to eddy currents are characterized by a correspondence between high values for the inphase component and positive out-of-phase components and/or low values for the inphase component and negative out-of-phase components. Also the inphase component may approach zero, but it does not become negative. In very long continuous conductors that are parallel to a grounded cable the effect of ground return currents may far exceed the effect of eddy currents. These ground return currents cause a lack of correspondence between the inphase and out-of-phase components and may cause negative inphase or anti-phase components. It becomes difficult to carry out the measurements and often difficult to interpret the results. Such results immediately suggest the presence of graphitic strata, however, since ore deposits are rarely extensive enough to accumulate sufficient ground return current to cause these results. A cable laid out perpendicular to the strike or an insulated loop is sometimes used in areas where graphitic schists and slates are present. Anomalies are then completely or almost entirely due to eddy currents and are easier to interpret. The measured voltage ratios are normalized by either subtracting or dividing by normal field ratios calculated from free space considerations. The normalized ratios are then plotted as individual profiles. When significant anomalies occur in the ratio measurements, the actual normalized fields are calculated by beginning with a measured or an assumed value for the field at a point near the cable and successively multiplying this value by the normalized ratios. There is a similarity between this process and a numerical integration of the ratio curve. Conversely, in many respects the ratio curve is similar to the first derivative of the field curve.

Jan 1, 1960

By J. Leja, J. H. Schulman

FROTH flotation is usually effected by the addition of a collector agent and a frothing agent to an aqueous suspension of suitably comminuted mineral ores. The action of collectors is to adsorb onto the surfaces of minerals to be separated, sensitizing them to bubble adherence. The action of frothers has, in the past, been accepted as that of froth formation only, brought about by a lowering of the air/water interfacial tension. Substances capable of producing froth are classed1a,b according to their relative capacities for production of froth-volume and froth stability in the simple frother-water system. The purpose of this paper is to show that the surface active agents acting as frothers become effective only when there is a suitable degree of molecular interaction taking place between collector molecules and frother molecules at the air/water and solid/ water interfaces. Further, the discussion will demonstrate that the actual mechanism of adherence of an air bubble to a suitably collector-coated particle is due to the molecular interaction collector-frother. This leads to the formation of a continuous interfacial film of associated molecules, anchored to the mineral by polar groups of the collector, and enveloping the whole bubble. The tenacity of adhesion mineral-to-bubble results from the strength and the visco-elasticity of this mixed film. Some 20 years ago Christman2 postulated mutual dependence of collector and frother in effecting flotation. This view was, however, strongly opposed by Wark,3 who pointed out that an addition of frother had no effect on the value of contact angle once this was established in the solution of collector. More recent work by Taggart and Hassialis' indicated that the presence of frother, namely, cresol, leads to the immediate establishment of a contact angle on sphalerite, partially coated with xanthate, whereas an air bubble fails to make contact in potassium ethyl xanthate solution alone, even after 60 min induction time. Wrobel5 raws attention to the selectivity of frothers in flotation. Many instances of antagonistic effects of certain mixtures of frothers (or collectors and frothers) on flotation froth have been known to flotation operators and have been reported in literature. Taggart6 and Cooke7 give several examples of incompatibility of certain ratios of frothers and collectors, e.g., oleate and long-chain sulphates, pine oil and soaps. Monolayer Penetration. Properties of insoluble films produced by molecules of surface active agents orientated at the air/liquid interface are conveniently studied by the Langmuir trough technique, described fully by Adam.' Using the trough technique Schulman and Hughes" and Schulman et al.10a. b, c, d,e established the existence of molecular interactions occur- ring between certain types of surface active agents. Their experiments revealed the phenomenon of penetration of an insoluble monolayer (e.g., a film of a long-chain alcohol) by a soluble agent (e.g., sodium alkyl sulphate) injected into the substrate (water or salt solution). The degree of molecular interaction taking place on penetration is determined by changes in the surface pressure of the resulting film, changes of its surface potential and its mechanical properties (viscosity and rigidity). When the interaction takes place between both polar groups and both hydrophobic groups of the two participating amphipathic molecules a molecular complex is formed. Complexes formed on penetration of the monolayer at interfaces are not necessarily true chemical compounds: they are labile in solution, the activity and reactivity of individual components are greatly different from those of the molecularly associated complex, and on crystallization they usually separate out into components. However, when formed in the orientated state at interfaces they are found to be very stable, although some mixed films spread as monolayers of stoichiometric complexes can show further penetration by subsequent additions of the soluble component injected into the substrate.'" The degree of association between two or more types of surface active agents is very sensitive even to small changes in electric (dipole) moment of the polar groups of the amphipathic molecules as influenced by magnitude and position of neighboring ions or dipoles, their size, concentration, and stereochemistry. In addition, the molecular association is greatly influenced by concentration and type of inorganic salts in the substrate, by its pH, and by temperature. The nonpolar groups of interacting molecules greatly affect the stability of molecular complexes. Progressive shortening of the aliphatic chain of one of the reacting molecules weakens (at an increasing rate) its tendency to form stable complexes. Similarly, introduction of a double bond of cis-form into one of the reacting chains, which changes the straight hydrocarbon chain into a kinked one, or introduction of a branched chain, reduces the stability of the associated complex. Monolayer Adsorption. Using the trough technique and injecting metal ions into the substrate (water or salt solution) underlying insoluble films of fatty acids, alkyl amines, and sulphates, Wolsten-holme and Schulman11a,b,e. ' and Thomas and Schulman" have established conditions, namely, pH, concentration. and steric factors, under which molecular interactions take place between the polar groups of the surface active agents and the metal ions. These interactions are marked by great changes in the solubility and mechanical properties of the monolayer of the agent; no surface pressure increases are observed as in monolayer penetration experiments. The results of these adsorption studies, correlated with flotation experiments, indicated that in the case of fatty acids and alkyl sulphates their adsorption onto minerals of base-metals takes place by a similar

Jan 1, 1955

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By E. F. Reed

CONSIDERABLE deep hole prospect drilling has been done in the last few years in the Globe-Miami mining district about 70 miles east of Phoenix, Arizona, and in the San Manuel-Tiger area about 50 miles south of the Globe-Miami region. More than 205,000 ft of churn drilling have been completed by the San Manuel Copper Corp. at their property in the Old Hat Mining District in southern Pinal County. The deepest hole on this property is 2850 ft; there are 49 holes deeper than 2000 ft. At the adjoining Houghton property of the Anaconda Copper Mining Co., where only one hole reached 2000-ft depth, there were 27,472 ft of churn drilling and 3436 ft of diamond drilling. Three churn drill holes were deepened by diamond drilling methods. Near Miami in the Globe-Miami district the Amico Mining Corp. drilled four holes by combined churn and rotary drilling methods, the total amounting to 13,879 ft, of which 2256 ft were drilled with a portable rotary rig. In the same district, besides doing a large amount of shallow prospect drilling, the Miami Copper Co. drilled two holes of 2560 and 3787 ft, respectively, which were completed by churn drilling methods. The rocks encountered in drilling at San Manuel and Tiger are described by Steele and Rubly in their paper on the San Manuel Prospect' and by Chapman in a report on the San Manuel Copper Deposit? The rocks are well-consolidated Gila conglomerate, quartz , monzonite, and monzonite porphyry. In some places these formations stand very well while being drilled, and three holes were drilled without casing, the deepest of which was 2200 ft. In other holes faulted and fractured ground made drilling difficult. In the Globe-Miami district the deep drilling was done in the down-faulted block of Gila conglomerate east of the Miami fault and in the underlying Pinal schist. The geology of this area is described by Ransome.3 In the Amico holes the conglomerate varied from material consisting entirely of granite boulders and fragments to a rock made up of schist fragments in a sandy matrix; in the Miami Copper Co. holes there were more granite boulders and the material was poorly consolidated. Drilling was much more difficult and expensive in the Miami area than in the San Manuel district, mainly because of the depth of the holes and the formations drilled. All the deep hole prospecting described in this paper was done with portable rigs. The churn drill rigs were of several types, of which the Bucyrus-Erie were the most popular. Bucyrus-Erie 28L, 29W, and 36L rigs were used on some of the deeper holes on the San Manuel property. A few Fort Worth spudder types were tried, and the deepest hole at San Manuel was drilled with a Fort Worth Jumbo H. The spudder type is considerably larger than most other rigs used on this work and required a larger location site. The spudders were belt-driven machines with separate power units, and time required for setting up and moving was much longer than with the more portable drills. All the churn drilling was done by contractors or with machinery leased from them. A few of the contractors had complete equipment, including most of the necessary fishing tools. Unusual and special, fishing tools were obtainable from the supply companies in the oil fields of New Mexico or in the Los Angeles area. Most of the contractors used equipment with standard API tool joints, so that much of it was interchangeable. Failure of tool joints is one of the principal causes of fishing jobs. It can be minimized if the joints are kept to the API specifications and the proper sized joints are used in the various holes. The minimum sizes that should be used with various bits are as follows: 12-in. and larger bits, 4x5-in. tool joints; 10-in. bits, 3 1/4x4 1/4-in. tool joints; 8-in. bits, 2 3/4x 3 3/4-in. tool joints; 6-in. bits, 2 1/4 x3 l/4 -in. tool joints; 4-in. bits, 1 5/8 x2 5/8-in. tool joints. Two rotary drill rigs were tried at San Manuel on the same hole, and a portable rotary drill rig was used on the Amico drilling for test coring the formation and for drilling in holes 3 and 4. Rotary drilling differs from churn drilling or cable tool drilling in that the bit is revolved by a string of drill pipe and the cuttings are removed from the hole by a thin solution of mud pumped through the drill pipe. The principal parts of a rotary rig are the power unit, a rotating table to revolve the drill pipe, hoists to raise and lower the pipe and to handle casing, and a pumping system to circulate the drilling liquid. The rig used on the Amico property at Miami was mounted on a truck. The larger rig used on the San Manuel property was hauled by several trucks and had separate turntable and pumping units. Diamond drill coring equipment was used successfully with the rotary rig in the holes on the Amico property, To allow for 2 3/8-in. drill pipe with tool joints, 3 1/2-in. core barrels and bits were used. With the standard 3 1/2-in. core barrel there was considerable difficulty in maintaining circulation with mud, so a barrel was designed with a smaller inner tube and a broad-faced bit. This allowed coarser material to circulate between the barrels. Rock bits of 5 5/8 to 3 7/8 in. were used with the rotary rig for drilling between core runs. Diamond drill equipment is much lighter than churn drill tools, so that fishing tools can usually be obtained from supply houses by air express when needed. Three churn drill holes on the Houghton property at Tiger were deepened by diamond drilling with Longyear UG Straitline gasoline-driven-machines. The open churn drill hole was cased with 2 1/2-in. black pipe. In deep hole churn drilling, casing is one of the most important items, especially in drilling in unconsolidated material like the formations drilled by

Jan 1, 1952

By R. R. Estill

THE rank of the Ruhr coal ranges from a high volatile bituminous coal to an anthracite, depending to some extent on the original depth of the seam. The average Ruhr coal corresponds to a soft bituminous American coal of a coking quality. The average thicknesses of individual coal seams being mined are also comparable (59 in. against 65 in. in the United States). However, consideration of seam conditions and mining conditions other than those just mentioned emphasizes differences rather than similarities with United States soft coal. In general, the Ruhr seams now being mined are much more folded and inclined than American seams. Dips of 20' and 30" are common in seams now being worked, and 30 pct of the coal reserves in the district are in seams dipping more than 35". Only on the tops and bottoms of folds do we find rather flat coal seams. In addition to the folding there is extensive displacement by cross faulting plus a certain amount of strike faulting of an overthrust nature, which results locally in doubling or omission of seams. Because of the long history of mining in the Ruhr, nearly all coal lying near the surface has long since been mined out, and we find that the average depth of mining is at present about 2300 ft below the surface. Deep mining, folding, and faulting result in seam conditions requiring a great deal more roof support than one finds in American soft coal mines. In fact only in the anthracite district and the Rocky Mountain and Pacific coal fields do we find somewhat similar conditions. It is easy to say, therefore, that the problem of mechanization of coal cutting and loading in the German mines is quite different from that which we have so effectively met in America with our mobile cutters and loaders, duck bill loaders, and a room and pillar system of mining our drift and slope mines. Partly because of more limited coal reserves, the traditional German mining system is largely the longwall method, which gives an almost complete coal recovery. Backfilling must be extensively practiced to protect the longwall faces, the over and underlying seams and workings, and especially the surface industrialized areas and barge canals. The German engineers have accordingly concentrated their efforts on the design of cutters, loaders, and conveyors suitable to longwall methods rather than room and pillar methods. Undercutters with cutter bars like American models have been in use in the Ruhr since well before World War 11. In 1941 they accounted for 8.5 pct of the production. This percentage, of course, includes coal which was undercut but nevertheless had to be broken down with air hammers or with explosives. The most common of these cutters is the Eickhoff Standard cutter (see fig. 1). This machine does about 95 pct of the undercutting in the Ruhr today, and is available with either compressed air or electrical power and in at least four different sizes. A variation of the cutter is this one with two cutter bars (fig. 2). At the end of 1947 about 200 of these machines and similar cutters were accounting for 13.2 pct of the total production, a production which was, however, only 60 pct of the 1941 production rate, so that the actual cutter tonnage was only up to a small amount over 1941. In 1941 about 3 pct of the production was accounted for by shearing machines making their cut perpendicular to the longwall face. They were similar to those used in the States. These machines are today considered obsolete and now account for only 0.7 pct of the total production. They are located at only a few mines and at present do not seem to have much of a future in the Ruhr. For the future, the Ruhr miner is looking forward to rather extensive mechanization of face work, with two major types of equipment being developed almost simultaneously. On one hand there is the development of cutter loaders for use in relatively hard coal. They represent the further extension of ideas developed after relatively long experience with the Eickhoff cutter. On the other hand there has been since 1942 an intense interest in the Ruhr in the development of face-stripping methods, particularly by the Kohlenhobel (coal plow) and its modification. At the end of 1947 these cutter loaders, Kohlen-hobels and scrapers together were actually accounting for only about 1.4 pct of total production while air hammers still broke 77.1 pct and as much as 1.2 pct was actually broken by hand picks. However,

Jan 1, 1951

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed' that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen' locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By H. Conrad, V. V. Damiano, G. J. London

The slip mode activated during the c axis compression of single crystals of commercial-purity ingot SR beryllium, high-purity (twelve-zone-pass) beryllium, and Be-4.4 wt pct Cu and Be-5.2 wt pct Ni alloys in the temperature range of 25° to 364°C was determined using two-surface slip trace analysis, slip-step height analysis, and electron transmission microscopy. All three techniques indicated the occurrence of copious pyramidal {1 122) (1123) slip in the alloys over the entire temperature range, the amount increasing with temperature. Pyramidal slip was also indicated in the high-purity beryllium by slip trace analysis and electron transmission microscopy, but the amount was somewhat less than in the alloys. For the commercial-purity ingot crystals, only a very small number of pyramidal slip lines were observed, and these were in the immediate vicinity of the fracture surface. No pyramidal dislocations could be detected by electron transmission microscopy in this material. Dislocatransmissiontions with Burgers vectors [0001] and +(ll20) were identified by electron transmission microscopy inthe (1122) slip bands, as well as those with the j (1123) vector. This was interpreted to indicate that the edge components of the 3(1123) vector dislocations activated during c axis compression dissociate upon unloading according to the reaction i (1123) — [0001] + 3(1120) THE microstrain c axis compression of single crystals of commercial-purity ingot SR beryllium (99.6 pct), high-purity twelve-zone-pass beryllium (99.98 pct), Be-5.24 pct Ni and Be-4.37 pct Cu alloys was described in a previous paper.1 This paper covers in detail the analysis of slip traces observed on two mutually perpendicular lateral surfaces of these specimens, and a detailed description of transmission electron microscopy studies performed on foils cut from the bulk crystals after they had been deformed to fracture in the c axis compression. Observation of slip traces on single surfaces of deformed single crystals are generally insufficient to positively identify slip or twinning modes. The use of two carefully cut and oriented perpendicular surfaces can greatly aid in the positive identification and index- ing of slip traces, although even this technique may be quite inadequate if more than one type of slip system operates and if an insufficient number of traces are observed on the surfaces. The problem is greatly simplified for symmetric cases like that for c axis compression of an hep crystal such as beryllium, in which the operating slip systems are all equally inclined to the direction of the applied stress, and each slip system of a given slip mode has an equal chance of operating. For such cases, the traces of any given slip mode observed on the surfaces cut parallel to the c axis are symmetrically tilted about the c axis. It is therefore possible to quickly determine whether one or more slip modes are operating. Confirmatory evidence in support of the observations made on the external surfaces can be obtained from foils cut from the deformed crystals and examined by transmission electron microscopy. This latter technique serves to identify not only the operating slip plane but also the Burgers vector of the dislocations which participate in the slip. For this purpose, a simplified technique based upon a double tetrahedron notation is used in the present paper. The planes and directions in the hep lattice are all designated by letters rather than indices and extinction conditions are easily determined if the Burgers vector lies in the plane contributing to the diffraction. RESULTS 1) Slip Trace Analysis. The standard (0001) stereo-graphic projection of beryllium is shown in Fig. 1. The two mutually perpendicular, lateral surfaces of the compression specimen are represented by the diametrical planes AA' and BB', also referred to as surface A and surface B. For the specific case represented (a Be-5.24 pct Ni specimen deformed by c axis compression at room temperature), the A surface is tilted 5 deg to the (10i0') plane and the B surface is tilted 5 deg to the (1120) plane. Two surface trace analyses may be facilitated by examining in turn the intersection of various great circle traces of specific pyramidal planes with two surfaces and comparing the angles made with the (0001) plane with those actually observed on the two surfaces. One then identifies the slip traces by trial and error on a best-fit basis. The (1122) type planes (it was found that slip occurred on these planes) are shown plotted on the stereographic projection in Fig. 1. One obtains directly the angles between the (0001) plane and the {1122) traces by measuring the angle from the periphery to the point of intersection along the lines

Jan 1, 1969

By J. G. Patchett, R. W. Rausch

Fresh waters and the presence of clay in many Rocky Mountain and West Coast sands require special methods of log analysis. Archie's saturation equation requires addition of a shale correction term, and the SP equation must also be modified to account for clays. Suitable equations were developed several years ago, but have not been widely used due to the algebraic complexity. A computer-oriented method has now been developed to overcome this problem. The basic shaly sand equations are rearranged in four different ways to permit solution for various sets of available input data. Essential to application of the method is the correction of observed SP values to those that would be observed if the resistivity of the formation waters were exactly interchangeable with the activity. A graphic method for doing this is given. Where conditions require consideration of the effect of clay in the sands, the method presented has been found to improve the accuracy of water-saturation determinations. INTRODUCTION Log interpretation in many Rocky Mountain and West Coast basins is complicated by rapid vertical and lateral changes in water resistivity. Calculation of formation water resistivity from the SP curve becomes difficult in zones that contain clay, since changes in SP deflection may be due to changes in either clay content or water salinity. In hydrocarbon-producing reservoirs, the problem is further complicated because hydrocarbon saturation also reduces the SP.1 A log interpretation system using computers has been developed to provide a solution to this problem, based on equations proposed by de Witte.2 Four different simultaneous solutions of de Witte's equations have been made. Each solution method uses a different set of input data as independent variables. Thus, a choice of solution method is possible, depending upon the logs run and the availability of other data. Two of the solutions do not require a knowledge of water resistivity. This system is intended to be used primarily in multiple sandstone-shale sequences of low and moderate resistivities where the principal contaminant in the sandstones is clay. However, where sufficient regional data are available, interpretation in single-zone sandstone reservoirs can also be improved by using the method. THEORY AND HISTORY OF SHALY SAND ANALYSIS The log interpretation formula originally proposed by Archie3 in 1941 is applicable only to rock-fluid systems wherein the rock has negligible electrical conductivity. In 1949, Patnode and Wyllie4 showed that if the rock itself can be considered conductive due to the presence of clay, a different calculation approach is necessary. During the following years, this problem was investigated at great length, as was the related problem of the effect of rock conductivity on the SP.5-11 These investigations established functional relationships between SP, resistivity, water saturation and water resistivity for such a formation. Refs. 2 and 12 provide summaries of these studies. Unfortunately, practical use of these relationships required that water resistivity be known independently from the SP. Although log interpretation methods for rock systems containing clay were proposed at that time,' they were not generally accepted for routine use. There are three principal reasons for this. First, in many field situations involving high-salinity water, rock conductivity may be neglected (even if present) without introducing appreciable error. This may be seen by considering the following expression for waier-saturated rock.' 1/R2=1/R1+1/FRn....(1) where 1/R, is conductivity due to clay. As Rw becomes small, I/FRw becomes much greater than 1/R, which may be neglected. Where 1/R, may be neglected, the sandstone is called clean. If the term may not be neglected, the sandstone is termed dirty or shaly. For resistivity purposes, the classification between clean and shaly sands then depends not only upon the conductivity due to shale in the sand, but also upon the resistivity of the associated water (shale is used here to mean surface condition due to disseminated clay). A sand of given conductivity might safely be treated as clean in association with high-salinity water, but would require shaly sand methods if associated with fresher waters. Shaly sand methods are not required in many areas having saline waters; but in Rocky Mountain and West Coast sands having relatively fresh waters (often more than 0.3 ohm-m resistivity at formation conditions), the shaly sand methods are needed. Errors Rw calculations from the SP due to the presence of shale are likewise related to water salinity. In saline water formations drilled with fresh mud, the ratio of mud filtrate resistivity to water resistivity is high, the SP is large and the presence of shale can introduce large errors in water resistivity calculated by the conventional method. When the resistivity ratio is low, the errors are smaller. At zero SP, no error would result from shale. Thus, from the SP viewpoint, a given rock could be shaly if associated with a saline water, and clean in association with a fresh water, which is the opposite of the resistivity-oriented definition above.

By E. L. Anders

The Mile Six pool is located on the La Brea-Parinas Cullcession of International Petroleum Co., Ltd., in northwestern Peru on the west coast of South America. The reservoir pressure in this pool has been maintained within 200 psi of its initial value throughout its history, and gravity drainage has played an important role in the production behavior. It has now produced 95 per cent of its estimated ultimate recovery. It is estimated that this interesting oil pool will ultimately produce 67 per cent of the initial oil in place and that the resulting residual oil saturation may be as low as 19 per cent of the pore volume (29 per cent of the hydrocarbon pore volume). An evaluation of reservoir rock and fluid characteristics and ultimate oil recovery is presented. INTRODUCTION This study of Mile Six pool was made to evaluate its performance according to latest available information. The production performance of this pool has been discussed in various articles in the past. and the reported behavior has been used as an example for application of computation procedures for gravity drainage depletion' and as an illustration of field behavior under gravity drainage or expanding gas cap drive. There have been wide variations in reported values of initial oil in place, reservoir oil volume factor. connate-water sauration, volume of effective sand, and ultimate recovery because of the paucity of reliable basic data. These various factors have been determined as accurately as practicable with the latest available information, and this evaluation is presented herein. The production history of Mile Six is an excellent example of gravity drainage depleion with effective pressure maintenance by gar injection. GENERAL Mile Six pool was discovered by cable-tool drilling in November. 1927. when well 1996 was completed in the Parinas sand. After slow development with cable tools and sporadic production. the pool was opened to continuous pro(iuction in November. 1933. and develpment was completed with rotary rigs. Pressure maintenance was started in December, 1933. by returning gas to upstructure wells. Most of the development was 'completed by 1937, but some additional wells were drilled in the period 1939-1947. and several old wells were deepened. A total of 46 oil and gas wells and 4 dry holes were drilled on approximately 7-acre spacing. Of the producers. 21 are now flowing. 2 are pumping. 44 are gas input wells. 3 are abandoned. I is a gas well shut in. and 15 are shut in because of non-commercial production or high gas-oil ratio. The locations of all wells are shown on the map of Fig. I. Total oil production on Dec. 31. 1952, was 30,867,373 bbl: cumulative gas production was 22,023,777 Mcf; and 26,410,946 Mcf of gas had been returned to the reservoir. These figures do not include oil and gas lost ill a blowout in January. 1940. GEOLOGICAL DESCRIPTION Mile Six pool is located on the northern end of a structural spur projecting from the La Brea-Negritos uplift.' The spur is probably a reflection of a basement structure. It plunges gently to the north, i broken into a complex series of fault blocks. and contain.; the Verdun Alto. Section Sixteen. and Mile Six pools. The Parinas handstone (lower Eocene!. which is the producing formation in Mile Six. occurs at an average depth of 2,200 ft in the pool and dips north and east at from 15' to 20". The pool covers an area of approximately 350 acres. Mile Six is downfaulted about 600 ft from Section Sixteen pool to the soutb. and a major fault forms its western boundarv. The north and east boundaries are formed by the intersection of the sand top with the water-oil contact which occurs at approximately 2.440 ft subsea. An original gas-oil contact probably existed at about 1.875 ft subsea. Fig. 1 presents the latest structural interpretation of the pool. and Fig. 2 is an isopach map showing thickness of the total Parinas formation above the original water-oil contact. The heavy lints of Fig. 1 are contours on the sand top, and the fine lines are contours on the fault planes. This type of straight-line structural map was developed 1)) International's geologists to reflect structural conditions where the bedding planes dip and have no curvature. 'The La Brea-Parinas Concession is highly faulted by normal fault.. The beds are flat wherever exposed. The Parinas formation is approximately 635 ft thick. and it is etimated that 62 percent II the formation is effective sand. The original oil zone was about 565 ft thick. Fig. 211 presents an electric log showing typical Parinas sand development ill Mile Six pool. The Parinas band in Mile Six i. a well-sorted. medium- to-coal-se-grained. cross-bedded sand with minor lenses of shale and small lenses and pockets of pebble conglomerate. The sand grains are subangular to rounded and consist chiefly of quartz with feldspars. biotite hornblende, and augite as accessory minerals. Because of faulting of the Parinas- formation to the east and north of the pool. there is probably l possibility of a significant, natural water drive in Mile six. The faults within the pool. as indicated in Figs. 1 and 2. are of smaller disI,laceInent and seem to act only , partial barriers to fluid movement within the reservoir. RESERVOIR CHARACTERISTICS Core analysis data are available from five wells. The data were obtained from three wells (Nos. 3401. 3586 and 3719) at the time of their completion and from well 1996 when the original liner was sidetracked and the well was deepened ill 1946. Data from well 2779 were obtained in 1943 from old cores taken when the well was deepened in 1934. From these core analyses. the average porosity was estimated to be 22.6 per cent. and the average permeability to dry ail. was estimated to be 780 and Measured productility indices varied from 3.1 to 71.4 B/D per psi differential. Specific productivity indices varied approximately from 0.1 to 0.3 B./D per psi per ft of sand.

Jan 1, 1953

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.' At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.'-' The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

By C. R. Watts

The feasibility of producing composites containing nickel or molybdenum fibers in a beryllium matrix was inrestigated. The composties studied were jabricaled by powder mallurgical techniques. The 1-mil-diarr nickel fibers reacled completely below 900°C, converling the fibers .from nickel to Ni5Be2,. As the /LO/-pressing temperalure as raised above 1110oC, tlie nickel diffused outward from the beryllide fibers. The solid solubility of nickel in beryllium was clboul 20 wt pet at the 1100°C pressing temperature a1 the zone-fiber interface. The 1.5-mil-diam molybdenum fibers slzolred no evidence of reaction and little evidence of diffitsion after pressing at 900°C. Between 1000° and 1050°C pressing conditions, the fibers began lo react , producing 1ayers of MoBe2 and MoBe12, respectively surrounding the molybdenurn core. The struture remained the same at 1100°C with no evidenre of solid solubility of the molybdenum in the berylium or vice versa. In recent years a considerable amount of attention has been devoted to the determination of methods for improving the mechanical properties of materials through the use of fiber or whisker reinforcement. Previous work with metal matrix composites indicates that the study of the chemical compatibility of the fiber and matrix is an area requiring greater understanding. The metal-metal or ceramic-metal interface is frequently subject to chemical reactions that may result in the formation of hard brittle intermetal-lic compounds and/or low melting point eutectic compositions. The reaction products may reduce both the low-temperature and elevated-temperature strength of the composite by weakening the fiber-matrix bond, producing premature failure at the interface. It is well-known that most metal-metal systems and many metal-ceramic systems of interest for structural composites are thermodynamically unstable,'-" particularly at elevated temperatures. If, however, the rate of reaction under the conditions of fabrication is sufficiently low. composites can be fabricated that can be used efficiently for indefinite periods at low temperatures and for short periods at elevated temperatures. This paper presents the results of a series of tests to determine the compatibility of nickel and molybdenum fibers with beryllium at various hot-pressing temperatures. Nickel was selected as a candidate fiber material primarily because the relatively ductile fibers might be useful as crack arresters in applications such as ballistic impact where crack growth can result in catastrophic failure. The high density and the reactivity of nickel were primary factors detracting from its selection as a possible reinforcement. Molybdenum with a modulus of elasticity of 52 Xlo6 psi is one of the few metallic materials having a modulus higher than beryllium (42 X lo6). Its high modulus, coupled with its refractory characteristics, made molybdenum an attractive candidate for a relatively stable fiber reinforcement for beryllium. Its density, being higher than that of nickel and over five times that of beryllium: detracted from its other characteristics. EXPERIMENTAL PROCEDURE The specimens were prepared from beryllium powder with a dispersed phase of fibers by powder metallurgical techniques. P-20 grade powder, Table I, from Berylco was used as the matrix material. Short lengths of 0.001-in.-nominal-diam nickel fibers supplied by the Sigmund Cohn Corp. and 0.0015-in.-nominal-diam molvbdenum fibers obtained from the General Electric Co. were used as the dispersed phase. The composite constituents were combined under an argon atmosphere by mechanically mixing the powders and fibers. The compositions used were nominally 1 vol pct fibers. After mixing. the composites were hot-pressed into a-in.-diam pellets under an argon atmosphere at 900°, 1000". 1050". and 1100°C at a pressure of 6000 psi with no hold time at these temperatures so that a comparison could be made between the resultant microstructure and hot-pressing temperature. The billet was heated at a rate on the order of 30°C per min to the desired temperature and then cooled at a somewhat slower rate. The microstructure obtained should be considered as characteristic of the integrated time-temperature history of the sample, as well as the maximum temperature attained. Upon removal from the hot-pressing dies. the specimens were cut. mounted. and polished by standard procedures. No etchant was used in specimen preparation. Photomicrographs, electron microprobe scans, and electron back-scatter pictures were made. X-ray dif-fractometer patterns were made of several of the specimens. but only the lines for beryllium could be resolved. Specimens for optical and electron microprobe examination were selected partially for the roundness of the cross section. A round cross section was taken to indicate that the body of the fiber was approximately normal to the surface and that therefore effects due to fiber material immediately below the surface could be neglected. RESULTS AND DISCUSSION The microprobe scans indicated that nickel reacted as low as 900°C, converting the entire fiber cross section to NisBe21. Fig. l(a). There was no evidence of further reaction from the optical or the back-scatter pictures, Figs. 2(n) and 3(a).

Jan 1, 1970

Trans. No. Place Date Vol. Page 1. Wilkes-Barre Pa......May.71 1 3 2. Bethlehem, Pa.........Aug., '71 I 10 3. Troy, N.Y............Nov..: 71 1 13 4. Philadelphia, Pa........Feb., 72.. 1 17 5. New York. N. Y.*......May, '72.. 1 20 6. Pittsburgh. Pa.........Oct..' 72.. 1 25 7. Boston, Mesa..........Feb., '73.. 1 28 8. Philadelhia, Pa.*......May, '73.. 2 3 9. Easton, is............Oct..' 73.. 2 7 10. New York, N. Y.......Feb..' 74 . . 2 11 11. St. Louie. Mo.*........May,' 74 . . 3 3 12. Hazleton, Pa...........Oct., '74.. 3 8 13. New Haven Conn......Feb., '75.. 3 15 14. Dover,N.J.*..........May, 75.. 4 3 15. Cleveland,O...........Oct. 75. 4 0 16. Washington D. C......Feb.'' 76.: 4 18 17. philadelphia, Pa.......June,: 76.. 5 3 18. Philadelphia Pa........Oct 76.. 5 19 19. New York, N. Y.......Feb: '77.. 5 27 20. Wilkes-Barre. Pa.*.....Mag :77.. 0 3 21. Amenia N. Y..........Oct. 77.. 6 10 22. Philadeiphia Pa........Feb.;' 78. . 6 18 23. Chattanooga' Term.*. . . May' 78. . 7 3 24. Lake George: N. Y....: Oct. 78. . 7 103 25. Baltimore, Md.*.......Feb:' 79.. 7 217 26. ~ittsburgi, Pa.........~a;' 79.. 6 3 27. Montreal, Canada......~ept.;' 79.. 8 121 28. New York, N. Y.*......Feb., '80.. 8 275 29. Lake Superior, Mich....Aug., '80. . 9 1 30. Philadelphia, Pa.*......Feb., '81. 9 275 31. Staunton, Va..........May, '81. .10 1 32. Harrisburg, Pa.........Oct.. '81..10 119 33. Washington, I). C.*....Feb., '82. . 10 226 34. Denver. Colo..........Aug.. '82. . ll 1 35. Boston. Mass.*.........Feb.. '83..11 217 38. Roanoke, Va...........June, '83.. 12 3 37. Troy, N. Y...........Oct.. '83. .12 175 38. Cincinnati. O.*.... Feb, '84..12 4 39. Chicago Ill............May, '84. . 13 1 40. philadelphia, Pa........Sept., '84. . 13 285 41. New York, N. Y.*......Feb., '85. . 13 586 42. Chattanooga, Tenn.....May, '85..14 1 43. Halifax, N. S..........Sept., '85.. 14 307 44. Pittsburgh, Pa.*........Feb.. '86 . . 14 587 45. Bethlehem. Pa.........May, '86 .. 15 Ixiii. 46. St. Louis, Mo..........Oct, 86.. 15 Ixx. 47. Scranton, Pa.*.........Feb.', '87. . 15 lxxvi 48. Utah and Montana.....July '87.. 16 xvii. 49. Duluth, Minn...........July' '87. -16 xxiv. 50. Boston. Mass.*.........Feb.: '88. . 16 xxviii. 51. Birmingham, Ala.......May, '88. .17 xix. 52. Buffalo N. Y..........Oct. '88.. 17 xxiv. 53. New york, N.Y........feb.' ;89 . . 17 xxxi. 54. Colorado..............June' 89 . . 18 xvii. 55. Ottawa, Canada........Oct., 89. . 18 xxiv. 56. Washington, I). C.*. . . Feb. 90. .18 xxx. 57. New York, N. Y........sept:, '93. .19 vii. 58. New York, N. Y.*......Feb. '91. . 19 xxv. 59. Cleveland, O.......... June, :91 . .a xvi. 60. Glen Summit, Pa.......Oct, 111. . 20 lxi. 61. Baltimore, Md.*.......Feb.: '92. .21 xix. 62. Plattsburg, N. Y.......June, '02. . 21 xxxiii. 03. Reading. Pa...........Oct., :92. .21 xliv. 64. Montreal. Canada*.....Feb. 93..21 65. Chicago, Ill............aug.: '93..22 XI. 66. Virginia Reach. Va.*. ...Feb., '04. .24 xwl. 67. Bridgeport Coon.......Oct., '94..24 xxx?. 08. Florida ...'............Mar., '95. .25 xix 69 Atlanta. Ga......... Oct 95. 25 xi 70. Pittsburgh. Pa.*........Feb., '96.. 26 xvii. Trans. No. Place Date Vol. Page 71. Colorado..............Sept. '96. .26 xxix. 72. Chicago, Ill............Feb.. "97.. 27 xvii. 73. Lake Superior..........July '97. .27 xxx. 74. Atlantic City, N. J.*. ..Feb.: :98. .28 xvii. 75. Buffalo N. Y..........Oct. 08. .28 XXXVI. 76. New York,N. Y.*......Feb.: '99. .29 xvii. 77. California.............Sept., ;99. . 29 xlix. 78. Washington, D. C.*.....Feb., 00. .30 xix. 79. Canada...............Aug.. '00. .30 xlv. 80. Richmond. Va.*........Feb.. '01. . 31 xix. 81. Mexico................Nov..'01.. 32 cxviii. 82. Philadelphia Pa. $......May, :02. . 33 xxxv. 83. New Haven, Conn......Oct.. 02.. 33 xlvii. 84. Albany N. Y.*........Feb '03. .34 xxiii. 85. New York, N. Y........Oct.': '03. .34 xi. 86. Atlantic City. N. J.*....Feb., '04. .35 XXIII. 87. Lake Superior..........Sept.'04. .35 dii. 88. Washington. D. C......May' '05. .36 xlii. 89. British Columbia.......July, '05. . 36 90. Bethlehem. Pa.........Feb. '06. .37 xli. 91. London, England.......July: '06. .37 xlviii. 92. New York, N. Y........April, '07. . 38 lii. 93. Toronto, Canada.......July. '07. .38 lix. 94. New York, N. Y........Feb., :08. .39 xli. 95. Chattanooga, Tenn.....Oct.. 08..39 xlviii. 06. New Haven Conn......Feb. '09. .40 xli. 97. Spokane,Wash.........Sept:.'09. .40 xlviii. 98. Pittsburgh, Pa.........Mar.,'10. .41 xxxviii. 99. Canal Zone............Nov.,'10. .41 dv. 100. Wilkes-Barre, Pa.......June. ' 11. . 42 xxxiv. 101. San Francisco, Cal......Oct.. '11..42 xliv. 102. New York. N. Y.*......Feb 12. .43 Ixxvii. 103. Cleveland, Ohio........0ct;' '12.. 44 wii. 104. New York, N. Y.*......Feb.. '13. .45 xv. 105. Butte, Mont...........Aug., '13. .46 ?' 108. New York, N. Y........Oct., 13..47 vii 107. New York. N. Y.*......Feb.. '14..48 xv. 108 Salt Lake City. Otah Aug. :l. 49 5: 109. Pittsburgh, Pa.........Oct., 14. .50 vii. 110. New York, N. Y.*......Feb., '15. .51 xvi. 111. San Francisco, Cal......Sept., '15. .52 xii. 112. New York,N. Y.*......Feb., '16..54 xvi. 1 Arizona...............Sept.,'l6. .55 VII 114. New York, N. Y.*......Feb., '17: .56 vii. 115. St. Louis, Mo..........Oct.. '17..57 vii. 116. NewYork,N. Y.*......Feb.. '18..59 xvii 117. Colorado.....:........Sept.,'18. .60 vii. 118. Milwaukee, Wis........Oct.. '18. .60 x:!: 119. NewYork,N. Y.*......Feb., '19..61 xi. 120. Chicago...............Sept.,' l9.. 62 VII. 121. New York, N. T.*......Feb., '20..63 ix. 122. Lake Superior District. .Aug., '20.. 66 ix. 123. New York, N. Y.*......Feb., '21. .66 xiii. 124. Wilkes-Barre, Pa...... Sept.. : 21.. 66 xix. 125. New York, N. Y.*......Feb., 22. .67 ix. 126. San Francisco. Cal......Sept.,:22. .68 xxix. 127. New York, N.Y.*.....Feb., 23. .69 xxix 128. Canada...............Aug., '23. .69 xxxv! 128.129. New York, N. Y.*......Feb., ;24. .70 xxxi. 130. Birmingham, Ala.......Oct. 24. .71 xxxiii 131. NewYork.N Y.*......Feb.: '25.. 71 xxxviii. 132. 131.Salt Lake City, Utah .. .Sept., '25. .73 xvi 133. New York, N. Y.*......Feb., '26. .73 xxii. 134. Pittsburgh Pa ....... Oct.. '26. .74 xv. 135. New York,' N. Y.*............Feb., '27. .75 x::: 135.136. NewYork,N. Y.*......Feb., '28..76 104 137 NewYork.N. Y.*......Feb., '29. .291 116 138.San FranciscoYork,N.Y. Cal..........Oct. 29..308 406 139. New York, N. Y.*...Feb., '30..30H 1321

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