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By G. Bhat, J. F. Libsch

lsoembrittlement curves depicting the influence of time and temperature in the range 800' to 1260°F (425' to 680°C) on the development of embrittlement in a commercial chromium alloy steel and a commercial molybdenum alloy steel are presented. Two distinct regions of embrittlement occur in the chromium alloy steel: I—at 800' to 1000°F (425' to 540°C) and 2—in the region just below the lower critical temperature. Embrittlement is most pronounced at 800' to 1000°F, decreasing very rapidly with increasing temperature above this region, only to increase again as the lower critical temperature is approached. The data suggest two distinct modes of embrittlement with possible superposition of the two modes at extended embrittling times in the temperature range 1100° to 1150°F (590' to 620°C). While the molybdenum alloy steel shows little susceptibility to embrittlement at 800' to 1000°F (425' to 540°C), considerable embrittlement may occur just below the lower critical temperature. THE subject of temper embrittlement in alloy steels has received considerable attention in the last few years. Points of view on the mechanism of embrittlement differ, however, resulting in part from the incompleteness of the data developed and in part from the speculation regarding the susceptibility of plain carbon steel to temper embrittlement. Libsch, Powers, and Bhat1 carried out short-time embrittling treatments on an AISI 1050 steel and demonstrated that hardened plain carbon steels are quite susceptible to embrittlement when tempered in the range from 850°F (455°C) to the lower critical temperature. The isoembrittlement diagram,' representing the embrittling characteristics of this steel, is reproduced in Fig. 1. It is evident from the shape of the curves shown that embrittlement in plain carbon steel increases progressively with both temperature and time in the embrittling range. A comparison of the isoembrittlement diagram for AISI 1050 steel with that presented by Jaffe and Buffum' for an SAE 3140 steel shows that up to 930°F (500°C) the isoembrittlement characteristics of the plain carbon steel are similar to those of SAE 3140 steel, although the embrittlement is much more severe in the latter steel. Above 930°F (500°C), the rate of embrittlement in the plain carbon steel increases continuously with increasing temperature; whereas, in the SAE 3140 steel, the embrittlement rapidly decreases. The influence of alloying elements upon embrittlement during tempering thus appears to cause a decrease in embrittlement above the region of maximum embrittlement, i.e., 850" to 1000°F. The question naturally arises as to what effect individual alloying elements have upon the embrittling characteristics of the plain carbon steel. Current knowledge on the influence of alloying elements on temper brittleness may be found in the review papers of Hollomon" and Woodfine. Hollo-mon," from the results of other investigators, has shown that, in general, the amount of embrittlement increases with increasing alloy content (except for molybdenum and possibly tungsten and columbium). Jaffe and Buffum," by a comparison of the embrittlement in a plain carbon steel with that of a SAE 3140 steel postulated that the presence of alloying elements in moderate amounts tends to retard the development of temper brittleness. It is difficult to determine what effect chromium has upon temper brittleness, since most of the information available has been based on the combined effect of other elements with chromium, particularly nickel and manganese. However, Wilten, and recently Jolivet and Vidal,' Vida1, and Woodfine have reported that chromium steels are temper brittle, that the embrittlement is reversible with a maximum rate of embrittlement at approximately 975°F (525"C)," and that the susceptibility increases with increasing amounts of chromium. Taber, Thorlin, and Wallacel" have found a large embrittling effect with increasing chromium content in a medium C-Mn-Ni steel. But Hultgren and Chang," from their experiments conducted on synthetically prepared ternary Fe-C-Cr alloys, could not conclude that these alloys are susceptible to temper embrittlement. However, on addition of manganese or phosphorus, these Fe-C-Cr alloys became susceptible, from which fact they concluded that the embrittlement developed in chromium-bearing Fe-C alloys is due chiefly to the presence of these elements. Considerable data are available to show that molybdenum decreases the susceptibility of steel to temper embrittlement. However, its effectiveness in preventing or decreasing embrittlement appears limited to its presence in small amounts. Vidal" has shown that a plain 2 pct Mo steel was susceptible. Hultgren and Chang" also have shown that molybdenum additions in excess of 2 pct to synthetically prepared Ni-Cr steels did not prevent embrittlement. Jolivet and Vidal' and Lea and Arnold found that molybdenum reduced temper brittleness. Lea and Arnold further stated that molybdenum decreased the rate of embrittlement rather than the total amount of embrittlement, whereas Preece and Carter" have shown that the presence of molybdenum greatly reduces the equilibrium extent of the change at a given temperature but does not appear to influence the rate of embrittlement. There appears to be very little information as to how molybdenum by itself affects the temper brittleness susceptibility of a plain carbon steel.

Jan 1, 1956

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

By Jaakko Kajamaa

Neutron diffraction was applied to determine sheet textures by the transmission method. Cold-rolled and recrystallized copper sheets were investigated. The amount of cube texture was determined for three compositions, in which the phosphorus content was, respectively, 0, 0.005, and 0.03 wt pct. The heat treatment was in every case 8 sec at 650°C. In the two latter cases the cube texture was prevented. In addition a comparison with the X-ray diffraction transmission method was made with the 96 pct cold-rolled copper sheet. Outer parts of both (111) pole figures can be considered to be rather identical. This is seen from the fact that the intensity ratio ITD/120" was 0.45 for neutron diffraction and 0.40 for X-ray diffraction. Differences between the methods were discussed in detail. Features peculiar to neutron and X-ray diffraction in texture studies were listed and compared. In this work neutron diffraction was applied to determine sheet textures. Specifically, it was desired to ascertain whether this method can be used to reveal differences when compared to other methods. In addition, the amount of the cube texture in copper sheets was determined as a function of phosphorus content. Previous applications of neutron diffraction to texture problems include the following: nickel wires,' wire of some bcc metals,' and uranium bars.3 In the neutron diffraction technique the greatest difference is in the sample—its method of production and its volume. A sample needs no treatment and its volume is roughly 105 times larger than the volume of an X-ray diffraction sample. The cold-rolled sheet was investigated both by neutron diffraction and by X-ray diffraction, because it is expected that, due to large number of defects, possible differences in the results of the two methods would be revealed. It is a well-known fact that X-ray lines show broadening when cold-worked. Analysis has shown that this is based chiefly on small crystalline size, micro-stresses, and/or faults.4'5 Neutrons are sensitive to the above-mentioned disturbing factors as well, but circumstances in diffraction are different from the X-ray case. Because the sample represents a larger volume, the result is an average over that volume. In addition, it can be assumed that the sample has preserved its original structure, because it needs no special preparation. The particular limitation of neutrons is the relatively low neutron intensity available from nuclear reactors. This decreases the resolution as compared to the X-ray diffraction methods. Furthermore, absorption mainly reduces diffracted X-ray intensity, while multiple scattering effects, i.e., secondary extinction, disturb neutron diffraction. SO neutrons and X-rays behave in a different way when interacting with matter. As in other structural investigations, one can utilize this difference in texture studies as well. One cold-rolled and three recrystallization textures in copper sheets were investigated by neutron diffraction. The samples were produced at the Outokumpu copper factory to the specifications shown in Table I. The paper is divided into five parts. The first deals with the theory of the measurement. In the second, experimental procedures are described. Results are presented in the third part. Both cold-rolled and re-crystallized samples are studied. Discussion is in the fourth part, and finally in the fifth part some conclusions are drawn. 1) THEORETICAL CONSIDERATIONS Properties peculiar to neutron diffraction are the following: a) the scattering length varies greatly between one element and another; b) many of the elements do not absorb neutrons appreciably. In this connection it is of primary interest to know the interaction of neutrons with lattice imperfections. As with X-rays this problem leads to diffraction analysis of deformed and recrystallized metals. From the physical point of view the main difference is that neutrons are scattered by nuclei (magnetic scattering is not considered here), whereas X-rays are scattered by electrons. The features peculiar to neutron and X-ray diffraction methods in texture studies are listed in Table 11. Pole figures are an important tool in performing structural analysis of deformed or recrystallized metal. Present texture research technology requires pole figures which are as precise as possible. The choice between these two methods depends on the technical information which is required. The X-ray diffraction transmission technique may give results which are not necessarily representative of the average physical state of the sample. Although foil samples normally contain enough crystallites for diffraction, they may not necessarily represent the whole structure. An example of this problem is the frequently observed difference between the "surface" and the "inside" texture of a sample. The production of foil samples may disturb the original structure of the parent material. The selection and orientation of the foil from the sample is quite arbitrary. Normally, a highly deformed piece of metal has several texture components. Different components are deformed in a slightly different manner. This is a re-

Jan 1, 1969

By R. E. Powers, E. H. Kinelski, H. A. Morrissey

A group of 17 American blast-furnace sinters, an American open-hearth sinter, an American iron ore, and a Swedish sinter were used to evaluate testing methods adapted to appraise sinter properties. Statistical calculations were performed on the data to determine correlation coefficients for several sets of sinter properties. Properties of strength and dusting were related to total porosity, slag ratio, and total slag. Reducibility was related to the degree of oxidation of the sinters. THIS report to the American iron and steel industry marks the completion of a 1949 survey of blast-furnace sinter practice sponsored by the Subcommittee on Agglomeration of Fines of the American Iron & Steel Institute. The use of sinter in blast furnaces, sinter properties, raw materials, and sinter plant operation have been reported recently.1,2 After preliminary research and study," test procedures were adapted to appraise the physical and chemical properties of sinter to determine what constitutes a good sinter. During the 1949 to 1950 plant survey each plant submitted a 400-lb grab sample to research personnel at Mellon Institute, Pittsburgh, Pa. A 400-lb sample was also submitted from Sweden. In addition, 2 tons of group 3 fines iron ore were obtained from a Pittsburgh steel plant. The following tests were performed on the iron ore sample and on the 19 sinter samples: chemical analysis; impact test for strength and dusting; reducibility test; surface area measurements, B.E.T. nitrogen adsorption method; S.K. porosity test; Davis tube magnetic analysis; X-ray diffraction analysis for magnetite and hematite; and microstructure. Results of these evaluations are discussed in this paper and supply a critical look at testing procedures used to determine sinter quality. Sinter Tests and Results Each 400-lb grab sample of sinter was secured at a time when it was believed to represent normal production practice at each plant. It was not possible to use the same sampling procedures throughout the survey; consequently samples were taken from blast-furnace bins, cooling tables, and railroad cars. These were very useful for evaluation of test methods, since they were obtained from plants with widely divergent operations. With the exception of Swedish sinter and sinter sample N, which were produced on the Greenawalt type of pans, all survey sinters were produced on the Dwight-Lloyd type of sintering machines. Sinters submitted for test were prepared in identical manner by crushing in a roll crusher (set at 1 in.), mixing, and quartering. To secure specific size fractions for tests, one quarter of the sample was crushed in a jaw crusher and hammer mill to obtain a —10 mesh size. The remainder was screened to obtain specific size fractions. The group 3 fines iron ore was dried and screened and samples were taken from selected screen sizes to be used for various tests. Prior to testing, each ore sample except the —100 mesh fraction was washed with water to remove all fine material and was then dried. This iron ore, a hematitic ore from the Lake Superior region, was used as a base line for comparing results of tests on sinters. The iron ore did not lend itself to impact testing, since it was compacted rather than crushed in the test, and no impact tests are reported. However, the iron ore was subjected to all remaining physical tests to be described. Chemical Analysis: Table I presents chemical analyses performed on the survey sinter samples. Included in this table are data obtained from determination of FeO and the slag relationships: CaO + MgO and total slag (CaO + MgO + SiO, SiO2 + Al2o3 + TiO2). The percentage of FeO was used as an indication of the percentage of magnetite in the sinter. It was believed that slag relationships could be correlated with sinter properties. During initial determination of FeO great disagreement arose among various laboratories, both as to the results and the methods of determining values. Table I lists the values of FeO resulting from the U. S. Steel Corp. method of chemical analysis,' which reports the total FeO soluble in hydrochloric and hydrofluoric acids (metallic iron not removed) with dry ice used to produce the protective atmosphere during digestion. Use of dry ice was a modification required to obtain reproducible results. In this method, the iron silicates and metallic iron are believed to go into solution and are therefore reported as FeO. This is important, for in the study of the microstructure of sinters, glassy constituents suspected of containing FeO as well as crystallized phases of undetermined identity which may also contain FeO have been observed. Strength Test by Impact: In evaluating sinter quality, one of the properties stressed most by blastfurnace operators is strength. This strength may be described as the resistance to breakage during handling of sinter between the sinter plant and the blast-furnace bins. It is also the strength necessary to withstand the burden in the blast-furnace. After

Jan 1, 1955

By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge' investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler' also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas' who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.'.' The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By F. F. Aplan, P. H. de Bruyn

The adsorption density of hexyl mercaptan was measured at the gold-solution and the gold-vapor interfaces. This collector is strongly adsorbed at low concentrations, a monomolecular layer being formed at the gold-solution interface at concentrations as low as 2 x 10'6 moles per liter. A maximum contact angle of 83 ± 3° is observed. From a thermodynamic analysis of the experimental data the changes in surface tension at the gold-gas and gold-solution interface are calculated. The data also suggest that the adsorption density of mercaptan at the gold-gas interface exceeds that at the gold-solution interface. In the equilibrium state, a simple flotation system consists of three phases, the solid to be floated, air, and an aqueous solution in stable contact along a line. During the process leading to this final state, a solid-gas interface is created at the expense of a portion of the liquid-gas and solid-liquid interfaces. This change of state is achieved by addition of a collector and, if necessary, suitable modifying agents to the system. By a combined application of the Gibbs Adsorption and the Young Equations, de Bruyn, Overbeek and Schuhmannl were able to show theoretically that the equilibrium distribution of the collector at all three interfaces determines the magnitude of the contact angle. Their analysis led them to conclude that the equilibrium adsorption density of the collector at the solid-gas interface exceeds its density at the solid- liquid interface. This paper succeeded in focussing attention on the neglected role of the solid-gas interface in flotation. In recent years the application of radiotracer, infrared, electrochemical and electro-kinetic techniques to studies of the solid-liquid interface2-5 enhanced our understanding of adsorption processes at this interface. Except for the measurement of contact angles, the solid-gas interface received no attention in fundamental flotation studies. In an attempt to apply the analysis of de Bruyn, Overbeek and Schuhmann to a simple flotation system, an investigation of the adsorption of hexyl mercaptan onto gold was undertaken. Gold was chosen as the solid phase in order to keep the number of dissolved chemical species in the solution phase to a minimum. Hexyl mercaptan (1 - hexanethiol) was selected as collector because its relatively high vapor pressure at room temperature makes it possible to obtain adsorption measurements at the solid-gas interface. This flotation system consists, therefore, of a pure solid phase (gold), an aqueous solution of a weakly dissociated collector (1 -hexanethiol), and a gaseous phase, nitrogen saturated with respect to both water vapor and mercaptan vapor. EXPERIMENTAL MATERIALS AND METHODS Materials: Liquid 1-hexanethiol (C6H13SH) was obtained from Distillation Products Industries and was further purified by double distillation. The purity of the final product was established by boiling point and refractive index measurements. For the adsorption studies from aqueous solution, the radiotracer element, sulfur-35, (half life 87.1 days, 0.169 Mev beta ray) was synthesized into the mercaptan by Tracerlab Inc., Boston, Mass. A close boiling fraction of the synthesized compound was used in the adsorption studies. The specific activity of the radioactive compound was 10 millicuries per gram.

Jan 1, 1963

By Robin O. Williams

AN investigation has been made of the Ni-Cr system for the purpose of elucidating certain points, namely the nature of aging in both terminal solid solutions and the nature of the phase diagram. Information pertaining to solubilities and precipitation has been obtained. Experimentation Five alloys, Table I, were arc melted in a cold copper crucible using electrolytic chromium and car-bony1 nickel, both dry hydrogen treated. These 100 g buttons were homogenized 24 hr at 1300°C in dry hydrogen and air cooled. Powders were prepared by filing or pulverizing and subsequent heat treatment was done in vacuum or helium using titanium chips as a getter. Powder of —80 mesh was filed from the 60 pct Ni alloy quenched from 1000°C and was sealed in silica under vacuum using a 250 °C outgassing. After aging as indicated in Table I1 the lattice parameters were measured on the quenched samples using the standard cos" 6 extrapolation. These parameters are considered accurate to roughly 0.0001A. In all cases chromium lines of 2.8812 ± 0.0005Å at 30°C were found. Drastic quenching from sufficiently high temperatures produced very sharp body-centered-cubic lines in the first four alloys without indications of transformations. Temperatures to 1250°C were used. Solid samples less than 1/16 in. thick were quenched in water without transformation and the powders could be adequately quenched in small helium filled thin wall silica tubing using a water quench. For those powder samples which were quenched from the two phase field the relative intensity of the body-centered-cubic lines and the face-centered-cubic lines were estimated and extrapolated to give the indicated solubility data in Fig. 1. The data for the two higher alloys were somewhat limited, the plotted points being the lowest temperature where no nickel phase was found. Neither filing, abrading, pulverizing, nor cooling to —190°C produced any new diffraction lines for solid samples quenched from the single phase region, nor did the character of the body-centered-cubic lines change Single phase body-centered-cubic powders likewise did not change on cooling to —190°C. Also, samples which had some precipitation due to inadequate quenching showed no additional changes under these conditions. The first change apparent by X-ray diffraction form samples quenched almost fast enough to prevent precipitation was the diffuseness of the body-centered-cubic lines, particularly on the low angle side, For slower cooling rates the diffuse face-centered-cubic lines appeared. Work on the large grained castings showed profuse streaking through some of the Laue spots while oscillating patterns showed broad body-centered-cubic and face-cen-tered-cubic lines as well as some new lines. For the 23.6 pct Ni alloy the new lines corresponded to 2.16, 1.96, and 1.86A and were more similar in character to the face-centered-cubic lines than the body-centered-cubic lines. Samples which were air cooled gave only face-centered-cubic and body-centered-cubic lines which were still broad. One pattern indicated that face-centered-cubic (111) plane was parallel to a body-centered-cubic (110) plane. For those samples which were examined by light microscopy there were details which were not resolved. However, varied and beautiful structures were obtained. Fig. 2 is of an alloy quenched in a helium filled silica tube from the single phase region and shows particles associated apparently with dislocations which are arranged in low angle boundaries. Finer, general precipitation has also taken place within the grains. Figs. 3 to 5 show the variety of structures produced in these alloys on continuous cooling. It appears that there are four distinct modes of precipitation as evidenced by these, figures. Annealing these structures at higher tem-peratures in the two phase field gives structures as shown in Fig. 6, which shows nickel plates in the chromium matrix which reprecipitated nickel on a much finer scale of the final quench. Lower annealing temperatures and shorter times naturally give finer plates of the nickel-rich phase. Samples of the first four alloys were annealed for appreciable times between 900º and 1250°C and gave structures like Fig. 6. The relative amounts of the two phases were measured and extrapolated to give solubility data as indicated in Fig. 1. The point at 1250°C was deduced from data of Oxx.1 These and most of the other samples were checked for ferromagnetism but none was apparent. In fact, it appeared that the magnetic susceptibilities were not more than three times that for paramagnetic chromium. Discussion In Fig. 1 it is seen that the solubility of nickel in chromium can be represented by a slightly curved line on the usual log X vs 1/T plot, These data are believed to be accurate to roughly 5 to 10º. There is only fair agreement with the data of Taylor and

Jan 1, 1958

By R. A. Deju, R. B. Bhappu

Further information on the surface characteristics of the silicate minerals was obtained by experimentally correlating the oxygen-silicon ratio of the silicates with their electrokinetic properties. Specifically, the behavior of the minerals in an electric field was investigated using zero point of charge as a parameter. A modified electrophoresis cell was used for the determination of electrophoretic mobilities. It was shown that there is an increase in the zero point of charge with increasing oxygen-silicon ratio in the silicates. Finally, a chemical interpretation was presented to describe the surface phenomena observed in the experiments. In recent years great interest in surface chemistry has produced a number of methods to study the surfaces of minerals and to observe the phenomena occurring at their interfaces. One such method is discussed in this paper. A rather complete review of the surface characteristics of the oxide minerals has been undertaken by parks,' but, a similar study has not been made for the silicate minerals. Two previous papers by the authors2'3 attempted to remedy this situation. In these papers it was demonstrated that the reaction between the silicate mineral particles and acidic water involves mainly an exchange of metal ions for hydrogen ions on the surface of the solid, leading to an increase in pH of the aqueous phase. Also, the degree of reaction was found to depend on the oxygen-silicon ratio of the silicate structure, being least for the quartz and greatest for the olivines. A hypothesis was then set forth explaining that upon the fracturing of a silicate mineral, the oxygen-metal bond (which is almost entirely ionic in character) will break more easily than the stronger oxygen-silicon bond. This results in the exposure of unsatisfied oxygen sites on one hand and active, exchangeable cations on the other. These active sites on the fractured surfaces are then available for reaction with the hydrogen ions in acidified aqueous solution. Thus, an increase in degree of adsorption of hydrogen ions occurs as the oxygen-silicon ratio increases due to the presence of a larger number of active sites on such minerals. A correlation between oxygen-silicon ratio and electrokinetic properties will be further pursued in this paper from both the theoretical and experimental points of view. Efforts will then be made to present a chemical interpretation of surface phenomena observed in the experiments. It is believed that this study may supply pertinent information on the behavior of silicate minerals in froth flotation systems. ELECTROKINETIC STUDIES Equipment: In a previous paper,2 Deju and Bhappu described a simple method for determing the zero point of charge using a potential across a cata-phoresis cell and observing particle movement by means of a Rayoscope* optical system. This setup is simple in design and operation and extremely reliable. With care, reproducible results within 1.5% accuracy may be obtained. A new setup has been developed, based partly on the design by Zeta-Meter Corp.4 and partly on previous cells used at the New Mexico Bureau of Mines. This new, modified cell is shown in Fig. 1. Although

Jan 1, 1967

By M. R. Tek, K. H. Coats, D. L. Katz

In natural gas storage operations, seasonal pressure fluctuations in the gas reservoir cause the water from the surrounding aquifer to flow into and out of the gas sand. The theory of unsteady-state liquid flow through porous media developed by Van Everdingen and Hurst' has been applied to predict the water movement into and out of the gar bubble for .several .postulated pressure cycles. Those cycles with as many pound-days above the original aquifer pressure as pound-days below, may cause the gas reservoir to slowly grow or shrink rather than hold to a constant volume. Applications to an actual field case study give the predicted gas reservoir monthly pressures and volumes as compared with the observed monthly pressures and volumes. INTRODUCTION A large number of natural gas storage reservoirs are bounded by or adjacent to large water-saturated formations called aquifers. The presence of these aquifers is usually evidenced by the production of water from wells delineating the gas-hearing sands. Some gas storage reservoirs in use today have been purposely developed on aquifers. Cyclic pressure variations in a gas storage reservoir cause water influx and efflux from the surrounding aquifer. This, in turn, results in a varying gas reservoir volume. The prediction of the effect of this aquifer fluid movement on the size and size variation of the gas reservoir can provide information valuable in the study of several reservoir engineering problems. The economics of gas storage operations are directly influenced by the influx of aquifer fluid into the reservoir since a shrinking storage reservoir requires increasing pressures for the storage of the same quantity of gas. Material balance and reserve or recovery calculations also obviously require knowledge of reservoir volume. Various other reservoir engineering calculations such as interpretation of well interference data, evaluation of physical characteristics of porous media, water coning, gas injection and pressure maintenance studies are typical problems where variations of volume due to edge or bottom-water encroachment becomes important. The solution of equations describing influx and efflux of water in the gas sand, application to gas storage reservoir behavior and interpretation of results are the main objectives of this paper. While this work was directed toward gas storage reservoirs, it applies equally well to repressuring of partially depleted oil reservoirs with an active water drive. MATHEMATICAL ANALYSIS As just mentioned, the cyclic pressure variations in an aquifer-surrounded gas storage reservoir cause water movement and varying gas reservoir volume. Prediction of this volume variation from the reservoir pressure cycles or the injection-production schedule requires adoption of a flow model, certain assumptions concerning reservoir and fluid properties, and formulation and solution of the governing differential equation. The flow model used in this study is a gas bubble located on a very large aquifer (Fig. la). Gas bubble radius and aquifer sand thickness are denoted by rr and h, respectively. Fig. lb shows the horizontal, radial two-dimensional porous reservoir attended by the unsteady, compressible motion of the aquifer liquid. Volume variation of the gas bubble is determined from aquifer water flow across the cylindrical boundary, r = r0

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By J. H. Faulk

An examination is made of the various factors influencing drilling rate and drill bit life in various diameter holes. It is concluded that drill bits in the size range 4% to 6 1/4 in. can be used to attain substantially the some daily drilling progress as conventional size bits in soft rock drilling operations. An examination of the most important factors influencing "hazard of losing the hole" in the different hole size results in the conclusion that the smaller hole sizes can probably be drilled at reasonably low risk. However, this risk will be somewhat greater in the smaller diameter holes, requiring that special drilling and mud engineering practices be used to make small diameter holes practicable in soft rock drilling operations. An engineering analysia is made of the power and hydraulic requirements of several drill string-hole combinations to test the feasibility of drilling .small diameter holes in soft rock areas. Large econormies in rig power requirements appear possible by drilling .smaller .size holes in these operations. INTRODUCTION The industry now is re-examining the utility of small diameter holes in the light of substantial technical advances made in recent years. Faced with increasing cost of finding reserves and with proration after developing them, the industry must either develop methods of economizing or receive a lower rate of return on investments. Small diameter holes appear to involve an attractive method of economizing. Our objective is to determine if this is technically possible in soft rock operations. Soft rock, as used in this report, refers to those formations of a "drill-ability" corresponding to that of all Gulf Coast formations shallower than and frequently including much of the Eocene rock system. An important phase of technology which we shall examine is relative drilling rate and bit footage which may be obtained with various size bits. Rig operating efficiency, particularly as influenced by hazard, is also discussed in detail. The technical conclusions resulting from these examinations are used to develop sample drill string design and rig horsepower requirements for drilling holes as smaH as 4 3/4 in. and larger. The principal criterion used for the drill string design is that approximately the same daily drilling progress would be possible in all size holes in soft rock operations. This facilitates a comparison of rig size required for drilling the hole sizes in the range between 4 3/4 and 8 3/4 in. BROAD PROBLEM OF DRILLING RATE AND BIT FOOTAGE The three factors controlling daily drilling progress are: (1) drilling rate of bit while on bottom turning, (2) bit footage, and (3) rig operating efficiency. Let us look now at the first two of these factors. Drilling technology has progressed to the point that a semi-quantitative analysis of the effect of various operating variables upon these factors can be made. Those factors which apparently limit both drilling rate and bit footage for bits now in use are: (1) bit design, (2) weight on bit, (3) hydraulic cleaning capacity for bit cutting surfaces and hole bottom, and (4) rotary speed. (We neglect the effect of mud and formation properties because these factors arc the same for the various size bits.

Jan 1, 1957

By N. F. Schulz

The purpose of this investigation was to evaluate the effects of variables in equipment and procedure on tube test results. This information was then to be used to formulate specifications, preferably within the practical ranges of existing machines, for test procedures capable of yielding precise and meaningful data concerning the magnetic separation of any magnetite ore, regardless of its origin. A survey of current practice was conducted among laboratories using the Davis tube test. Many tube tests were performed to experimentally evaluate the variables most likely to affect test results. A simple method was then sought for adequately interpreting tube test results. The Davis magnetic tube concentrator is a laboratory machine designed to separate a small sample of pulverized magnetic iron ore into magnetic and non-magnetic fractions. It was developed in 1921 by mechanization of a test previously performed manually No significant changes have been made in the design of the apparatus since that time. The Davis magnetic tube test continues to serve as a practical basis for judging the amenability of an ore to magnetic separation and for controlling magnetic separation plant operations. The apparatus consists of an inclined cylindrical glass tube supported adjacent to closely spaced pointed poles of a powerful C-magnet. (Fig. 1). To conduct a tube test, a sample of suitably prepared ore is poured into the water-filled tube. With wash water flowing through, the tube is oscillated to gradually reject the non-magnetic and weakly magnetic ore particles until the desired degree of separation is attained. Both the magnetic concentrate and the tailings may be recovered for examination. MAGNETIC SEPARATION BY THE DAVIS TUBE Mechanical separation of a specified mineral component from an ore usually requires comminution to fine sizes for sufficient liberation. Some distinguish- ing property of the mineral is then exploited to sort the desired mineral particles from the gangue particles. The magnetic separation of iron ores is based on the fact that magnetite, Fe3O4, is strongly attracted by a magnetic field while the gangue minerals are not. Maghemite, ?-Fe2O3, which may occur in certain chemically processed ores, responds similarly to magnetite. The magnetic process is practical only when the loss of iron in the form of relatively nonmagnetic hematite, Fe2O3, goethite, Fe2O3.nH2O, or other iron mineral can be tolerated. In the Davis magnetic tube concentrator, magnetic attraction holds magnetically susceptible particles in a magnetic field. Forces due to gravity, inertia, and fluid-solid friction tend to remove the less susceptible particles from the field. The probability that a given middling particle will be rejected from the tube in a given period of time is an inverse function of its magnetite content, with some modification due to particle size and mineral specific gravities. The net result is that ore particles tend to be rejected in their order of increasing magnetite content, while the retained portion or magnetic concentrate increases in grade continuously during the process. MAGNETIC SEPARATION CHARACTERISTIC The magnetic separation characteristic or MSC of a magnetite ore is the correlation between concentrate

Jan 1, 1964

By Edward B. Hughes, Frank G. Norris

OXIDATION is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the most recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a, compound such as C02-or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct, method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is introduced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steelmaking," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath. A recent article12 reviewing the current

Jan 1, 1948

By Homer N. Mead

This report develops equations for decline curve analysis based upon the premise that the rate of change of the reciprocal of decline for succeeding time intervals is constant when the reservoir is produced under a fixed set of conditions. A method is shown for predicting maximum production rate against cumulative production for any reservoir. A method is also presented for predicting future production rate by an analysis of past production performance after decline has been esrahlished. INTRODUCTION No significant contribution to the analysis of decline curves by the loss-ratio method has been made since J. J. Arps paper1. The concept of loss-ratio that was developed by Arps and his contemporaries has been redefined in another way and the concept of instantaneous loss-ratio at time zero has been added. In the mathematical developmerit by Arps, production rate was related as a continuous function with time and his equatlons were developed on that basis. In this paper, production is considered to be a series of segments for equal time intervals and equations have been developed based upon these finite differences. It is realized that decline curve analysis is not the answer to all predictions of reservoir behavior. However, as production must decline from an initial maximum rate to zero in any reservoir, if such decline can be expressed as an infinite series, this series should accurately predict production. Decline curve analysis should be considered a valuable tool that may be used in conjunction with predictions of future recoveries by other methods. Various uses of the decline curve method will be discussed in this paper. Equations predicting production rate at any time and cumulative production by exponential and hyperbolic decline will be developed. Characteristic values of b related to various types of drive will be discussed. After that a hypothetical reservoir will be studied and ultimate recovery by natural depletion and pressure maintenance compared, then actual field examples will be shown and discussed. The rate-cumulative curve introduced by H. N. Marshs in 1928 is an important one for use in estimating future production rate and ultimate recovery. This graphical method is the one that is used in conjunction with the equations to be developed for predicting production behavior. EXPONENTIAL DECLINE In exponential decline each succeeding production rate per unit of time is a constant percentage of the production rate just before it. Since (1 — r) is the common ratio, where r is the constant decline rate, this condition may be expressed as a geometrical progression; thus Pn = P (1 - r)n-1 . ......(1) Where r is less than unity, r Since P1 (1 - r)n = Pn+1 P1 - Pn+1 C =P1-Pn+1/r........(2) LOSS-RATIO In this paper the calculation for loss-ratio has been changed from the method presented by Johnson and Bollens2. The first loss-ratio to be calculated is a,; it is the initial production per unit of time after decline has set in divided by the difference between the initial and the second production rate. This loss-ratio is for the first time interval. After b (which is the constant change

Jan 1, 1957

By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By P. E. Fitzgerald, Dana G. Hefley

An apparatus has been developed which permits selective acidizing of producing formations and determination of the relative permeability of a formation by fluid injection. This apparatus, known as the "Electric Pilot," is an electrical fluid-interface locator, the electrical circuit of which is completed when the elec-tcodes in the well are in contact with a conductive fluid, but is not completed when immersed in a nonconductive fluid. Results are given for a number of typical acidizing applications in which the interface locator was used to control the acid. Description of the method used in making a permeability survey and the data obtained are also included. Introduction Early in the development of the acidizing industry it was recognized that one of the most important problems to be solved in the chemical treatment of any well was the determination of what part of the exposed section in the well should be treated and the selection of the technique that would insure treatment of the desired section. One of the first techniques adopted for assisting in proper placement of the acid, which is still widely used, is the method of confining the acid to the producing section by means of a column of oil, which is known as the Carr1 method of treatment, named for its inventor. In the Carr method it is not possible to selectively acidize a specific horizon in a multiple pay zone, so many improvements and modifications of the basic Carr technique were devised to accomplish this result. In order to overcome the possibility of the acid entering an undesirable section at the bottom of the well, organic gel plugs2 were introduced into the bottom of the well, which served to halt the entrance of the treating solution into these zones.3 These chemical gels later liquefied because of bacterial action and were removed from the well with the produced fluid. In fields where a gas cap existed, as in the Goldsmith field of Ector County, Texas) it was imperative that a treating technique be evolved that would confine the acid to the oil-producing zone below the gas cap. By so doing the oil-productive capacity of the wells could be improved without greatly increasing the gas production and this would lower the gas-oil ratio of the well. ~h, technique employed4 to achieve this effect utilized two pumps, one for pumping the chemicals down the tubing, the other to simultaneously force oil down the annular space to confine the acid to the oil pay, thus preventing the chemicals from entering the upper gas-bearing zones. Experience has indicated that gas wells and certain types of oil wells respond better to ''stage treating.'' This technique utilizes the introduction of a certain volume of acid and then allows the well to ''clean up99 before introduction of the next and usually successively larger stages. Where such methods are employed steps must be taken to keep a disproportionate share of the acid from entering the most permeable and previously treated Zones. A special tool

Jan 1, 1944

By N. E. Grosvenor

Several methods have been proposed for determining the tensile strength of rock. These have been tried out over the past several years, but the results have been erratic and of doubtful value. The tensile strength of rock is its weakest property, and this property apparently enters into all failure phenomena, whether underground or on the slope of an open pit. Therefore, it is essential that detailed quantitative information is known about the tensile strength of rock if the design engineer is going to select the proper pit slope, pit orientation, or orientation of underground workings so as to give the most economical and safest mining condition. This quantitative information may be used to orient the pit in such a manner as to allow steep slopes along two sides. This information possibly may be used to orient the direction of either underground workings or open pits so as to decrease powder consumption and to increase blasting efficiency. Hence it is of prime importance that a method of determining accurately the tensile strength of rocks be developed. The U. S. Bureau of Mines states' that no standard methods have been proposed by the ASTM for testing the tensile strength of rock. The method described in the Bureau publication is said by them to be unsatisfactory. A similar test that has been used in our laboratory in place of the USBM test is shown in Figs. 1 and 2. h this test the core is placed in a set of grips that has been designed for one particular size core. The grips are designed to distribute the stress around the core if they are tightened correctly. A universal joint or a flexible cable may be used in conjunction with the apparatus to prevent bending or twisting of the specimen. The main difficulty encountered with the system shown is the failure of the specimen within the grips. The possible cause of the failure within the grips may be due to a stress concentration set up by the uneven tightening of the grips. This method can be used only for tests on cores, and even then has been found to be totally unsatisfactory because of the failure within the grips. The U. S. Bureau of Reclamation has been using a test similar to the sketch shown in Fig. 3. Sulfur is cast around each end of the specimen to form a bearing surface and then a ring grip is used to apply a tensile stress. The grips are in contact with the sulfur cast and do not touch the specimen. This method is unsatisfactory, apparently because a large number of the specimens appear to break within the sulfur cast. Professor Wuerker of the University of Illinois uses the test shown in Fig. 4.' Professor Wuerker states2 that this method has given definite and reproducible results with the weakest as well as with the strongest rocks. The test is a supplement in all cases where cores cannot be obtained. The principle and equipment are the same as for the test for tensile strength of hydraulic-cement mortar. Soft

Jan 1, 1961

By Joseph L. Gillson

Bentonite, designating a distinct type of clay, is a young name in mineral nomenclature in the light of the age-old names of most other useful nonmetallics. The earliest references in literature are to "soap clay" (1873) "taylorite" (1888) and finally "bentonite" in 1897, from its occurrence in the Fort Benton series of rocks near Rock Creek, Albany County, Wyoming. Bentonite is a rock term and consists largely of montmorillonite clay. The latter name was proposed in 1847 for a plastic clay found at Montmorillon, France. A clay of apparently identical properties was described by Cronstedt of Sweden in 1788 and a number of other similar clays found in France were given other names in publications from 1853 to 1856. The mineral name montmorillonite was recognized by Dana in 1892. The recognition of "clay mineral" distinctions which led to the present-day classifications of clays by their chief mineral content, dawned in the early part of the twentieth century. Grim6 has aptly said: About 1924, Ross10 and some colleagues of the U. S. Geological Survey began a study of the mineral composition of clays that led to a series of monumental papers on the subject. By the early 1930's what has come to be known as the clay-mineral concept became firmly established in the minds of a great many people actively studying clay materials. The clay mineral concept designates the major clays as kaolins, montmorillonites and illites and by this concept bentonites are now defined as "fine-grained clays containing not less than 85 pct montmorillonite" and a wide variety of clays found all over the world are included in that classification. They could all properly be called "montmorillonite clays" but the common commercial name is bentonite. For a period of over forty years from the time of the earlier discoveries, bentonite was thought to be only the sodium type highswelling clay produced principally in Wyoming. By the clay mineral concept, non-swelling montmorillonite clays also became known as bentonite. In the trade there are two broad divisions-sodium bentonite, often called Wyoming or "western," which expands in water and carries sodium as its predominant exchangeable ion, and calcium bentonite often called "southern," which has negligible swelling and carries calcium as its principal exchangeable ion. There are many intermediate gradations. Properties The mineralogy and chemistry of the clays are so complex that the subject cannot be summarized briefly. The reader is referred to Chapter 12 of this volume in which the subject is treated at some length. Grim6 gave the formula for montmorillonite as (OH)4Si8AL4020.nH2O. He wrote: Montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. . . . Exchangeable rations occur between the silicate layers. . . . The words "tetrahedral" and "octahedral" refer to the coordination number of the cations in the unit cell in the crystallographic lattice. Carroll5a stated: That the montmorillonite structure is the same as that of mica, but the layers are not held together by K+ ions; and water and other polar molecules, such as organic molecules, can enter between the unit layers and cause expansion. Ex-

Jan 1, 1960

By N. Mungan

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

Jan 1, 1965