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By H. Leslie Bullock

From aluminum to zirconium, the quantitative preponderance of quartz as a gangue material is well recognized. lf this material is to be efficiently removed, its variations must be understood. Variations with temperature are especially important. Too little attention has been given to the thermal polarization of quartz. Under closely controlled conditions, electrostatic upgrading is very reliable. For efficient separation, contact charges must be fostered and charges due to radiation, surface coatings, or thermal polarization avoided. This paper lists thermal transition points of quartz and shows their effect on actual separations. Simple separation tests with all factors except temperature held constant are recommended for determining transition points. With silica making up more than 27% of the earth's crust, its oxides comprising more than 59% of all igneous rocks, and quartz accounting for most of the main free oxides, the mining engineer is in constant contact with quartz, which may occur as a valuable mineral to be purified or, far more frequently, as a gangue material to be removed as completely and economically as possible. As a means of effecting such purification or removal, dry beneficiation is becoming more and more desirable owing to local water scarcities, wet waste disposal problems, or freezing conditions. One method that has been gaining particularly rapid acceptance is electrostatic beneficiation, or the separation of dry free-flowing materials by means of opposite surface charges, differences in potential, or differences in conductivity. Electrostatic beneficiation dates back to the 1870's, but only in recent years have newly developed methods and apparatus and a growing knowledge of solid-state physics widened the field for its economical application. Because the term "electrostatic beneficiation" has been rather loosely used in the literature, it has come to include both electrostatic and electrodynamic procedures. Attracting type separators, however, in which oper- ation is based on differences of surface charge or potential, are truly electrostatic, because the separation occurs in a substantially static field set up between oppositely charged surfaces. Separations with this type of equipment may occur at potentials as low as 1000 v and seldom require potentials as high as 30,000 v. In the new contact charge dielectric separators1 the variation in charge is produced by continuous contact and separation of the particles in the moving feed stream and these charges are fostered by the use of non-conducting support and feed surfaces and by handling the feed in the form of streams of appreciable depth. This favors uniformity of feed and allows higher production rates. The distinctive surface charge differences are set up on the separation of the particles according to Coehn's Law,2 which states that equal and opposite charges are generated on the separation of any two materials in contact and that the substance having the highest dielectric constant will be positively charged. The basic contact charge concept is reliable, but all electrical charges are transient and modified by the electrical conditions of the surroundings. Pyro-electric, photoelectric and radiant effects may modify or totally destroy the contact charges necessary for efficient separation, or contact with conducting surfaces may neutralize them. Such hostile conditions must be carefully guarded against, since they have led to many costly failures in the past. The most consistent difference in surface charges to insure good separation is produced by repeated uniform contact and separation of particles in the moving stream. The thickness of the feed stream possible with this method reduces the effect of contact with the supporting surfaces, but as some contact is inevitable, the best results may be assured by having the dielectric constants of the supporting surfaces between the dielectric constants of the substances to be separated. In general, the hard smooth surface of quartz makes it an ideal substance for electrostatic separation from most minerals. For instance, with calcite, starting with a feed containing 1.9% acid insolubles, one can produce a concentrate containing 0.30% acid insolubles with a tailings containing 21.7% acid insolubles and a yield of 92.8%. The color can be held at 92 or above and the tint at 1.7 or lower. Working with specularite iron ore, laboratory work has given a concentrate of 68.8% Fe., with an iron unit recovery of 96.7%. Excellent results are also in pros-

Jan 1, 1969

By PAUL AUDIBERT

THE downward trend of metal prices seems to act something like a reagent that precipitates selfishness in most business men's hearts; in the same way the upward trend precipitates altruism. Operators do not say: "I continue working my mine without curtailment because I can afford the present prices while my neighbor cannot and thus will give me way." They say: "I continue working my mine because 1 consider it a service for consumers. They will get better prices on a free market. Any curtail¬ment would be an attempt to raise prices artificially, that is to say, bad economics." Copper producers have learned how fallacious is such an opinion. It perhaps was not fallacious in olden times when all mines were worked on a small scale even if operating on a big deposit. At that time the supply and demand law played fair. When prices were too low and profits were vanishing for many mines, they would. shut at once, then little by little the metal scarcity would induce prices to climb up again; finally these prices would reach the point when it became profitable to again work the closed mines. Re-opening and shutting down mines was then a normal custom. Workers and operators weakly deplored this unstability, but there was nothing effective they could, do about it.

Jan 1, 1931

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By T. E. Leontis

The specific effect of various rare-earth metals on the room- and elevated-temperature properties of magnesium has been evaluated. Alloys containing didymium exhibit the highest tensile and compressive strengths at room and elevated temperatures. All the rare-earth metals increase the creep resistance of extruded magnesium at temperatures in the range of 400° to 600°F, but the degree of enhancement depends on the temperature and on the concentration of the added metal. THE effects of rare-earth metals on the properties of sand-cast magnesium were discussed in some detail in earlier paper by the author.' The present paper deals with the effect of the same alloying elements on the properties of extruded magnesium. This investigation also had as its aim the development of a wrought alloy having a better combination of room-temperature strength and ductility and elevated-temperature strength and creep resistance than is found in magnesium-Mischmetal-manganese alloys, which have been reported earlier.2-5 The only known attempt to study wrought magnesium alloys containing pure cerium instead of Mischmetal was made by Mellor and Ridley.6 They found that in the form of rolled bars there is a definite, optimum cerium content for creep resistance at 200 °C and that the creep resistance of these alloys at 200 °C is significantly Improved by heat treatment at 550" to 580"C. In the present investigation the compositional variation in mechanical properties of the following alloy systems is presented: I—magnesium-Misch-metal. 2—magnesium-cerium-free Mischmetal. 3— magnesium-didymium. 4—magnesium-cerium. 5— magnesium-lanthanum. Alloys containing predominately praseodymium are not included in this series because of the lack of this material. Experimental Procedures The alloying ingredients used in preparing the alloys described herein are the same as those reported in the earlier paper.' Cerium-free Mischmetal is the rare-earth mixture remaining when the cerium is removed from Mischmetal, which contains all the rare-earth metals as they occur naturally in mon-azite sand, the ore from which Mischmetal is produced. Removal of both cerium and lanthanum from Mischmetal leaves what is commonly called "didym-ium," consisting predominantly of neodymium and praseodymium. Although the composition of the particular batch of each metal used may differ somewhat from the analysis presented previously, these differences are not great enough to warrant repeat- ing the specific composition of each material. The electrolytic magnesium used as the starting material in these alloys has the same typical analysis as that given in the earlier paper.' The alloys were prepared in small laboratory melts applying all the necessary precautions for alloying rare-earth metals with magnesium described by Marande.' Most melts were large enough to cast one 3 in. diam billet 10 in. long. In a few cases, particularly the didymium-containing alloys, the lack of sufficient amounts of the rare-earth metal limited the size of the billet to 6 to 8 in. All billets were scalped to a diameter of 2 15/16 in. and faced to a length of 9 ¼ in. as limited by the size of the extrusion container. The alloys were extruded into ½ in. diam rod on a 500-ton direct-extrusion press using a 3 in. container. The details of the extrusion step are: billet preheat, 925°F (2 hr); container temperature, 900°F; die temperature, 900°F; extrusion speed, 10 ft per min; reduction ratio, 36:1; and percent reduction, 97.3. The lower melting point of alloys containing didymium' necessitated reduction of the extrusion speed to 5 ft per min in order to prevent hot shorting during extrusion. Adequate lengths were cropped from both ends of each extruded rod to assure that all the material used for tests was extruded under uniform conditions. Tensile and compressive properties at room temperature are reported in the several conditions of heat treatment. The ASTM designations are used to distinguish these conditions as follows: T5—Direct age at 400°F (16 hr) T4—Heat treat at 950°F (4 hr) for alloys containing didymium T4—Heat treat at 1050°F (4 hr) for all other alloys T6—T4 + age at 400 °F (16 hr) The lower heat-treating temperature for alloys containing didymium is necessitated by the lower melting point of these alloys. All heat treatments were conducted in electrically heated, circulating-air furnaces. A protective atmosphere containing 0.5 to 1.0 pct sulphur dioxide was used for the high temperature heat treatments. Tension and creep specimens 6 Yz in. long and compression specimens 1½ in. long were cut from the extruded rod. A reduced section of ? in. diam was machined on the tension specimens, whereas on the creep specimens a reduced section of 0.450 in. diam

Jan 1, 1952

By H. Y. Jennings

An extensive field and laboratory experimental program was carried out to compare the waterflood behavior of carefully preserved soft and unconsolidated cores with measurements on the same cores after extraction. Results obtained from using idealized consolidated and unconsolidated porous media in which wettability could be carefully controlled were contrasted with the preserved core data. The controlled tests on idealized porous media investigated the effect of wettability, flood rate, core length, core permeability and consolidation on the displacement of high viscosity oils. It was concluded from these studies that waterfloods are more favorable when carried out with crude oil in preserved soft and unconsolidated cores than with the same cores after they have been extracted and re-saturated. Waterfloods are usually more favorable when carried out with crude oil in extracted .soft and unconsolidated cores than with refined oil of the .same viscosity in the same cores. The less favorable behavior of extracted soft and unconsolidated cores compared to preserved cores is due to alteration of the core by extraction. Preserved cores saturated with native water and oil should be used for laboratory displacement experiments because they more accurately reflect true reservoir behavior INTRODUCTION The demand for low gravity crude oil created by refinery modernization has focused attention on increasing the production of this viscous crude oil. Billions of barrels are in place in fields that are depleted, or nearly depleted, by primary production mechanisms. Since low gravity reservoirs are relatively recent, geologically, the solid matrix material is usually soft and unconsolidated sand. Such formations are also characterized by a high clay content. Evaluation of sophisticated oil recovery processes with the associated high capital investments has increased the demand for special core analysis tests on material from these soft and unconsolidated sand reservoirs. Data in this paper have resulted from an extensive field and laboratory experimental program. The initial objective vras to provide soft and unconsolidated sand cores for laboratory measurements with as little alteration as possible from their reservoir condition. A secondary objective was to compare the waterflood behavior of these carefully preserved cores with measurements on the same cores after they had been extracted and resaturated. When the comparison showed markedly different behavior the final objective was to attempt to explain the difference by making measurements on idealized porous media free of clay in which initial wettability could be carefully controlled. EXPERIMENTS MATERIALS Core Material The preserved cores used in this study were obtained with as little alteration as possible from their reservoir conditions. Special techniques were developed to satisfy this objective. The cores were cut with native crude whenever the crude had the necessary properties to satisfy the minimum drilling fluid requirements. A pure hydrocarbon chromatographic tracer was added to the crude to provide a simple, safe and inexpensive method to distinguish between oil filtrate and formation oil. Details of the tracer technique used in this study and the procedures used to handle and process the soft, unconsolidated cores have been published.' The core samples were then preserved and packaged at the well site with a dip-applied strippable plastic, or by using a rubber sleeve from a rubber-sleeve core barrel. The final step was to insure that the carefully taken and preserved samples were not altered by processing in the laboratory. Some soft and poorly consolidated sands were carefully shaped in the lab and encased in a protective mounting without disturbing their three-dimensional integrity. Many samples were so poorly consolidated that they literally flowed from the package when the seal was broken. A technique was developed to obtain cylindrical plugs from these samples by using liquid nitrogen as the drilling fluid in a conventional core-drill, drill-press assembly. The idealized porous media consisted of sintered rods of Alundum RA 139, outcrop sandstone identified as Al-hambra sandstone and packs of No. 130 Nevada sand. This sand is 95 per cent 140-200 mesh. (Physical properties of these porous media with those representative of preserved cores are in Table 1.) The natural cores and most of the idealized porous media were 1 1/2-in. in diameter and 3-in. long. The samples used to study the effect of core length were 1 1/2-in. in diameter and 12-in. long. Liquids Water and oil produced from the formations being studied were protected from the atmosphere and collected in carefully cleaned glass or plastic-lined containers. The production was free of chemical additives such as emulsion breakers and corrosion inhibitors. The crude oil was

Jan 1, 1967

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By E. V. Potter

For a nurnber of years, it has been known that manganese made by electro-deposition under certain conditions is ductile while under other conditions it is very brittle. The ductile metal is gamma manganese normally stable only between 1100 and 1138°C1; the brittle metal is alpha manganese, stable up to 727OC. The ductile metal is not stable, but gradually changes to the brittle form; the time required to complete the transfornlation is about 20 days at room temperature. Other observations have indicated that the transformation is completed in 10 to 15 min. at about 125°C, while at — 10°C, no appreciable change occurs in 9 months. The properties of gainma and alpha Illanganese in the pure state are ordinarilj difficult to determine because the gamma structure cannot be retained by normal quenching procedures and alpha manganese is so brittle, it is difficult to obtain specimens free from flaws. In a recent investigation2 some properties of gamma and alpha manganese were determined by studying the ductile electrolytic metal and determining the changes in its properties as it transformed to the brittle alpha form. These investigations provided an excellent opportunity for following the progress of the transition and studying its mechanism. The results of a series of such investigations are reported in this paper. Procedure Various properties of manganese were determined starting with the metal in the original ductile gamma form and following the subsequent changes in its properties as the metal transformed to the brittle alpha form. These observations were made at various temperatures, the data providing information regartling the mechanism of the transformation as well as the effect of temperature 011 the transition rate. Structure and resistivity values gave the most significant results, so this paper is concerned primarily with them. The structure was studied microscopically as well as by X ray diffraction. The resistivity was determined on strips of the metal by measuring the potential drop across a given length of the specimen. Current was passed through the specimen by wires soldered to its ends, and the potential connections were made by wires looped around the specimen near its center. The current was determined by the potential drop across a standard resistor connected in series with the specimen, the potential drop being measured on a potentiometer. In the temperature range from room temperature to 100°C an ordinary drying oven was used to heat the specimen. This was entirely satisfactory except at 100°C, where the time required to heat the specimen was long compared to the transition time, making the initial section of the resistivity curve unsatisfactory. To overcome this limitation, at 100°C and higher a thermostatically controlled oil bath was used to heat the specimens. The block on which the specimen was mountetl was plunged into the hot oil at the start of each test. The heating time was thereby reduced from 5 min. to about 6 sec, and dependable resistivity values could be obtained through 160°C. At this point the whole transition, including the warm-up time for the specimen, required only about 20 sec and it was not considered worth while trying to extend the temperature range further. Aside from the heating problem, the problem of making a sufficient number of accurate resistivity determinations became more and more difficult as the temperature was raised. Using the manually operated potentiometer, 100°C was about as far as it was possible to go. At this temperature and above, a self-balancing photoelectric recording potentiometer was used. Its response was quite rapid, and it proved to be entirely satisfactory all the way through 160°C, where the tests were stopped because of the specimen heating problem rather than any limitation of the potentiometer recorder. The metal used in these tests was prepared at the Salt Lake City laboratory of the Bureau of Mines. The method of preparation is discussed in a paper by Schlain and Prater.3 The sheets were about 2 3/8 by 5 3/16 in. and varied from 10 to 16 mils in thickness. They could be cut readily into pieces suitable for the various tests. X ray and microstructure determinations were made on pieces about 1/8 to 1/4 in. wide and about 1 in. long, while resistivity measurements were made on strips as long as possible and about 55 in. wide. The thickness of each sheet was not uniform over all its surface. This had no bearing on the X ray and microstructure determinations, but sections as nearly uniform and free from flaws as possible were chosen for the resistivity determinations. The gamma manganese was electro-deposited at 30°C, the time of deposition ranging from 5 to 12 hr for each sheet. Whenever possible, the tests were started directly after the metal was stripped from the cathode; otherwise the sheet was placed immediately

Jan 1, 1950

By R. G. Aspden

The cold rolling and annealing textures were studied for 3 pct Si-Fe grains initially (001) [hkl]. A concentration of (001) [loo] primaries were observed only in the annealing textures of crystals initially having [loo] within 8 deg of the rolling direction. Eke annealing textures of the (001) [I101 cold rolling textures were sensitive to the initial orientation of the grains. Single crystal data were used to explain the formation of (001) [loo] in poly-crystalline malerial. CUBE texture formation in 3 pet Si-Fe sheet occurs during the final high temperature anneal. Its formation is dependent on the proper distribution of (001) plane primaries with reference to the rolling direction&apos; and on the growth of these primaries by secondary recrystallization. The selective driving force for these primaries with (001) within 7 deg of rolling plane is derived from the difference in surface energy between the annealing atmosphere and the crystallographic planes exposed at the surface of the sheet.&apos;-= The alignment of [loo] directions of (001) secondaries with the rolling direction is required for optimum magnetic characteristics7 and is dependent on processing.&apos; A high degree of alignment has been observed when the final cold rolled texture has a strong (111) [ll2] type component3 and the normal grain growth texture prior to secondary recrystallization has components with a [loo] parallel to the rolling direction and planes from (001) to (110) parallel to the rolling plane.1,3,8,9 Generally, this (001) component is much weaker than the (110) component. The growth rate of (001) plane primaries to secondaries has been found to be independent of the orientation of the primaries with reference to the rolling direction, i.e., the secondaries have the same degree of alignment of [loo] directions with the rolling direction as the (001) primaries.&apos; Hence, the rolling and annealing textures of individual grains or single crystals are of interest in understanding the development of the (001) [loo] secondary recrystallization texture. (001) components have been observed in the annealing textures of cold rolled grains initially having a [loo] parallel to the rolling direction and an (001) rotated up to 30 deg from the rolling plane. Crystals initially near the (001) [loo] orientation when rolled under the influence of constraints imposed by neighboring grains form deformation bands and ro- tate in both directions toward (001) <110>.10,11 Deformation bands have been reported also for crystals initially with an (001) within 1 deg of the rolling plane and a [loo] within 1 deg of the rolling direction when rolled as a free single crystal.12 These crystals have weak recrystallization textures and contain near an (001) [loo] component.10-12 When near (001) [loo] crystals are rolled as free single crystals no deformation bands form and the crystals rotate by a single rotation toward (001) [110]. Recrystallization after a 70 pct cold reduction yielded near an (001) [loo] component13 and after a 90 pct cold reduction an (001) [I201 component." Crystals initially near (210) [001] had a texture after a reduction of 70 and 84 pct which was similar to the (111) [li2] but rotated 10 to 15 deg in the transverse direction. These crystals recrystallize to (210) [OOl] or (410) [001] and contain an (001) [loo] component.10,13 An (001) component has not been detected in the normal grain growth textures of other single crystals. Crystals initially having orientations between (110) [001] and (111) [ll2] have a cold rolled texture of principally (111) [ll2] .10>16 Other crystals with a [I101 parallel to the cross direction rotate to (111) [112] and/or (001) [110] stable end orientations. Crystals initially having from (001) [110] to (111) [lie] retain this orientation after cold rolling.15 The cold rolled textures having [I101 directions parallel to the rolling direction had components in the annealing textures related to the deformation textures by 25 to 30 deg rotations about common (1 10) poles. Cold rolled textures of the (111) (112) type recrys-tallized to (120) [001] or (110) [00l]. The purpose of the present work was to further the understanding of the alignment of [loo] directions of (001) secondaries with the rolling direction. The cold rolling and annealing textures of grains initially (001) [hkl] were studied. These data were applied to the formation of (001) [loo] by secondary recrystallization. PROCEDURES AND EXPERIMENTAL TECHNIQUES The (001) poles near the sheet normal and rolling direction are given in Fig. 1 for the 10 grains studied. Each of these grains was located in the center of a polycrystalline specimen approximately 25 mm wide and 50 mm long. The lower case lettered grains, a through dl were about 1.2 mm in diam and near the (001) [loo] orientation. Specimens containing these grains were from a commercial 3 pct Si-Fe alloy with the principle orientation of (110) [001] as obtained by impurity inhibition of growth with manganese sulfide inclusions.17,18 Upper case lettered grains, A through F, were about 6 mm in diam and had (001) planes near the rolling plane and [hkl] di-

Jan 1, 1963

By P. G. Shewmon, F. N. Rhines

THE determination of the self-diffusion coefficient of magnesium has been made possible recently by discovery1-1 of a radioactive isotope, Mg28 having a half-life of 21.3 hr,1 and subject to manufacture in useful quantity. In the present research this material was condensed from the vapor phase upon a surface of high purity magnesium. The progress of diffusion of the tracer atoms into polycrystalline magnesium was followed by machining layers and measuring the change in the intensity of radiation as a function of the distance of each layer from the surface. The self-diffusion coefficient was found to be 2.1 X 10-8 sq cm per sec at 627°C, 3.6 X 10-9 sq cm per sec at 551°C, and 4.4 X 10-10sq cm per sec at 468°C; the activation energy is about 32,000 cal per mol. Experimental Procedure Since there was no other published measurement of a diffusion velocity in any magnesium-base material, is was necessary to employ a number of new experimental techniques. The short half-life of Mg28 made it necessary to complete the entire experimental procedure within three or four days. This meant that the work had to be done where a cyclotron was readily accessible and that all operations, prior to the diffusion heat treatment, had to be so designed as to minimize their time requirements. Unusual problems were imposed also by the chemical reactivity of magnesium, its high vapor pressure, and the fact that no satisfactory method for elec-trodepositing magnesium on magnesium is presently available. Finally, the machining and handling of the easily air-borne radioactive-magnesium chips involved certain health hazards, resulting in the need for further experimental restrictions. Preparation of Mg28 The Mg28 was produced in the Carnegie Institute of Technology syncrocyclotron by the neutron spallation of chlorine.5 his involved bombarding a 2 gram crystal of high purity NaCl with a beam of 350 mev protons for a period of 2 hr, after which the crystal was dissolved in warm water and the Mg28 was concentrated and purified by chemical means (see Appendix). About 50 microcuries of Mg28 thus were obtained in the form of magnesium oxinate (8 hydroxyquin-olatc?), which was ignited in air to produce MgO. This in turn was reduced to magnesium metal vapor, by the method of Russell, Taylor, and Cooper," in the vacuum apparatus shown schematically in Fig. 1. Here the essential part is a tantalum ribbon, slightly dished to receive the MgO. The ribbon, pre- viously outgassed at high temperature, is heated to about 1700°C by passing an electric current through it, whereupon tantalum oxide is formed, magnesium vapor is released almost instantaneously, and condensed partly upon the diffusion sample. Diffusion-Sample Preparation: Hot-extruded magnesium rod, 21/32 in. round was used in making the diffusion specimens. The magnesium analyzed as follows: 0.004 pct Al, 0.027 pct Fe, 0.040 pct Mn, 0.0004 pct Cu, 0.0002 pct Ni, and less than 0.01 pct Ca, 0.0004 pct Pb, 0.0011 pct Si, 0.001 pct Sn, and 0.001 pct Zn. A brief study of the crystal texture of this material revealed a sharp fiber texture with the (001) plane roughly parallel to the extrusion axis. Cylindrical samples 1/2 in. long by 5/8 in. were machined from this rod, the end faces dressed on 3/0 emery, and lightly etched with 20 pct HC1 in water. These samples then were annealed for at least twice the intended time of diffusion, at the intended diffusion temperature, in order to stabilize the grain structure at about 1 mm average diameter. The annealing treatments were conducted in argon in the same apparatus and in the same manner as the subsequent diffusion treatments, which will be described presently. Thus, a strain-free plane surface was produced, but there remained a layer of MgO which had largely to be removed before the layer of Mg28 was deposited. Most of this layer was taken off by two light passes over 3/0 emery paper. The balance of the oxide and a thin layer of metal were then removed by etching 5 to 10 min in 4 pct nital (4 pct HNO3 and 96 pct ethyl alcohol) made with absolute alcohol. There followed immediately three quick rinses in: 1-49 1/2 pct methanol, 49 1/2 pct acetone, and 1 pct formic acid, 2-50 pct methanol and 50 pct acetone, and 3-pure benzene. This procedure is essentially that of Sturkey.7 The resulting surface, which was of almost elec-tropolished brightness, remained plane and was free of cold work. It could be kept clean by storing under benzene, or in a desiccator; short exposure

Jan 1, 1955

By Carrol M. Beeson

Reasons are given for using a Boyle&apos;s-law porosimeter in conducting core analysis for either routine or research purposes. Among other things, it is pointed out that such a porosimeter permits the measurement of all basic properties on the same sample, thereby eliminating the sources of error inherent in the use of adjacent samples. References are made to investigations of gas adsorption on various porous materials, to show that the use of helium in Boyle&apos;s-law porosimeters reduces to negligible proportions the error due to the adsorption or desorption of the operating gas. Two Boyle&apos;s-law instruments are described. which permit accurate and rapid measurements of porosity. Schematic sketches and explanation:; are included, along with derivations of equations required in performing precise determinations. Summaries of data obtained during calibration are tabulated and analyses of the data are resented as indications of the precision and accuracy of each device. Comparisons are also shown for measurements made with each of the instruments on the same test pieces and cores. INTRODUCTION An accurate porosimeter, operating on the principle of Boyle&apos;s law. is of considerable value in the analysis of cores for either routine or research purposes. This is due primarily to the fact that the measurement of porosity with such an instrument leaves the sample free of contamination by any liquid. When used in conjunction with an extraction apparatus&apos; for determining oil and water saturations, a Boyle&apos;s-law porosimeter permits the measurement of all basic properties on the same sample. This eliminates the sources of error inherent in the use of adjacent samples, or the necessity of determining porosity after all other properties have been obtained. Large errors may result from combining measurements made on adjacent samples in order to obtain a single property. This type of error is definitely involved when oil and water are measured with one sample, and the pore vo1ume is measured with an adjacent one. Furthermore, the source of error would be present to some extent, even if the analyst could choose the samples so they were truly adjacent from a geological standpoint. The use of adjacent samples in routine core analysis also necessarily decreases the probability of correlating core properties. For example, the chance of correlating the "irreducible" interstitial-water saturation with permeability, is bound to be greatly reduced by measuring these properties on "adjacent" samples. For research purposes, amplification is scarcely required concerning the greater flexibility of a method for measuring porosity which leaves the core free of contamination by any liquid. Even under those circumstances which require that the core be saturated with a liquid, a previous measurement of porosity with a gas is useful in determining the degree of saturation that has been attained in the process. Furthermore, for comparable accuracy, porosity usually may be determined more rapidly with a gas than with a liquid. This advantage of the Boyle&apos;s-law instrument is most outstanding when the determination time is compared with that required in obtaining porosity by evacuation of the core followed by saturation with a liquid of known density. Several porosimeters which operate on the principle of Boyle&apos;s law have been described2,3,4,5,6,7 in the literature. No comparison will be attempted between those instruments and the ones described herein. Before helium gas became readily available, Boyle&apos;s-law porosimeters were subject to an appreciable error due to the adsorption of the operating gas on the surface of the core solids. There is considerable direct and indirect evidence in the literature to support the contention that the adsorption of helium on porous solids is negligible at room temperature. In discussing the use of Boyle&apos;s-law porosimeters, Washburn and Bunting2 stated that "for most ceramic bodies dry air is a satisfactory gas, but hydrogen will be required in some instances. Helium could, of course, be employed for all types of porous materials at room temperatures or above." Howard and Hulett8 obtained evidence that the adsorption of helium was negligible at room temperatures, even on activated carbon ; for the density measured with this gas was unaffected by changes in pressure or by changes in temperature from 25 °C to 75 °C. For oil-well cores, Taliaferro, Johnson, and Dewees" obtained lower porosities with helium than with air, but apparently did not study helium adsorption. From the work of these investigators, it follows that the use of helium in Boyle&apos;s-law porosimeters reduces the error due to gas adsorption to negligible proportions. This makes it possible to construct instruments which permit the determination of porosity with (1) a high degree of accuracy, (2) with great rapidity, and (3) without contamination. THE KOBE POROSIMETER The fundamental design of the Kobe Porosimeter was developed by Kobe, Inc., which firm built about 12 of the instruments during 1936 and 1937. Since that time, seven or eight more have been constructed with their permission, making a total of about 20 that have been put into operation.

Jan 1, 1950

By W. M. Robertson

The formation of grain boundary grooves on surfaces of poly crystalline samples of cobalt and iron immersed in liquid lead has been studied. The grooves form by volume diffusion of the solutes cobalt and iron in the liquid. The diffusion coefficients of the solutes in liquid lead are derived from the measured rate of grooving. The diffusion coefficients are described by the relation D = Do exp (-Q/RT), with, for cobalt, Do = 4.6 x 10-4 sq cm per sec and Q = 5300 ± 800 cal per mole, and for iron, DO = 4.9 x 10-3 sq cm per sec and Q = 10,500 ± 1500 cal per mole. LIQUID metal-solid metal interactions occur at solid-liquid interfaces. Interfacial energy provides a driving force to change the morphology of the interface. Mullins1,2 has derived expressions for the kinetics of interface morphology changes driven by capillarity. These expressions can be applied to an isothermal system of a solid in equilibrium with a liquid saturated with the solid. Surface profile changes can occur by volume diffusion of the solute in the liquid, by volume self-diffusion in the solid, and by interfacial diffusion at the liquid-solid interface. A groove will form at the intersection of a grain boundary with a solid-liquid interface, reducing the total interfacial free energy of the system. The solid-liquid interfacial energy ? must be greater than half the grain boundary energy of the solid ?6 for Mullins&apos; calculations to apply. If ? is less than ?b/2, then the liquid penetrates the boundaries, separating the grains rather than forming grooves. Boundary penetration did not occur in the work described here. where CO is the equilibrium volume concentration of the solid in the liquid, Dv the volume diffusion coefficient of the solid in the liquid, ? the interfacial free energy of the solid-liquid interface, O the atomic volume of the solid crystal, k Boltzmann&apos;s constant and T the absolute temperature. Eqs. [1] and [2 ] also apply to grooving by volume self-diffusion in the solid,1 with CoODv = D Self, where DSelf is the volume self-diffusion coefficient of the solid. For a grooving mechanism of interfacial diffusion at the solid-liquid interface, the groove width is given by2 where CS is the interfacial concentration of the diffusing species, and DS is the interfacial diffusion coefficient. Eqs. [1] and [3] can be used to determine the mechanism of groove growth. A t1/3 dependence of the growth indicates volume diffusion and t1/4 indicates interfacial diffusion. In some cases, volume diffusion and interfacial diffusion both can contribute substantially to the grooving process, causing the time dependence to be intermediate between t 1/3 and t1/4.3 For these cases, the relative contributions of the two processes can be separated.4 However, in many cases, one process will be dominant, and the data can be analyzed on the basis of Eq. [1] or Eq. [3] alone. The time dependences for volume diffusion in a liquid and volume self-diffusion in a solid are the same. However, the self-diffusion contribution of the solid is usually negligible compared to volume diffusion in the liquid. After the grooving mechanism has been determined, Eq. [1] or Eq. [3 ] yields the kinetic parameter A or B. The kinetic parameter can be used to calculate values for the unknown quantities in the product CD?. Usually C is known or can be estimated. If ? is known, then D can be calculated. In a measurement of grain boundary grooving of copper in liquid lead,&apos; the time dependence indicated volume diffusion in the liquid. The quantities Co, Dv, and ? were obtained from the literature, giving excellent agreement between the observed values of A and the values calculated from Eq. [2 ].5 In a study of the grooving of several refractory metals in liquid tin and liquid silver, A1len6 educed that grooves formed by volume diffusion in the liquid. In a study of nickel in a nickel sulfide melt, Steidel, Li, and spencer7 found volume diffusion grooving kinetics. Both Dv and ? were unknown, so they could not obtain either one separately, though they did obtain a reasonable value for the temperature dependence of the product Dv ?. Several methods have been used to obtain surface profiles. It can be done by sectioning through the interface7 or by chemically removing the liquid from the solid surface after solidification of the liquid.6 However, if the liquid dewets the solid on removing the solid from the melt, then the interface can be observed directly. This method was used previously&apos; and was utilized also in the present study. EXPERIMENTAL PROCEDURE Lead of 99.999 pct purity was obtained from American Smelting and Refining Co. Cobalt sheet was obtained from Sherritt-Gordon Mines, Ltd., with a nominal purity of 99.9 pct, the principal impurities being nickel, iron, copper, carbon, and sulfur. The sheet was

Jan 1, 1969

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe&apos; first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-&apos; have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 &apos; sec-&apos; although at lo-&apos; sec-&apos; the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations&apos;. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown&apos; * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram&apos; shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By G. L. Fisher, R. H. Geils

The effect of small amounts of columbium (<0.01 to 0.10 pct) on the ?-a transformation occurring during the continuous cooling of a low carbon Ni-Cu steel was investigated. Dilatometer specimens were aus-tenitized at 950" and 1068?C and cooled at 17? and 375 C° per min. Columbium caused a marked depression in the ?-a transformation temperature except when cooling at the slower rate from 950°C. The effec of columbium on the transformation temperature was greater the higher the austenitizing temperature and rate of cooling. A maximum depression of 92 C" was observed. Metallographic examination of specimens of <0.01 and 0.07pct Cb steels heated at 1200°C for 1 hr and cooled at various rates showed that columbium had a major effect on the ferrite morphology. The fer rite in the columbium -free steel remained equiaxed at cooling rates as high as 440 C? per min while the columbium-bearing steel exhibited mixed structures o equiaxed and bainitic ferrite at cooling rates as low as 130 C° per min. The ? grain boundaries in the columbium -free steel provided the ferrite nucleation sites in rapidly cooled specimens. There was a complete absence of nucleation at these sites in the colum bium-bearing steel. It is concluded that columbium depresses the transformation temperature by suppressing ferrite nucleation at the austenite grain bound-aries. In this respect the effects of columbium are analogous to those of boron in low C-Mo steels. It is well known that small columbium additions can substantially strengthen plain carbon steels. As little as 0.02 pct Cb can increase the yield strength of mild steels by 10,000 psi.1 A fine precipitate of CbC has been observed in columbium-bearing steels2 and is generally thought to be responsible for the strengthening. Little attention has been devoted to the effect of columbium on the ?-a transformation. Webster and woodhead3 have studied the effect of columbium on the isothermal proeutectoid ferrite reaction in mild steels. They found similar transformation behavior in steels both with and without columbium additions. However, as the austenitizing temperature increased, the incubation time for the start of the ferrite transformation became longer in the columbium-containing steel. Morrison1 found that the addition of 0.03 pct Cb to a C-Mn steel lowered the transformation temperature by 50 C° during cooling from 1200°C at a rate of 80 C" per min. The strengthening effect of columbium has recently been utilized in an age-hardenable, low-alloy steel containing copper and nickel.4 A small amount of columbium has a substantial effect on the as-rolled strength of this steel. By increasing the columbium level from <0.01 to 0.13 pct the as-rolled yield strength is increased by 15,000 psi. Columbium also significantly lowers the ?-to-a transformation temperature of this steel during continuous cooling from the austenitizing temperature. Because of the low carbon level in this steel (0.05 pct max), it is almost entirely ferritic. Thus, it offers the opportunity of studying the effect of small columbium additions on the proeutectoid ferrite reaction. Of particular interest in this study was the reason for the marked lowering of the transformation temperature by columbium during continuous cooling. EXPERIMENTAL PROCEDURE Materials. The compositions of the steels used in this investigation are shown in Table I. The steels were 30-lb air induction melts. They were forged to 4 by 8 by 1 in. plate at 1230°C, air cooled, and then reheated to 1230°C and cross-rolled in two passes to in. plates. Dilatometry. A Leitz Bollenrath dilatometer was used to record the transformation during continuous cooling from two different austenitizing temperatures. The dilatometer specimens were + in. in diam and 2 in. long. Oxidation and decarburization of the specimens was prevented by maintaining a small positive pressure of dry argon in the dilatometer furnace and by plating the specimens with 1 mil of Cu. For the lowest cooling rate, 17 C" per min, the temperature of the specimen was measured with a Pt-Pt 10 pct Rh thermocouple placed in a & in. diam well in the center of the specimen. During air cooling, 375 C° per min, this method of measuring the temperature interfered with the operation of the dilatometer. However, it was found that the temperature of the specimen could be measured accurately by placing a thermocouple in an identical specimen in a holder adjacent to the one being used to operate the dilatometer mechanism. The dilation-temperature curves were recorded on photographic film and then converted to volume percent ferrite-vs-temper-ature curves. The cooling rates obtained with the dilatometer are shown in Table 11. Cooling rates of

Jan 1, 1970

By N. Mungan

Formation damage, i.e.. reduclion in permeability, has been generally attribuled to clay minerals which expand or disperse upon contact with water that is less saline than the connate water. Luboratory, studies show that penneahility reduction can also occur in formalions containing only nonexpandable clays such as illite or kaolinite, and can be caused also by changes in pH. Furthermore, pH changes can damage even formations that are essentially free of clays. It is suggested that permeability reduction is due to the small passages being blocked by particles, which may be dispersed clays, cemenlion material or other fine parricles. These particles are dislodged by dispersion of clays due to changes in salinity or by dissolution of calcareous cement by acids, or of silicaceous cement by alkaline solutions. In working with reservoir cores, it was found that extracted cores damaged more easily and extensively than nonextracted cores. The extent of damage depended also on tenlperatltre. INTRODUCTION Permeability is an important property of porous media and has been the subject of many studies by engineers and geologists. Many of these studies are conccrned with formation damage, i.e., reduction in permeability, resulting from exposure of oil-producing formations to water substantially less saline than the connate water. This effect causes understandable concern since during drilling, completion and production phases formations are often exposed to fresh water. The damage resulting from contact with relatively fresh water has been attributed to expansion and dispersion oF clay minerals. During laboratory investigation of the use of NaOH as a wettability reversal agent to increase oil recovery from oil-wet reservoirs, several cores used in the displacement studies suffered loss in permeability. Despite the traditional usage of NaOH for conditioning aqueous mud systems, the role of the caustic filtrate in wellbore damage seems to have been overlooked. Browning2 as recently reported on the effects of NaOH in dispersing clay minerals but he was concerned only with complications that may arise in drilling massive shale beds. The following study was made to examine the role of pH and salinity changes in core damage. Where cores from reservoirs were used, tests were performed with extracted and nonextracted cores both at room and reser- voir temperatures, since it was felt that the test environment and core condition may affect the results. Because of its limited coverage and exploratory nature, this study is not intended to provide answers to field formation damage problems. It is hoped that it will encourage research into new aspects of the permeability reduction problems, particularly those allied to new recovery and production processes. PROCEDURE In all permeability tests, fluids were pumped through the cores at a constant volumetric rate. Only deaerated fluids and reagent grade chemicals were used. The fluids were passed through two ultrafine filters before injection to remove any entrained particles. The cores, with the exception of the unconsolidated cores, were mounted in Hassler holders. Water was used to transmit pressure to the sleeve. The inlet endpiece had two entry ports which permitted scavenging one fluid with another to avoid any mixing in the small holdup volume. The cores were flushed with CO2 gas, evacuated for 5 to 6 hours and saturated with the first liquid at a pressure of 1,000 psi for 24 hours to eliminate any free gas from the cores. Pressure differences up to 20 psi were measured by transducers, calibrated in inches of water and continuously recorded. For greater pressure drops, gauges were used. All reservoir cores were cleaned with a light refined mineral oil, then with heptane, and finally dried with CO2. Compatibility tests showed that no precipitates formed when mineral oil and the crudes were mixed. Some cores were extracted in Dean-Stark-type solvent extractors using xylene and trichloroethane and dried in a vacuum oven at 450F. Each test consisted of a sequence of water, test solution, and again water flow. RESULTS AND DISCUSSION STUDIES IN BEREA CORES Salinity Contrast Berea cores 2-in. in diameter and 12-in. long were cut from sandstone quarried in Cleveland, Ohio. The clay minerals were identified by X-ray diffraction to be chlorite, kaolinite, illite and incerlayered illite. Flow of fresh water or 30,000 ppm brinc does not cause any permeability reduction (Fig. 1). However, after injection of brine the core is readily damaged by fresh water. Damage starts almost instantly as the fresh water injection is begun, and at a cumulative injection of 1.2 PV fresh water, the permeability has dropped from 190 to 0.9 md. Upon continued injection, the effluent contains clay minerals dislodged from the core. The final core per-

Jan 1, 1966

By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.&apos; The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

By Thomas C. Wilder, Walter E. Galin

Measurements of the electromotive force of the cell at 995°C have shown that the cell may be used to detennine the zinc content of molten Cu-Zn alloys to the nearest 0.05 wt pct. The cell is used for brass melts to which no ZnO is added intentionally, because essentially all oxygen in the Cu-Zn-O system is present in the form of ZnO. The cell is also used to detev,nine the thernodynamic activity of zinc for Cu-Zn al1oys of the brass composition range, from which the equilibrium partial pressure of zinc for such alloy may also be calculated. The electrochemical measurement of the concentration of the most active metal in other engneering- alloy systems by a similar technique is also considered. IN recent years there have been many studies concerning the direct electrochemical measurement of oxygen content in molten engineering metals.&apos; These investigations employ galvanic cells in which the electrolytes are various solid mixed-oxides which conduct current by movement of oxide ion vacancies under the influence of an oxygen potential gradient. Similar cells have also been used to measure the thermodynamic properties of mixing of solid alloys,&apos; one component of which has a much greater affinity for oxygen than the other component(s). One alloy system of obvious engineering importance comprised of two metals of greatly differing affinity for oxygen is copper-zinc. At the casting temperature of molten brasses, the zinc concentration is very difficult to control not only because its vapor pressure is very high, but also because of its high affinity for oxygen to form ZnO. Inasmuch as brass castings may be required to have a zinc concentration within very narrow limits, it would be advantageous for the brass industry to have a means for quickly measuring the zinc content in the molten alloy just prior to pouring. A calculation based on earlier thermodynamic studies of oxygen and zinc in dilute solution in binary Cu-O and CU-Z&apos; alloys indicates that the oxygen concentration of molten 70 wt pct Cu-30 wt pct Zn brass must be much less than 1 ppm for the separate phase ZnO not to exist in the ternary Cu-Zn-O system. Thus it can be assumed that all molten brasses, both in the laboratory and in the foundry, are sufficiently saturated with oxygen for the separate phase ZnO to be present. In view of the foregoing reasons, the cell investigated at 995°C for the purpose of measuring the zinc concentration in molten copper-zinc alloys, particularly those of brass compositions. In this cell the left hand electrode is a reference electrode comprised of a mixture of the pure powders of nickel and nickel oxide, to which a platinum contact is made. The electrode of interest is a molten Cu-Zn alloy of unknown zinc concentration with a tantalum wire contact. The electrolyte is the commercially available (Zircoa) calcia stabilized zirconia. The ZnO in the Cu-Zn electrode compartment is not intentionally added, but is naturally present as a result of the infinitesimal amount of oxygen required for its formation in this alloy system. In cell [A] nickel oxide is reduced at the cathode where O= represents the electrolyte. At the anode dissolved zinc of the Cu-Zn alloy is oxidized to form ZnO(s) in its standard state Thus the overall reaction is for which the molar free energy change is where 5 is the Faraday equivalent (23,063 cal per v equivalent), is the electromotive force of the cell in volts after correction for the Pt-Ta thermocouple, FOf (ZO) and AFF (NO) are the standard molar free energies of formation of the respective oxides, and a2n is the thermodynamic activity of zinc in the molten Cu-Zn alloy. The reference state of zinc in this case is taken to be the pure liquid. At constant temperature all the terms of Eq. [I] are constant except and azn Thus since all other participants in the electrochemical reaction are in their standard states, the change in the electromotive force of Cell [A] is represented only by a change of the thermodynamic activity of zinc at constant temperature. The zinc concentration is related to the activity by sampling the alloy for chemical analysis after cell measurements are taken. EXPERIMENTAL A typical cell construction is shown in Fig. 1. This and other experimental details were similar to that described earlier with the exception of some minor modifications which are detailed below.

Jan 1, 1970

Allan Gibb, Queensland, Australia (communication to the Secretary*):—It is gratifying that Mr. Edward Keller,&apos; who has clone so much work elucidating the principles of copper-metnllurgy, should have subjected only that portion of our investigation relating to magnetic iron oxide to anything like adverse criticism. Situated as we were on a rnining-camp, it was impossible to undertake work that would cover all the intricate possibilities connected with the materials commonly classed as matte. We therefore began the investigation on matte produced from ores that contained no other components than the sulphides of copper and iron that would be likely to enter into the composition of matte. We were, accordingly, free from ally possibility of magnetic iron oxide entering the matte, unless it were formed in the operation itself. The work done on this subject was incomplete, and the results thereof recorded as giving only negative evidence as to the absence of magnetic iron oxide. It would have been better to have left the matter open, as " not proven." The trend of the investigation was to account for the insufficiency of sulphur in matte to satisfy the requirements of ferrous and cuprous sulphides. So far as our deductions are correct, it was unnecessary to consider the (in our samples) somewhat doubtful constituent, magnetic iron oxide. The mattes that mere investigated were among those mentioned by Mr. Keller, " which scarcely show ally magnetic property." The samples showed no such property. There was no unaccountable variation in the specific gravity, which only varied, as would be expected, with the proportion of ferrous sulphide. I have had experience in smelting ores of which the gangue was a siliceous magnetite, both in blast- and rever-beratory furuace. The mattes so produced contained magnetic

Jan 1, 1908

By M. R. Annis, P. H. Monaghan

The control of mud properties affords two practical means of tnitigating pipe sticking caused by differential pressure: (I) teducing weight and, therefore, differential pressure; and (2) reducing the friction berween the pipe and mud cake. This paper describes investigation of the second of these—the friction between the pipe and the mud cake. Friction between a steel plate and a mud cake, held in contact by a differential pressure, was measured in the laboratory while maintaining a constant area of contact. Experiments were performed to determine how this friction varied with changes in mud composition and with changes in experimental conditions such as the differential pressure, time of contact of plate and mud cake, and filter-cake thickness. It was found that the apparent coefficient of friction, or the "sticking" coeficient, was not a constant; instead, it increased with increased time of contact between plate and mud cake, and with increased barite content of the Mud. The sticking coeficient varied from about 0.05 to 0.2 afer 20 , and eventually reached values of 0.1 to 0.3 after two Hours. Quehracho or ferrochrome lignosulfonate reduced the sticking coefficient at short .set times but did not reduce the maximum value. Carboxy-~t~etlz~lcellulose had no effect on the sticking coeficient. Emulsification of oil in the mud reduced the sticking coefficient. Some oils reduced the sticking coefficient to about one-third of its Value in the oil- free base mud, while other oils reduced it only slightly. Addition of certain surfactants with the oils further reduced the sticking coefficient. Spotting a clean fluid over the stuck plate caused a reduction in sticking coefficient only if the differential presslrrr was reduced, either temporarily or- permanently. INTRODUCTION Often during drilling operations the drill string becomes stuck and cannot be raised, lowered, or rotated. This condition can be brought about by a number of causes, such as sloughing of the hole wall, settling of large particles carried by the mud, accumulation of mud filter cake during long stoppage of circulation and, finally, sticking by pressure of the mud column holding the pipe against the filter cake on the hole wall. This paper is concerned with the last-mentioned phenomenon. Helmick 2nd Longley&apos; in 1957 suggested that a pressure differential from the wellbore to a permeable formation covered with mud cake could hold the drill pipe against the borehole wall with great force. This situation occurs when a portion of the drill string rests against the wall of the borehole, imbedding itself in the filter cake. The area of the drill pipe in contact with filter cake is then sealed from the full hydrostatic pressure of the mud column. The pressure difference between the mud-column pressure and the formation pressure acts on the area of drill pipe in contact with the filter cake to hold the drill pipe against the wall of the borehole. Helmick and Longley also presented laboratory cxperiments which showed that the force required to move steel across a mud cake increased with increasing differential pressure and with the time the stcel and mud cake had been In cuntact. Their data indicated that replacing the bulk mud with oil reduced the force required for movement. Field evidence was rcported that spotting oil over the stuck interval sometimes freed the pipe. Outmans- in 1958 presented a theoretical paper which described the sticking mechanism and explained the increase of sticking force with time with equations derived from consolidation theory. Since publication of these papers, there has been interest in the differential pressure sticking of drill strings, and several mud additives to reduce sticking or special equipment to free stuck pipe have been proposed."" Haden and Welch" have recently reported laboratory evidence showing that the composition of the filter cake influences the force necessary to move steel on the filter cake. There seems no doubt that differential pressure sticking is a real phenomenon and that its severity depends on the magnitude of the pressure differential across the mud cake, the area of contact and the friction between pipe and mud cake. The mud weight required to control a well is determined by the highest formation pressure in the well: hence, the magnitude of the differential pressure opposite normal or subnormal pressure formations cannot bc reduced. The area of contact may be minimized in several ways (control of filter-cake thickness, use of stabilizers and spirally grooved drill collars), but there arc practical limitations which prevent reduction of contact area from becoming a complete solution of the problem. However. the mud composition might bc altered to reduce the friction between pipe and mud cake. This paper presents quantitative measurements of the friction between steel and mud filter cake and shows how the friction varies with mud composition for given experimental conditions.