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By E. H. Griswold

PETROLEUM production engineering is essentially the application of the laws of 'physics and mechanics to the production of oil. A true production engineer is one who can apply the principles of mechanics, hydraulics, thermodynamics, and other physical arts so as to facilitate' the efficient and economical recovery of oil. To this end he must have wide knowledge of practical field operations and a working knowledge of geology, with a thorough understanding of the underground state of the fluids which he seeks to control. Generally speaking, there have been two schools of production engineering, the California development and the Mid-Continent development. In California the preliminary production engineering was done by representatives of the U. S. Bureau of Mines and the State Mining Bureau, and was essentially subsurface work in regard to casing patterns, water shut-offs, and completion procedure, inasmuch as these were problems of the utmost immediate importance to the California industry. The oil companies were impressed with the value of such work and placed engineers, or more strictly speaking, engineering geologists on their field staffs. These men, realizing the need of further technical study in the mechanical phases of producing operations, added mechanical and mining engineers, and out of the blend developed what is now known as a production engineer.

Jan 1, 1932

By WALTER B. JONES

PIG iron was first produced in Alabama in 1818 from limonite or brown ore and since then much of this ore has come from the so-called mineral district of northern Alabama, especially along the Cretaceous-Paleozoic contact. For many years the Russellville district in Franklin County, where the first blast furnace was erected, produced more than 100,000 tons of brown ore annually. Limonite has been reported at many places in the Coastal Plain region, where the formations are of Mesozoic and Cenozoic age, but these scattered deposits were never considered to be of much commercial importance. However, in the last three years a considerable quantity of this ore has been scraped up and shipped, particularly from the city of Greenville in Butler County.

Jan 1, 1938

By Willard C. Lacy

Survival of the mining industry as a viable economic entity in the United States is being seriously threatened by declining grades of ore reserves, rising operational and capital costs, and increased governmental taxes, restrictions, and subsidizing of third world competition. Discovery of major high-grade deposits is becoming increasingly unlikely. International competitiveness of the U.S. deposits will depend upon 'Yankee Ingenuity, ' innovations in mining methods, metallurgical treatment, and financial arrangements, and a viable national strategy. This will require not only effective management for control of operations, but management that encourages breakthroughs in technology, financing, labor relations, and in public and governmental understanding. The mine geologist and the exploration geologist both have important roles to play in all aspects of this fight for survival of the industry.

Jan 1, 1985

By William M. Sheehan

TRANSPORTATION is one of the most important problems of the mine operator and the possibilities of cost reduction in this field should not be overlooked. In the railroad industry, cars and locomotives have been improved greatly, and the progress there made is well worthy of study by the mine operator looking for maximum efficiency in every branch of his activities. One of the outstanding developments in the construction of railroad equipment in recent years has been the wide-spread adoption of large one-piece steel castings for the framework of locomotives, passenger and freight cars. Some of the advantages and applications of this type of construction will be outlined in this paper, with particular thought of the needs of the mining industry. The inherent qualities of cast steel: homogeneity, unrestricted size and shape, high tensile strength, flexibility of metal distribution, resistance to corrosion, and gracefulness of outline, make it the most versatile member of the ferrous group. Not only is it a strength-giving element, but it is corrosion resistant, a combination that makes for large economies in equipment maintenance. Flexibility of metal distribution allows the integral foundation to be in the shape best suited for the purpose. These cast structures are really assembled in the mold in liquid form and the metal can be placed in the right pro¬portion exactly where it is needed, thus securing weight economy and uniformity of fibre stress. Such a process permits the incorporation, with ease, of necessary brackets, utilizing them to provide not only greater strength for the derail part itself, but often to add to the value of the entire unit. Laps, seams, and joints, which are necessary in all fabricated forms, are eliminated.

Jan 1, 1933

THE metal iron has physical arid chemical properties which are some- what different from those of steels, but a knowledge of the pure metal is a useful starting point in studying the behavior of steels. Solid iron exists in two different crystalline forms, called alpha (a) and gamma (?) iron the former being the ordinary form at room temperature. When heated above the "A2 point," 769 C (1416 F), the metal becomes nonmagnetic, and at the "A3 point," 911 C (1672 F), it undergoes a change in crystalline form to become gamma iron. 111 the range 769 to 911 C, it is sometimes called beta (ß) iron to distinguish it from the magnetic alpha, but the two are identical in crystal structure. When gamma iron is further heated to 1392 C (2538 F), it changes into delta (d) iron, which is identical with beta or nonmagnetic alpha iron. Pure iron melts (in an inert atmosphere) at 1536 C (2797 F); the melting point is generally lowered by alloys or impurities. PHYSICAL AND THERMAL PROPERTIES OF IRON Many of the properties of iron undergo abrupt changes at the transition temperatures.1 For example, in heating through the A3 point, a sudden shrinkage in volume occurs. Similarly, melting is attended by sharp physical changes such as an increase in volume. Table 16-1 contains a summary of the measured physical properties of pure iron at several temperatures. Usually the properties change smoothly with the range of stability of a given form, but this is not always true. For ex- ample, the specific heat reaches a sharp maximum at the A2 point al- though no transformation occurs. (See Fig. 14-1.) Solvent Powers of Liquid Iron. Liquid iron is capable of dissolving most of the other metals and many nonmetallic elements as well. Of the metals that are liquid at the melting point of iron, only lead, silver, and bismuth refuse to dissolve to an appreciable extent. Table 16-2 contains a list of the common elements classified with respect to their solubility in liquid iron. Those which are very soluble or practically insoluble require no further discussion, but several of the nonmetals that are gases and exhibit limited solubility are of considerable importance to us and merit more detailed consideration.

Jan 1, 1964

By Lo-Ching Chang, J. Chipman

C. B. POST*—Just what are you showing that has not been shown by fixing the attention on molecular species and choosing the molecular species to give you a perfect solution? J. CHIPMAN (authors' reply)—In general a fairly satisfactory thermody-uamic treatment of slag-metal equilibria can be worked out on the basis of assumed molecular species in the slag. This has been the method used by Shenck and more recently by White. Winkler and I also used it in studying dephosphoriza-tion. Darken and Gurry found that it did not fit satisfactorily in the case of their data on iron oxides. The ionic formulas used here conform to the data much better and probably correspond somewhat more closely with the actual structure of the slags. C. B. POST—It does seem to be similar to you? J. CHIPMAN—It is alternative, and may lead to a more complete understanding. C. B. POST—Have you had a chance to talk to glass technologists on this? Have they been using this type of set-up for glass solutions? J. CHIPMAN—Yes, and the ionic formulas have given them a little better understanding of what liquid glass is like. C. B. POST—Nelson Taylor always said we were going- about slag reactions from the wrong viewpoint when using molecular species. Evidently the glass technologists use ionic species exclusively when dealing with liquid glass reactions. J. CHIPMAN—I agree that it seems more rational and more accurate to use ionic rather than molecular formulas. We should be cautious, however, and not suppose that we really understand the structure of a slag just because we are able to fit its reactions by ionic equations.

Jan 1, 1950

By Thomas L. Kesler

IF all of the 14 million tons of kaolin produced in Georgia through 1949 had been mined from a single deposit 20 ft thick, it would represent a mined-out area of less than 1 sq mile. This measure of depletion is in such strong contrast with the large size of the area shown in Fig. 1, from which most of the output has come, that there has developed an optimistic outlook concerning future supplies of kaolin equal in grade to that already mined. Dozens of mines are widely but not evenly distributed within this area, which consists mostly of parts of Twiggs, Wilkinson, and Washington counties. There are scarcely half a dozen kaolin mines elsewhere in the state that have been appreciably productive, although the areas in which they occur may have good possibilities. Most of the efforts to find new deposits, therefore, will be confined to the area shown in Fig. 1, for it is here that the industry has established its facilities, and prospecting is encouraged by relatively numerous outcrops and opened deposits of kaolin.

Jan 10, 1951

By Albert Sauveur

Some writers believe that when austenite transforms completely into pearlite on slow cooling through the thermal critical range, such transformation does not imply the formation of any of the so-called transition constituents: martensite, troostite and sorbite. Might it not be claimed with as much justification that when water freezes it does so suddenly, solid ice being obtained without passing through the intermediate stages of ice and water? Obviously, regardless of the speed of solidification, this would be erroneous. Before reaching the completed solid condition, this must of necessity pass through an unbroken series of stages when the system consists of mixtures of water and of ice, the former decreasing and the latter increasing in amount. Are not these "transitionV stages in the freezing of water similar to the transition stages occurring in the transformation of austenite into pearlite? To clarify, let us consider in Fig. 1 the mechanism of the transformation of eutectoid steel from its austenitic to its pearlitic condition as it cools slowly through its thermal critical range. It is generally admitted that this transformation is the result of two distinct phenomena: (1) the allotropic change of gamma iron into alpha iron and (2) the crystallizing out of solution of the carbide Fe3C. Whether this crystallizing of Fe3C implies also its formation is immaterial for our purpose. In other words, whether it is the carbon in atomic dispersion which is present in gamma iron or molecules of Fe3C has no bearing upon the matter to be discussed. The transformation of gamma iron into alpha iron cannot take place suddenly. It must of necessity be progressive, regardless of the speed with which it may take place. At A, for instance, there would be present AB gamma iron and BC alpha iron. The distance MN does not refer to falling temperature, but to the passage of time. It may be assumed that the transformation takes place at a constant temperature (the Ar321 point). In a similar way, the crystallization of Fe3C out of the austenite solid solution must be progressive as depicted between M and N. At A there would be present AB gamma iron, BC alpha iron, CD carbon dissolved in gamma and in alpha iron and DE Fe3C. This condition may be described according to individual preference as martensite or troostite. To sum up, can the metal pass from condition

Jan 1, 1931

By Gilbert L. Eggert

The effects of reactor irradiation on age hardening in a Cu-2 wt pct Be alloy have been investigated in two neutron-energy ranges. During some of the irradiations, specimens were exposed to high-energy fission neutrons which passed through a boron-10 shield; during other bombardments, the boron-10 was omitted and specimens were irradiated in a reactor thermal column, or the fuel configuration was modified to increase the thermal-neutron flux at a location in the core. Differences in length, X-ray diffraction angle, and hardness indicated that low-energy neutron irradiation made a small contribution to changes in the measured properties. The influence of defects generated by knock-om with less than the Brinkman critical energy or by prompt (n,y) recoil is suggested as the cause of this effect. EXPERIMENTS designed to test the effects of reactor irradiation on the properties of age-hardening alloys have to the present time employed fluxes un-differentiated according to neutron energy. Billing-ton and Siegell in 1950 were the first to perform such an experiment and to compare the results with those obtained by thermal aging. These authors concluded that precipitation in a Cu-2 wt pct Be alloy was not enhanced by the radiation. However, 4 years later, Murray and Taylor,2 working with specimens of the same Cu-2 wt pct Be alloy, reported that an increase in density, hardness, and resistivity which followed reactor irradiation resembled changes associated with thermal aging at about 100°C. (It should be noted that these authors reported that higher aging temperatures caused a decrease in resistivity.) cupp3 reported hardness results similar to those of Murray and Taylor. Koppenaal4 showed that irradiation-enhanced precipitation and irradiation defect hardening were not simply additive but that they acted separately in an irradiated alloy. Kernohan et a1.,5 working with Ni-Be, offered evidence that beryllium was removed from solid solution by reactor irradiation and suggested that the mechanism was one of increased diffusion through the use of vacancies in the structure. piercy6 also found that more precipitate particles were formed by fission-neutron irradiation of a Cu-Co alloy which contained a small amount of particles before irradiation. He proposed that the additional particles were caused by an appreciable amount of diffusion during the final cooling of displacement spikes. The retrogression of extant precipitate particles found by Murray and Taylor2 and Boltax7 as well as piercy6 indicated that nuclei were dissolved within a high-energy spike region and, upon resolidification of the perturbed volume, new nuclei precipitate and grow by enhanced diffusion. Bleiberg et al.' and Konobeevski et al.' explained phase changes obtained by irradiating fissionable alloys in terms of retrogression and re-precipitation in regions of high-energy spikes. Parsons and Balluffi10 used electron microscopy to verify that crystallization did indeed occur in displacement spikes which were formed in amorphous germanium by fast-neutron irradiation. The concept that low-energy neutron irradiation might cause structure-sensitive property changes in semiconductors by atomic recoil associated with the (n, y) reaction was first proposed by Schweinler" and walker." This thesis was tested by Cleland and crawford" and found to be valid. Coltman et al.14 exposed a variety of pure metals to thermal-neutron irradiation at cryogenic temperatures and attributed the resulting resistivity changes to the action of defects created by (n, y) recoil. The present work was undertaken to extend the concepts of Schweinler," walker," and Coltman et al.I4 to the case of an age-hardening alloy and to determine whether or not the action of defects produced by thermal-neutron irradiation would en-hance age hardening. EXPERIMENTAL PROCEDURE Omeea West Reactor Irradiations.* Thermal-

Jan 1, 1965

By M. Ahlers, Horace Pops

Slip features and formation of stress-induced mm-tensite have been studied in single crystals of fl phase Cu-Zn alloys in the composition range between 43 and 48 at. pct Zn. A phenomenological analysis is presented in which the glide planes and directions that me associated with the inhomogeneous shear in the martensite phase are predicted from the experimentally determined habit planes and macroscopic shear directions. It is shozun that the resolved shew component of the applied stress on the secondary shew system is a very important factor governing the formation of stress-induced martensite. A comparison is made between martensitic phases that form spontaneously upon cooling and those phases that arise from deformation. THE ß phase in Cu-Zn alloys is unstable and may transform spontaneously by a martensitic transformation1-3 during cooling. Thermoelastic and burst-type spontaneous martensitic phases have been observed3 in the composition range between 38 and 42 at. pct Zn. Martensite forms in alloys containing more than 42 at. pct Zn only by cold work below a temperature denoted as Md.4 Thus, alloys near the equiatomic composition can undergo a stress-induced transformation upon cold work at room temperature. Although data have been obtained concerning the effect of temperature5 and composition4 on the deformation of polycrystalline Cu-Zn alloys, it is rather surprising that few detailed studies6-8 on 6 brass have been conducted for single crystals where the stresses acting on crystallographic planes can be determined. A thorough understanding of transformation mechanisms requires knowledge of the role of stress and plastic strain. With this objective in mind we have made an investigation of the stress-induced rnartensite transformation in single crystals of 0 brass in the composition range between 43 and 48 at. pct Zn. Particular emphasis is given to the morphology and crystallographic features and a comparison is made between stress-induced and spontaneous martensite. I) EXPERIMENTAL PROCEDURE Master alloys having nominal zinc contents of 43, 45, and 48 at. pct were prepared from spectroscop-ically pure metals (>99.999 pct) in sealed quartz tubes under a partial pressure of helium. These alloys were cut into several pieces and converted into small rods by melting in quartz tubes. Subsequently, single crystals were grown from the rods by the Bridgman technique and homogenized for 3 hr at 820°C. Lattice parameter measurements were made from stress- relieved filings. Compositions, as determined from the reported variation of lattice parameter with atomic percent zinc,' indicated a zinc loss of less than approximately 0.25 at. pct. The single crystals were electroturned using a phosphoric acid electrolyte into tensile specimens each with a center section of 1 mm diam and 1 cm gage length. Cylindrical specimens approximately 3 mm in diam and 10 mm long and spark-machined rectangular blocks approximately 3 by 3 by 10 mm were prepared for compression studies. These blocks were stress-relieved and electropolished to eliminate any stresses introduced by spark machining. Crystal orientations were determined to an accuracy of ±2 deg primarily from back-reflection Laue photographs, and sometimes by the rotating single-crystal method. Figs. 1 to 3 show the location of the tension and compression axes within unit stereographic triangles. All specimens were deformed plastically at room temperature using an Instron machine, the crosshead speed being 0.02 or 0.05 cm per min. A hard steel hemisphere was placed at the upper end of the compression samples to achieve uniaxial loading. Trace normals of slip markings and habit planes of strain-induced martensite were determined to an accuracy of ±4 deg from the rectangular blocks by a two-surface analysis and from cylindrical specimens by measuring the angle between the tensile (or compression) axis and the tangent to the surface trace for different rotations about the deformation axis. Slip

Jan 1, 1969

By P. A. Beck, Hsun Hu

It has been known for many years that in cold drawn polycrystalline aluminum the recrystallization texture is practically identical with the deformation texture.l,2,3 V. Goeler and Sachs4 stated that in cold rolled polycrystalline aluminum, too, the deformation texture is retained upon recrystallization. This behavior was interpreted by Dehlinger9 as an indication that each recrystallized grain inherits the orientation of the matrix in which it grew. However, Burgers and Basart showed6 that in deformed aluminum single crystals the orientation of the recrystallized grains strongly deviates from that of the matrix. Barrett demonstrated8 that even in deformed polycrystalline aggregates the local orientation within each deformed grain changes on recrystallization. No explanation has as yet been offered of how the aggregate texture can be retained, while the local texture is everywhere changing. According to Burgers and Louwerse6 the orientation change on recrystallization in compressed and rolled aluminum single crystals corresponds to a rotation around [112] axes lying in the active slip planes and perpendicular to active slip directions. This orientation change was rationalized by them on the assumption that the orientation of the recrystallized grains is determined by the orientation of the available nuclei, and that these nuclei are small fragments of the deformed crystal, rotated in the deformation process. Barrett pointed out,? however, that these assumptions were by no means proven, and that the total volume of material necessary for the nuclei is so small, that it must be available in any orien- tation whatever. It is, therefore, unlikely that an "oriented nucleation" theory could satisfactorily explain the orientation changes in recrystallization of a deformed crystal. Furthermore, in contradiction to Burgers and LOU-werse's conclusions, Barrett's results for the orientation change could be best expressed in terms of rotations around. [Ill] axes. Thus agreement is lacking not only in the interpretations but apparently even in the experimental results contributed by the various investigators. The orientation relationships on coarsening* in a highly oriented polycrystalline matrix were first investigated by Burgers and Basart.5 They produced a fine grained highly oriented matrix by the recrystallization of a compressed or rolled single crystal of aluminum, and studied the orientation relationships in three successive generations of crystals: the "deformation texture" in the single crystal, the recrystallization texture, and the coarsening texture. Burgers24 showed that the preferred orientation of each successive generation was almost always widely different from that of the preceding one, but that the coarse grains often approximately reverted to the orientation of their grandparent, the deformed single crystal. This observation, and the idea that the orientation of the coarse grains is determined by that of the available "nuclei," led to the concept that the coarse grains are nucleated by the remnants of the deformation texture.12,15 On the other hand, Bowles and Boas16 found, in a carefully conducted experiment, that in recrystallized fine grained copper of cube texture coarse grains grow in orientations which can be derived from the orientation of the recrystallized matrix by rotation around a [lll].] direction: the coarsening texture here does not appear to be related in any simple manner to the original rolling texture from which the cube texture had been obtained by recrystallization. It may be assumed that in a recrystallized material, even with a strong texture, there always are present some grains of practically any orientation. These may serve as "nuclei" for the coarse grains, provided that the conditions are favorable for their growth. The existence of a coarsening texture may be considered as an indication that grains with certain relative orientations with respect to the preferred orientation of their neighbors can grow much faster than others. This "oriented growth" theory was briefly suggested by van Arkel, as early as 1936,13 and it was mentioned by Burgers." Recently, C. G. Dunn produced direct

Jan 1, 1950

By Charles W. Frey

OF all the machinery used in mining work, mine cars are probably the most abused. They are hauled through water and muck, up hill and down grade, whipped around curves, bumped and jerked, and exposed to the ravages of the weather. However, as a general rule their lubrication is not altogether neglected. The mine operator may not heed the extra drag that a frozen conveyor bearing gives, but he is all too aware of the increased load that faulty mine car wheels put on his power plant. When the circuit breakers begin to fly, and when his mine loco- motives come out with only half the cars that they were able to carry a month before, then neglected mine car wheel lubrication becomes apparent, and woe to the person responsible.

Jan 1, 1938

By G. M. BUTLER

TWENTY-ONE of the states in the Union, the Territory of Hawaii, and seven provinces of Canada now have in operation laws requiring that professional engineers be registered or licensed. In addition, two states require that civil engineers be registered, and one other state demands registration of structural engineers. Moreover, nearly every year sees additions made to the list. The registration movement, fostered by the American Association of Engineers, now has the powerful, energetic backing of the An1,erican Society of Civil Engineers, which is itself now fostering registration legislation, and there is a strong sentiment in favor of registration in the American Institute of Electrical Engineers and the American Society of Mechanical Engineers. Only in the American Institute of Mining and Metallurgical Engineers is anti-registration sentiment, strongly dominant, but many members of this organization are enthusiastic advocates of registration.

Jan 1, 1930

By P. D. Hunt, B. Tani, M. G. Chasanov, R. Schablaske

The Zn-Vphase diagram was studied by thermal. metallographic, X-ray, and sampling techniques. Three ternary phase equilibria were observed: Mutual solid solubilities in vanadium and zinc appear to be negligible. The liquidus line is retrograde from 670° to 756°C. 1 HE only information in the literature relating to the Zn-V system was a study of corrosion of vanadium by liquid zinc' and an examination of the effectiveness of zinc coatings in protecting vanadium-base alloys from oxidation at high temperatures.2 Establishment of the Zn-V phase diagram was undertaken as part of a study of transition metal solubilities in liquid metal solvents. Chemical, metallographic, thermal, and X-ray diffraction analyses were used to determine the diagram. MATERIALS AND EXPERIMENTAL PROCEDURES Vanadium (99.86 pct) in the form of powder and small chips was employed. Stick zinc (99.99 pct; major impurities: 10 to 15 ppm Pb and 20 ppm Cu) was used in the liquidus determinations and thermal analyses; zinc powder (98.80 pct) was used to prepare intermediate compositions. The liquidus lines were determined by chemical analysis of filtered samples of the saturated melts. The apparatus and sampling techniques were similar to those described by Martin, et al.3 The entire metal sample was dissolved to preclude analytical errors due to segregation on cooling. Vanadium was determined amperometrically, using iron (11) as the titrant,4 to an estimated accuracy of 1 pct. Standard techniques of thermal analysis were employed to examine alloy specimens contained in alumina crucibles under helium. Heating and cooling rates were about 1°C per min. At least five heating and cooling cycles over the range 420° to 700°C were performed for each of two Zn-15 pct V alloys. A Zn-0.2 pct V alloy was used in the determination of the eutectic temperature. The separation of intermediate phases from zinc-rich alloys was carried out by selective leaching with ammonium nitrate solutions. For further investigation of intermediate phases 1/4 in. diam powder compacts were prepared by pressing at 80,000 psi and were annealed in argon at 415" to 450°C for 10 days. Larger quantities of intermediate phases were prepared in sealed tantalum capsules heated in a rocking furnace. Temperatures were determined to an estimated accuracy of 0.5°C with a Pt/Pt-10 pct Rh thermo-

Jan 1, 1963

By James W. Guider

Of all the technology available to the iron blast furnace operator, raw materials preparation [(Fig. 1)] is by far the most important. Superior raw materials have been basic to the success of the Japanese steel industry, and they are just as essential to the American steel industry in winning its competitive battle against foreign government subsidized steel imports. Therefore, the mine operator and the ore beneficiation engineer must strive to produce the highest quality raw materials possible to meet the precise demands of the modem blast furnace and steel plant.

Jan 1, 1982

By Albert Sauveur

SOME writers believe that when austenite transforms completely into pearlite on slow cooling through the thermal critical range, such transformation does not imply the formation of any of the so-called transition constituents: martensite, troostite and sorbite. Might it not be claimed with as much justification that when water freezes it does so suddenly, solid ice being obtained without passing through the intermediate stages of ice and water? Obviously, regardless of the speed of solidification, this would be erroneous. Before reaching the completed solid condition, this must of necessity pass through an unbroken series of stages when the system consists of mixtures of water and of ice, the former decreasing and the latter increasing in amount. Are not these "transition" stages in the freezing of water similar to the transition stages occurring in the transformation of austenite into pearlite? To clarify, let us consider in Fig. 1 the mechanism of the transformation of eutectoid steel from its austenitic to its pearlitic condition as it cools slowly through its thermal critical range. It is generally admitted that this transformation is the result of two distinct phenomena: (1) the allotropic change of gamma iron into alpha iron and (2) the crystallizing out of solution of the carbide Fe3C. Whether this crystallizing of Fe3C implies also its formation is immaterial for our purpose. In other words, whether it is the carbon in atomic dispersion which is present in gamma iron or molecules of Fe3C has no bearing upon the matter to be discussed. The transformation of gamma iron into alpha iron cannot take place suddenly. It must of necessity be progressive, regardless of the speed with which it may take place. At A, for instance, there would be present AB gamma iron and BC alpha iron. The distance MN does not refer to falling temperature, but to the passage of time. It may be assumed that the transformation takes place at a constant temperature (the Ar321 point). In a similar way, the crystallization of Fe3C out of the austenite solid solution must be progressive as depicted between M and N. At A there would be present AB gamma iron, BC alpha iron, CD carbon dissolved in gamma and in alpha iron and DE Fe3C. This condition may be described according to individual preference as martensite or troostite. To sum up, can the metal pass from condition

Jan 1, 1931

By P. B. Mee

The secondary re crystallization behavior of two vacuum-melted, nominally 3 pct Si-Fe alloys has been studied, one alloy being produced from pure electrolytic iron and semiconductor-grade silicon and the other from commercial-purity hot band. The vacuum-melted and vacuum-remelted alloys were found to develop {110}(hhl) and {lll)(hkl), respectively, on annealing in high vacuum and {100}(0kl) and {11l}(hkl), respectively on annealing in pure hydrogen of dew point, < — 60°C. H2S doping of the hydrogen or annealing in commercial argon was found to effect a reversal for the vacuum-remelted alloy from (111) to (100) secondary recrys-tallization, while prolonged vacuum annealing at 2 x 10-6 Tow resulted in a tertiary re crystallization from (111} to (110). The growth selection of the {lll}(hkl) component was found to be governed predominantly by the {111}/planar misorientation, the maximum deviation of the resulting secondaries being 5 deg. It is considered that the driving force for {111}(hkl) secondary recrystallization arises from the preferential lowering of ?111, possibly by phosphorus or nitrogen diffusion, just as oxygen and sulfur under certain conditions have been found to preferentially lower ?100. When heavily cold-rolled metals are annealed at high temperatures, primary recrystallization usually occurs rapidly and may be followed by considerable grain growth. However, in the presence of a fine dispersion of inclusions1"3 or with a strong matrix preferred orientation4&apos;&apos; the matrix may be stabilized and a secondary recrystallization may then be effected. Also, in vacuum-melted Si-Fe it has been shown possible to develop {100}(001) and {110}(001)6 surface energy driven secondary recrystallization textures. Further, it has been found that, on annealing very pure metals, grain growth normally ceases when a grain size approximately twice the strip thickness is acquired, due to the formation of V-shaped thermal grooves which result in an equilibrium being set up between surface and grain boundary stresses. If, however, a surface energy difference ??s, exists between adjacent grains (of the order of a few percent of the grain boundary energy ?b), then according to Mullins8 a secondary recrystallization may be effected, since the grains having lowest ?s would grow at the expense of their higher-energy neighbors. For clean bee metal surfaces ?110 should be lowest; however, for 3 pct Fe-Si (100) secondary structures have frequently been developed and have been attributed by Walter and Dunn9 to an alteration of the relative surface energies due to the preferential chemisorption of oxygen on (100) planes. Kohler,10 however, indicated that this reversal may be achieved by employing minute quantities of highly polar compounds in the annealing atmosphere, i.e., sulfur compounds, in par- ticular H2S being beneficial in (100) growth. This work has been verified by Kramer" using {100)/{110} bicrystals, while Mager12 demonstrated the importance of sulfur diffusion within the strip. Detert13 has intimated that carbon may be responsible for the preferential lowering of ?110 although no direct evidence has appeared yet to support this supposition. It must , be appreciated that the above-mentioned examples of surface energy driven secondary recrystallization were obtained with very pure vacuum-melted materials with oxygen contents (which is now known to be a critical factor") less than 35 ppm. During the course of a textural study on Si-Fe it has been found that under certain conditions (111) secondary recrystallization can be obtained by what is believed to be a surface energy growth selection mechanism. The purpose of the present paper is to briefly describe this result and to try and postulate the possible causes. EXPERIMENTAL Two vacuum-induction-melted, nominally 3 pct Si-Fe alloys were produced, one from pure electrolytic iron and semiconductor-grade silicon designated A and the other from commercial-purity hot band, designated B.

Jan 1, 1969

By A. Rosen, P. Wynblatt, J. E. Dorn

The temperature, strain rate, and structure dependence of the flow stress in a poly crystalline Fe-2 pct Mn alloy was investigated between 77" and 370°K. It was possible to identify the low-temperature data from 77° to 160°K with Dorn and Rajnak&apos;s theory of the Peierls mechanism of plastic deformation. Above 160°K one or more thermally activated mechanisms must he operative; however, these were not identified in this investigation. The mechanistic basis for the rapid decrease in the flow stress of bcc metals with an increase in temperature over the low-temperature range is yet being debated. Various dislocation mechanisms have been suggested in the past but the agreement between the various proposed theories and the experimental results have not been definitive. In the present paper, the authors will demonstrate that the plastic behavior of polycrystalline iron containing 2 wt pct Mn plus interstitials agrees excellently with predictions based on the Peierls mechanism from 77" to 160°K whereas from 160" to about 370°K other as yet unidentified thermally activated mechanisms take over. Undoubtedly, the overlap of these mechanisms with the Peierls mechanism contributed to the difficulties of rationalizing the low-temperature behavior of iron and its alloys. I) EXPERIMENTAL TECHNIQUES AND RESULTS Although extensive data are now available on the effect of temperature and strain rate on the flow stress of various bcc metals and alloys, it was, nevertheless, deemed necessary for the objectives of the present study to obtain highly accurate data of the type most pertinent for checking the theories on a series of well-documented work-hardened states. Iron containing 2 wt pct Mn was used in this investigation in order to obtain a lower ductile to brittle transition temperature than that for iron.&apos; The additional elements present were 0.004 pct C, 0.05 pct 0, 0.004 pct S, 0.003 pct P, 0.006 pct N, and 0.001 pct Si. The as-received 3/8 by 3/4 in. bars were cold-rolled to 0.100-in. thickness, recrystallized under argon for 30 min at 1073"~, further cold-rolled to 0.063-in. thickness, and finally recrystallized under argon for 30 min at 1000°K. This treatment gave a stable reproducible equiaxed grain structure having an average grain diameter of about 90 p. Prior to the final recrystallization treatment, the sheet was machined into tensile specimens 1/4 in. wide having a 1.625-in.-long gage section. All specimens were tested in controlled-temperature baths on an Instron Testing Machine. For convenience in the theoretical analyses the data will be given in terms of the shear stress for flow, 7, the shear strain rate, f, and the shear strain, y. A series of three standard strain-hardened states were obtained by prestraining specimens at 300°K and at a shear strain rate of 7.68 x lo-&apos; per sec to three stress levels of 6.89 X l08, 10.3 X lo8, and 14.5 x 10&apos; dynes per sq cm, respectively. Immediately following this prestrain the temperature bath was changed and each specimen was pulled in tension at either f = 7.68 X lo-&apos; or f = 3.06 X 10"3 per sec. In terms of the accuracy that was achieved, the values obtained did not deviate more than *0.1 X 10&apos; dynes per sq cm and * 1°K from the reported values of stress and temperature and not more than *5 pct in the reported values of the strain rate. The tensile stresses were converted to shear stresses using a factor of 1/2. The shear stress for the initiation of flow at the test temperature was determined by taking a y = 6.16 x 10&apos;3 offset. from the modulus line at which point good accuracy could be achieved in determining y and the associated flow stress 7, with only a negligible increase in the pre-

Jan 1, 1965

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.&apos; The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8&apos;10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By Donald L. Katz

The compressing of gas into a partially depleted gas drive oil reservoir to bring the contents to a single phase miscible with gas is proposed as a process worthy of serious study. The compressed gas and vaporized oil would be recovered by cycling. This paper explores the Possibility of recovering oil from reservoirs of 6,000 ft or more by this method. INTRODUCTION Many new methods for increasing the recovery of oil from reservoirs are under consideration in the various research laboratories. One method which should be considered for recovering oil From partially depleted gas drive fields is to compress gas into the reservoir until the contents become a single phase miscible with more gas. Natural gas then may be cycled through the reservoir to recover the oil. This procedure ideally will eliminate the capillary effects of the liquid ill the porous media and should permit recoveries similar to those obtained in cycling operations, probably of the order of 80 per cent. This paper explores the information now available for the prediction of the performance of such a project and discusses the problems likely to be encountered in recovering oil by cycling. For many years dry natural gas has been passed through oil reservoirs to recover natural gasoline which would vaporize from the oil. Recently a process of recovering more of the high boiling hydrocarbons has been described by employing high pressures at which the heavier hydrocarbons have a higher volatility. Nevertheless. this reported method does not eliminate the differential nature of the vaporization process and capillary forces are still present in the reservoir. The process under discussion in this paper would minimize differential vaporization and would remove capillary forces which are responsible for low oil recoveries. Higher gas pressures are required to accomplish this removal of the miniscus, but it does not follow that more gas is required for oil recovery. The process is limited to reservoirs deep enough to permit the use of the required pressure — Probabably 6,000 it and deeper. DESCRIPTION OF THE PROCESS Briefly, the process is to compress natural gas into an oil reservoir which is partially depleted so that it has an oil saturation in the range of 40 to 60 per cent of the hydrocarbon pore space. The injected gas will pass through the channels formerly carrying gas to the wells to build up the pressure and dissolve in the oil phase. This injection will continue without production from the field until the reservoir reaches a single phase. If one were to select unique conditions such that the gas composition, the reservoir oil composition and the Per cent saturation would bring the mixture in the reservoir to the critical temperature and pressure simultaneously the phase behavior accompanying injection is shown by Fig. 1. The oil-gas mixture in the depleted reservoir has a critical temperature at C,. Addition of natural gas to the mixture will give a new critical temperature for each addition. Mixture No. 3 is shown to have its critical temperature at the reservoir temperature and reservoir pressure at P: the critical pressure. Under ideal behavior, the entire reservoir would be at iti critical temperature and pressure and the entire hydrocarbon content would be at a single phase. If the reservoir content were a binary system of methane and a heavy constituent. it would be miscible with more methane. However, for complex mixtures the critical locus does not confine the two phase region, and the dew point curves of Fig. 1 occur above the critical locus. If fluid which was injected into the rezervoir at the critical point were of the

Jan 1, 1952