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By Arthur Phillips, R. M. Brick, A. J. Smith

A previous publication1§ has described the effect of quenching stresses on the lattice parameter values of high-purity aluminum-copper alloys particularly with reference to the solution and precipitation of CuAl². A similar study has been made of the aluminum-rich aluminum-magnesium alloys. Attention has been directed in the present investigation to the magnitude of the quenching stresses as affected by the specimen size and shape, the number of solute atoms and the quenching rate. The effect of cooling stresses in causing plastic defomation or cracking has been considered in relation to the physical properties of the alloy On reheating alloys in the two-phase field, the time required for precipitation to occur has been observed in connection with the degrec of supersaturation, the rate of diffusion of the solute atoms as a function of the comparative atomic radii, degree of strain, temperature of reheating and grain size. A few qualitative comparisons on the relative effect of these factors have been drawn between the aluminum-copper alloys and the aluminum-magnesium alloys. Strain in Solid-solution Alloys A 10 per cent magnesium alloy ill the form of chill-cast bars was furnished by the Aluminum Company of America through the courtesy of L. W. Kempf. Additional alloys were prepared using alllminum (99.95 per cent Al) and high-grade magnesium. The alloys listed in Table 1 were melted in an Acheson graphite crucible under a flux of fused MgCl², CaC12, NaCI. Chill-cast rods were sealed under vacuum in Pyrex glass, homogenized several days at 450' C., air-cooled and machined to rods of from 1/8 to ¾-in. dia. Metal powders taken from these rods with a fine-toothed saw were again sealed under vacuum in

Jan 1, 1935

By R. M. Brick, Arthur Phillips, A. J. Smith

A previous publication1§ has described the effect of quenching stresses on the lattice parameter values of high-purity aluminum-copper alloys particularly with reference to the solution and precipitation of CuAl². A similar study has been made of the aluminum-rich aluminum-magnesium alloys. Attention has been directed in the present investigation to the magnitude of the quenching stresses as affected by the specimen size and shape, the number of solute atoms and the quenching rate. The effect of cooling stresses in causing plastic defomation or cracking has been considered in relation to the physical properties of the alloy On reheating alloys in the two-phase field, the time required for precipitation to occur has been observed in connection with the degrec of supersaturation, the rate of diffusion of the solute atoms as a function of the comparative atomic radii, degree of strain, temperature of reheating and grain size. A few qualitative comparisons on the relative effect of these factors have been drawn between the aluminum-copper alloys and the aluminum-magnesium alloys. Strain in Solid-solution Alloys A 10 per cent magnesium alloy ill the form of chill-cast bars was furnished by the Aluminum Company of America through the courtesy of L. W. Kempf. Additional alloys were prepared using alllminum (99.95 per cent Al) and high-grade magnesium. The alloys listed in Table 1 were melted in an Acheson graphite crucible under a flux of fused MgCl², CaC12, NaCI. Chill-cast rods were sealed under vacuum in Pyrex glass, homogenized several days at 450' C., air-cooled and machined to rods of from 1/8 to ¾-in. dia. Metal powders taken from these rods with a fine-toothed saw were again sealed under vacuum in

Jan 1, 1935

By G. H. Edmunds, C. H. Mathewson

About fifty pages of Henry M. Howe's profound treatise, "The Metallography of Steel and Cast Iron," are devoted to twinning with special reference to the origin, nature and general significance of the Neumann bands in ferrite. Howe believed with Osmond and Cartaud1 that the Neumanns are mechanical twins and his careful observations leave no doubt that these straight-sided narrow bands habitually occur parallel to trapezohedral planes of form {211). Attempts to develop the structure of the bands by various methods SO that their identity could be established beyond question have not been conspicuously successful. Howe thought that they deflected slip bands. Some of the etching figures which have been developed within and adjacent to Neumann bands support the contention that they are twins. A good example of this effect in ferrite containing 0.6 per cent, of niekel and 1.3 per cent. of phosphorus, originally due to Harnecker and Rassow,2 was reproduced in the 1928 lecture before the Institute of Metals Division on twinning in metals.3 In this case, the sides of the figures might represent the traces of cubic planes laid bare by etching a properly oriented grain of ferrite, twinned along a plane of form (211). Our own observations in this direction may be represented by Fig. 1 which shows in a deeply etched cavity in the boundary region between a Neumann band and the original crystal two small crystal surfaces which resemble the faces meeting at a reentrant angle in the simple cube twinned along a bisecting plane of form (211) as sketched in Fig. 2. Rosenhain and McMinn4 in 1925, after a careful study of slip bands in ferrite containing Neumanns previously produced by shock, concluded

By Charles Barrett

PLASTIC flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following funda-mental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the lattice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals -"grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by vari-ous investigators for more than 25 years, ? yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of mate-rial that was used in the earlier compression experiments1-hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By J. E. Hackford

In some research work carried out by the writer, certain results have been obtained which bear on the fundamental nature and origin of coal and the relationship between coal and petroleum. Without entering into a discussion of the details of the experiments, which were conducted on petroleum and derived bitumens, there are given here, by way of definition, some of the relations that the writer has established between certain classes of bitumens of petroliferous origin. Bitumen.—-A natural organic substance, gaseous, liquid, or solid, consisting of hydrocarbons and the oxy-or thionic derivatives of the same, or of a mixture of all three. Diaspha1tenes.—-Those portions of bitumens that are soluble in ether or carbon disulfide, but are insoluble in a mixture of equal parts of ether and alcohol. Diasphaltenes are produced by the oxidation or thionization of petroleum oils; they have, as the name indicates, twice the molecular weight of asphaltenes, into which they are converted when subjected to moderate temperature. For example, an artificially produced diasphaltene, which was readily soluble in pentane and ether, was quite insoluble in either of these solvents after heating for three weeks at a temperature of 100" C., and was converted into an insoluble asphaltene. Aspha1tenes.—Those portions of bitumen that are insoluble in ether or ether alcohol but are soluble in carbon disulfide. Aspha1tites.—Those solid or semisolid natural bitumens that are composed, for the most part, of asphaltenes or diasphaltenes. A pure asphaltitel would be composed wholly of asphaltenes and diasphaltenes, but most asphaltites contain small percentages of oil and wax, which have not yet been converted into asphaltenes; they may also contain A small percent.age of kerotenes, which represent the next stage of the metamorphosis of asphaltenes. Among the naturally occurring oxyasphaltites may be mentioned grahamite; and among the thioasphaltites, gilsonite.

Jan 1, 1921

By A. J. Lyon, J. B. Johnson, Samuel Daniels

The wrought alloys of aluminum with small amounts of copper and of magnesium have, with the development of the automotive and aircraft industries, sprung into prominence through the medium of duralumin; but the cast alloys remained in the background because their possibilities in the heat-treated condition were either not recognized or not fully investigated. In 1919, the Bureau of Standards published a preliminary survey1 of this field, which pointed out that, in general, the ultimate strength and the percentage of elongation of the alloys of aluminum with and without magnesium could be improved by so simple a treatment as heating at 932' F. (500" C.) for 2 hr., cooling in air, and aging at room temperature for several days. British investigators, too, working with chill-cast material, found that" considerable improvement in the mechanical properties of copper-aluminum alloys may be obtained from suitable heat treatment applied to castings."' Jeffries and Gibson8 made the first contribution to the literature dealing exclusively with the heat treatment of sand-cast aluminum-base alloys, describing the effect of small additions or of combinations of copper, magnesium, and iron on the response to a short heat treatment comprising heating at 932" F. in a nitrate bath for 1 hr., quenching in fish oil, and reheating at 300' F. for for 1 hr. Their results disclosed the facts that the ultimate strength and the percentage of elongation of sound alloys were usually, and quite uniformly, improved by heat treatment; that with the iron content ranging between 0.36 and 0.88 per cent. and the silicon content between 0.24 and 0.60 per cent. the effect of increasing the copper content (Tables 10

Jan 1, 1925

By Norman Brown, Victor V. Damiano

ThE present paper proposes a mechanism of dislocation multiplication at internal inclusions or cavities and presents experimental evidence of such sources in zinc. Using an etching technique recently described by Damiano, Tint, and Herman1 to study the three-dimensional aspects of dislocations in bulk zinc crystals, an investigation was made of helically shaped and closed-loop etch patterns found to be associated with inclusions. Crystals containing 0.1 pet Cd and grown from the melt were deformed slightly by bending and then aged at room temperature to precipitate cadmium at the dislocations. The crystals were cleaved along the (0001) plane and then etched with Gilman's2 etch. Crystals were continuously viewed on the (0001) plane while the etching was in progress and numerous helical and closed-loops etch patterns were continuously recorded as shown in the sequences printed directly from the cine film in Fig. l(a) and (6). These etch patterns are not to be confused with the etch patterns previously reported by Damiano and Herman3 which revealed dissolution spirals on the (0001) plane of high-purity zinc crystals. In the present case, precipitates arranged in the form of closed loops or helicies are progressively uncovered by etching after suitable aging of cadmium doped zinc crystals. Viewed with dark-field illumination as shown in Fig. 2, portions of a helical figure and subboundaries were revealed simultaneously. Continuous viewing while the etching was in progress revealed in Fig. 1(b) that the short line segments observed on single photomicrographs were in fact continuous and described a helix which had its terminus at an inclusion. The observations suggested that a dislocation once nucleated at the interface between the inclusion and matrix may act in such a way as to produce ad-

Jan 1, 1964

By J. O. McCaldin, P. Duwez

ALLOTROPIC transformations between 1000° and 1900°C have recently been reported for several metallic elements. Since the proposed transformations are based on limited evidence, it was decided to examine the elements in question as well as some refractory metals by thermal analysis with a photoelectric technique similar to that described by Hug-gins, Roll, and Udin.1 In this method, a lead sulphide cell was used to detect thermal radiation from an electric-resistance heated strip specimen. A thermocouple spot welded to the specimen was used to calibrate the temperature of the system under steady temperature conditions, and recording was accomplished with a cathode ray oscilloscope. In the method used by the present authors, the temperature calibration was omitted and the cathode ray oscilloscope was replaced by a recording galvanometer. This technique, in which electric current passing through the specimen heats it, will be referred to henceforth as Method 1. Another arrangement was required for those cases where the specimen could not be formed into a wire or strip suitable for resistance heating. In such cases the specimen was a sintered compact heated by thermal radiation from a hot tungsten strip, Fig. 1. The specimen was insulated from the heating strip with a thin layer of thoria powder or suspended on 0.004 in. tungsten wires. The take-up spring had just sufficient tension to prevent buckling of the heating strip due to thermal expansion. This technique will be called Method 2. Both methods were tested with specimens of iron and titanium and the well known allotropic transformations, a toy and ? to 8 in iron and a to in titanium, were very clearly detected. Fig. 2 shows one of the records obtained for titanium. For this particular experiment, the iodide titanium specimen was a square rod 0.080 in. on an edge and 3 in. long.

Jan 1, 1955

By T. F. Witherbee

ON the 22d of November, „1879, white iron unexpectedly appeared while working the Cedar Point Furnace, Port Henry, N Y., on the following burden, calculated to turn out mill and foundry iron: Anthracite coal, - 3000 pounds. Connellsville coke, - 1500 pounds. Total, - 4500 pounds. Old Bed ore, - 3750 pounds. New Bed fine ore, - 2000 pounds. New Bed chunk ore, - 1000 pounds. Kearnev hematite ore, - 750 pounds. Total, - 7500 pounds. Magnesian limestone, - 1865 pounds. Common limestone, - 885 pounds. Total, - 2500 pounds. The production per week since making mill iron-from September 1st, 1879, to date, seven weeks-was 412 gross tons. Ore was not immediately taken off, as nothing serious was looked for. The iron for the next week graded from No. 4 to white, and in. six days the make was 274 1/2 tons. At 10 P.M., Friday, the 28th, a slip of-..4 feet occurred, and on Saturday, at 5 A.M., another of 3 feet on the south side and. 7- feet on the north side took place. At this time it was found that the south side had been hanging for over a week--a fact which had not been reported. Throwing off the wind, to produce slips. and reduce pressure, had been tried with no effect. The stock, as seen through the tuyeres, seemed to consist almost entirely of coal, with just enough infusible cinder to cement it into a mass through which the blast could not be forced. At 3.50 A.M., Sunday, the 30th, the first cinder seen in seventeen hours came into tuyeres Nos. 1, 2, 3, and 6, At 9.30 A.M. No. 3 was taken out to see if the stock

Jan 1, 1881

Forty-three years ago a record for low cost was made at the Spanish mine, in Nevada county, California. In 22 days of September, 1887, there was mined 2796 tons of ore at a cost of 37.5 cents per ton, of which 32.4 cents was for labor and 5.1 cents for supplies. The mill treated this ore for 23 cents per ton, of which 12.3 cents was for labor and 10.7 cents for supplies. Thus the total operating cost was 60.5 cents per ton. The yield was $1.16 in gold per ton, leaving a profit of 56 cents per ton, or 48 per cent of the yield. The mine was an open-cut in a schist formation on a hillside and the work was done by Chinese laborers that were paid $1.40 per shift. The ore was soft, and could be ground effectively in four Hunting- ton mills, supplemented by silvered amalgamating plates.* The engineer in charge was F. W. Bradley, a student from the University of California. As has been indicated, the conditions were unusually favorable in respect of softness of ore, accessibility to the mill, metallurgic simplicity, with cheap labor and power, but even at that the results were so remark- able as to attract general attention, which, as might be expected, was magnified, for advertising purposes, by the manufacturers of the Huntington mill, the firm of Parke & Lacy, at San Francisco. The record made at the Spanish mine therefore found its way into many textbooks on mining published at that time. The editor of the 'Mining and Scientific Press'† (at that date, Charles G. Yale) evidently took a warm interest in. the

Jan 1, 1932

By W. E. C. Coxe

AT the meeting of the Institute in Philadelphia, in June, 1876, it was my pleasure to read a paper on the "Manufacture and Endurance of Iron Rails." I then spoke of some trial rails which had been placed in the down track of the Philadelphia and Reading Railroad, over which passed, in addition to merchandise and passengers, most of the heavy coal traffic of that company. One of these rails, made at the Philadelphia and Reading Rolling Mill in 1870, and then placed in the track, was removed in 1876, after having carried about 55,000,000 gross tons, and was on exhibition at the Centennial Exhibition. A piece of this worn rail, twisted cold, was also shown there. One of the same series of rails was allowed to remain in the track until 1878, and short sections of this rail, as well as one not worn, to show its original shape, are presented for your inspection. A comparison of the two will show that the top of the head or tread has worn down 3/16 ths of an inch during its nine years of service. It carried in that time 67,000,000 gross tons of freight, passengers, cars, and engines. This rail was made in the usual way of manufacturing iron rails at the Philadelphia and Reading Rolling Mill. The head was made from puddled iron bars, piled, heated, and rolled into bars, 4 1/2 and 3 inches wide by 1 inch thick, these bars, breaking joints, were made into a pile in section 9 inches square, heated and rolled into slabs 9 inches wide and 2 inches thick; the balance of the rail-pile was made of 4 1/2 and 3-inch bars, rolled from two-thirds old rails and one-third puddled iron, the

Jan 1, 1880

By J. E. Powers, T. D. Taylor, N. E. Wood

A computer program has been developed to simulate a gas transmission 1ine operating under transient conditions. The program was developed by application of the basic mass and momentum balance equations. The nonlinear equations thus obtained were transformed by the method of characteristics and finite-difference techniques to make them suitable for machine computation. Three tests of the computer program were made. In each of these, the initial condition was assumed to be steady-state flow, the inlet density was held constant at the initial condition, and the outlet mass flow rate was varied with time. One test was theoretical in nature, but the others were made for direct comparison with actual field data. Results of the tests are presented in graphical form. INTRODUCTION Theoretical investigations of the transient flow of gas in long pipelines have been limited in number. In 1951, Olds and Sage4 developed a gaphical method of solving the nonlinear flow equations describing transient gas flow in a long pipeline. Research in this field at the U. of Oklahoma was initiated by Nelson1 in 1956. Nelson utilized a computer to solve numerical equations involving a lengthy trial-and-error procedure, and his results have been reported in the literature? It does not seem likely that Nelson's method can be extended to the analysis of transient behavior of pipeline networks; therefore, the investigation to be discussed in this paper was undertaken to improve and extend the previous work. The following discussion presents, briefly: (1) the basic differential equations governing transient flow, (2) transformation of these equations into a form suitable for machine computation. (3) role of boundary conditions in the calculations, (4) a very brief description of the computer program which was developed to simulate the pipeline and (5) results of tests of the computer program.

By Willard C. Lacy

Rather than attempting to present a summary of the many and highly varied papers that have been presented at this symposium on sampling and grade control, I will attempt to extract the general philosophy of analysis and approach, and attempt to identify the trend of future developments. First, the term "sampling" is used with its broadest connotations. A sample consists of a representative portion of a larger mass, and must represent the mass not only in the grade of contained metals or minerals, but also in all other respects in terms of mineralogy and mineral quality (1, 5), deleterious materials, recoverability of economic components, physical behavior, geophysical response (I), and even archaeological and environmental aspects (7, 11). The sample must be taken from a locality and in such a manner and quantity that it is representative of the larger rock mass. This calls for complete and accurate geological control and an understanding of the nature and distribution of the contained chemical and physical elements and a record of the effectiveness of the different sampling methods. Second, value of a given mass of ore material is based upon its profitability - the difference between recoverable value and costs to achieve recovery, beneficiation and sale. There is a strong movement in mining geology control toward more complete analysis in determining cutoff grades and in grade control, as illustrated by the kriging of metallurgical recovery factors as well as grade at the Mercur Mine (8). To achieve a "profit- ability factor" as a guide for economic mining practice requires further integration of: 1) the value of contained metal or mineral, 2) percentage recovery of values, 3) dilution of ore with waste rock, 4) addition to, or loss of value as a consequence of by-product materials or deleterious components, 5) cost of producing a saleable product plus mini- mum profit to justify the effort (cutoff), and 6) cost of land restoration (7, 11). All these parameters vary with the rock type, rock structure, mineralogy, depth, geometry, mining and metallurgical methods, but they must be sampled and analyzed if sampling and grade control are to reflect profitability. A wide variety of deposits has been presented at this symposium; each deposit with its own problems and special solutions. Deposits containing high unit-value components, e.g. precious metals and diamonds, present special problems in the obtaining of accurate samples and generally require statistical analysis control methods or may disregard or modify occasional high or occasional low values, based upon experience (12 ) Grade control may be accurate for the long term but may vary for the short term. Bulk sampling is always essential. Deposits containing metals or minerals with low unit value are very sensitive to transport costs, and they are often very sensitive to small amounts of deleterious components or differences in physical or chemical behavior. Problems of sampling and grade control change with the genetic type of deposit, with the stage of deposit development and with the size of the information base. Precious metal epithermal deposits (2, 6, 8), because of rapid vertical zonation and erratic lateral distribution of values, have always been difficult to evaluate and maintain grade control and ore reserves. On the other hand, evaluation and grade control are relatively easy in bulk-low- grade deposits (4, 13). However, these deposits generally have a low margin of profit and are sensitive to mining and beneficiaton costs, price fluctuations and political costs. Industrial mineral deposits (5) often must be evaluated on the basis of their behavior, rather than by chemical analysis. Environmental impact generally increases with the scale of the operation, but certain elements or minerals have especially high impact effects (7, 11). In the exploration phase there is no production control of sampling procedures and careful geological observations are particularly essential. The greatest number of problems is related to the oxidized outcrop where the chemical environment of the ore body has changed and the contained values may have been enriched, depleted or values left unchanged (2, 6). Present evidence suggests that gold values may be very mobile under certain conditions (2, 6) and stable under others. Everything must be sampled in detail. Principal values and by-product or deleterious elements may vary dependent upon their position within the soil profile. Such factors as geomorphic position, erosion rate, vegetation, climate, etc., may affect the interpretation (1, 3). During the development phase it is equally easy to overtest, to have "paralysis by analysis," as to undertest (3, 6). Bulk samplng and testing are

Jan 1, 1985

By R. D. Nelson, J. C. Shyne

The ß and a ß transformations in plutonium were studied with particular emphasis on the transformation kinetics and microstructure. Significant observations are: 1) The kinetic data show conclusively that the ß — a transformation in high-purity plutonium can proceed isothermally with no athermal component. 2) Plastic deformation of the stable (3 phase retards the subsequent (3 — a transformation. 3) Plastic deformation of the stable a phase accelerates the a — ß transformation; the acceleration is attributed only to residual stresses. 4) The a and a?a volume changes occur anisotroPically in textured plutonium. 5) An apparent crystallogvaphic relationship exists between the parent and the product phases of the and (3 — a transformations. 6) Both applied uniaxial compressive stresses and uniaxial tensile stresses raise the starting temperature for the ß — a transformation. 7) A given uniaxial tensile stress favors the a — ß transformation more than an equivalent applied uniaxial compressive stress opposes the transformation. These observations of the (ß —a and a — ß phase changes in plutonium are consistent with known mar-tensitic transformations. ThIS paper elucidates some of the characteristics of the a— ß and ß —a transformations in plutonium. Because considerable conjecture exists about the mechanisms by which the phase transformations occur in plutonium, experiments have been performed to provide indirect information concerning the mechanisms responsible for the a —ß and ß -a transformations. Indirect information is of particular value in the study of plutonium because of the experimental difficulties presented by the metal. Single crystals have not been produced in any of the allotropes. The large density results in high X-ray and electron-absorption factors and consequently complicating X-ray and electron diffraction. The kinetics of ß — a and a — ß transformations of plutonium and the behavior of the transformations under a variety of conditions have been investigated in detail. Information about the mechanisms of the allo-tropic transformations of plutonium was obtained indirectly from three sources: 1) the effect of plastic deformation of the stable parent phase upon the transformation kinetics; 2) the behavior of the metal transforming under applied stresses; and 3) the microstruc-tural and crystallographic features between parent and product phases. PHASE-TRANSFORMATION CHARACTERISTICS In characterizing solid-state phase transformations in metals and alloys, it is useful to define several types of transformations. An aim of the present work was to identify the low-temperature transformations in plutonium by type, i.e., as martensitic or nonmar-tensitic. Practical definitions for these terms follow. The terms commonly used to categorize phase transformations lack universally accepted definitions. This confusion arises doubtlessly because some terms specify crystallographic or morphological character while other words have a kinetic or a thermodynamic connotation. For example, martensitic specifies certain definite crystallographic restrictions. Unfortunately, martensitic is sometimes used in an ill-defined way to imply kinetic characteristics. Further confusion attends the use of such expressions as nucleation and growth, diffusional, and massive. From time to time new systems of phase-transformation nomenclature are suggested; unfortunately none of these has gained general acceptance.1,2 The authors of the present paper have no intention of entering the controversy. We recognize that some readers may object to the nomencliture used here. For exampie, the terms military and civilian have recently been used in much the same way as martensitic and non-martensitic are used in this paper. This paper is intended to describe several specific details of the low-temperature phase transformations in plutonium. The authors have found it useful to identify these transformations as martensitic; the term was chosen as the best available to describe the experimentally observed features of the transformations studied. A martensitic transformation is one that occurs by the cooperative movement of many atoms; the rearrangement of atoms from parent to product crystal structure occurs by the passage of a mobile semico-herent growth interface. The geometric features characteristic of a martensitic transformation are a specific orientation relationship between the product and parent phase lattices, a specific habit-plane orientation for the growth interface, and a shape change with a specifically oriented shear component. There is no alloy partition between the parent and product phases in a martensitic transformation. Martensitic transformations may display either athermal kinetic behavior or thermally activated isothermal kinetic behavior. Some martensitic transformations occur isothermally, although more commonly martensitic transformations are athermal. Isothermal martensitic transformations are suppressible by rapid cooling. In athermal martensitic transformations, nucleation and growth are not thermally activated and the transformations are essentially time-independent. Nucleation, growth, or both can be thermally activated in isothermal martensitic reactions. Transformation of the parent phase into a marten-

Jan 1, 1967

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. A. Stickels, C. M. Yen

Secondary recrystallization was investigated in vacuum-melted electrolytic iron to which 70 pm N was vacuum-meltedadded. The secondary texture is "near {554}<225>" for material cold-rolled 75 to 90 pct, the sharpness of the texture increasing with increased rolling reduction and with decreased annealing temperature. At reductions of 95 and 97.5 pct the secondary texture is &apos;"near {322)(296)". Both secondary orientations also exist as major components of the primary re-crystallization texture. Development of a strong "near {554) (225)" secondary texture appears to depend on the evolution of the Primary texture to a transition texture depleted in orientations near the secondary orientation before the onset of secondary growth. A variety of qualitative experinzents have been used to show that nitrogen is important in limiling primary grain growth. The presence of nitrogen does not seem essential for the establishment of a transition texture, but a loss of nitrogen during annealing may facilitate growth of grains in the secondary orientation. Secondary grains we shown to form initially at the specimen surface. This is not thought to indicate that surface energies are important in the growth process. It is proposed that the quasi-two-dimensional character of surface grains permits discontinuous growth parallel to the surface before secondary growth of interior grains is possible. An earlier study of recrystallization textures in 90 pct cold-rolled electrolytic iron showed that secondary recrystallization occurred after annealing for several days at 700C1 This type of secondary recrystallization, which had not been reported previously, results in the formation of a strong texture, best described by the indices "near {554}(225)". The purpose of the present work was to investigate the effect of various processing variables on secondary recrystallization in this material and determine the mechanism of secondary grain growth. LITERATURE REVIEW An understanding of the mechanism of a secondary recrystallization process depends on knowing: 1) how grains in the secondary orientation come to be in the primary recrystallization texture; 2) why normal grain growth does not occur; and 3) what factors determine the strength of the secondary texture. For secondary growth of grains of a particular orientation, a certain minimum fraction of the grains must be in that orientation after primary recrystallization. This requirement is apparently satisfied "naturally" in certain systems, i.e., when the primary texture obtained by rolling and recrystallizing material initially randomly oriented contains a sufficient fraction of primaries in the secondary orientation. However, in other cases, e.g., {110}<001> and {100}<001> secondary growth in silicon iron,2 it is necessary to enhance the fraction of primary grains in the secondary orientation by rolling and recrystallizing textured material. In the present case, the "near {554}<225>" orientation is contained within the spread of orientations found in the primary recrystallization texture of iron or bbc iron-base alloys. In systems where the main driving force for secondary growth is the reduction in total grain boundary energy, secondary growth is observed only when normal grain growth is minimized. Four ways in which normal grain growth can be limited are: 1) Limitation by a strong primary texture. When a very strong primary texture consisting of a single component or twin-related components develop, most primary grains are separated from one another by relatively immobile small-angle grain boundaries. The classic instance of this is secondary growth into the primary cube texture in some fcc metals. 2) Limitation by precipitates. Precipitates present in the proper volume fraction with a suitable dispersion will limit primary grain growth. The role of MnS inclusions in impeding normal grain growth in Si-Fe is well-documented.5 3) Limitation by sheet thickness. Normal grain growth slows drastically when the mean grain diameter is of the same order as the sheet thickness. This effect has been used to obtain secondary recrystallization in thin sheets of high-purity silicon iron.&apos; 4) Limitation by solute impurities. It is well-established that certain impurity elements in solution can have a large effect on grain boundary mobility.&apos; However, there does not seem to be any secondary recrystallization process in which primary grain size stabilization has been shown to be due to the drag exerted on grain boundaries by dissolved impurities. In certain systems, e.g., secondary recrystallization in silver,&apos; the means by which normal grain growth is limited has not been identified, and solute-impurity limitation might be suspected. In order to understand the factors which determine secondary texture strength in three-dimensional growth, it is necessary to examine in more detail the current picture of general secondary recrystallization processes. Following Cahn,9 it is assumed that the primary grains have a range of sizes and that secondary growth of one of the large grains in this distribution is possible when it exceeds a critical size with respect to its neighboring grains. The critical size depends on the ratio ?S/?p, where ?s is some sort of average grain boundary energy between the potential secondary and the primary grains and ?p is some sort of average grain boundary energy between primary grains. For a constant primary grain size, the critical size for secondary growth increases as ?$/?p increases. May and Turnbull5 have incorporated the

Jan 1, 1969

By Gregory Dybalski

The purpose of this paper is to illustrate the forecast capability of the econometric model of the cobalt industry1/ as utilized by the Federal Preparedness Agency. Forecasts from this model are illustrated from the premise that the leading producer continues production of cobalt. An alternate forecast is presented where the model structure is altered to reflect the condition where the leading producer leaves the market. All estimations and forecasts presented here are shown for illustrative purposes. The cobalt industry is highly concentrated; one company, owned by the Zaire government, accounts for approximately three-fifths of world production. The cobalt supply outside of Zaire is determined by the level of activity of copper or nickel markets, as cobalt is mined as a by-product of copper or nickel. The demand for cobalt reflects a diversified usage pattern; cobalt is used mainly in heat and corrosion-resistant materials, high- strength materials and permanent magnets. According to 1974 U.S. consumption data superalloys accounted for 22%, magnetic alloys 18%, cutting and wear-resistant materials 13%, and catalyst 7%. Foreign consumption is probably similar in terms of usage categories, but the relative order of the categories is in variance.2/ The Cobalt Model The cobalt model&apos;s object is to explain consumption, supply and price movements by utilizing statistically estimated equations. Central to the econometric model is the role of Zaire as the profit-maximizing "dominant firm". Zaire sets the price that is most profitable for itself. The price of cobalt depends on industrial demand, production of other firms, and net exogenous purchases, such as government

Jan 1, 1977

By J. B. Clark, A. S. Yue

The zone-melting technique can be adapted for the de-termination of the eutectic composition in complex metal systerrzs. The application of this method is demonstrated in a simple eutectic system, Mg-AE, in which the eutectic composition is known and in a complex ternary system, Mg-Al-Zn, in which the literature is uncertain as to the composition of the ternary eutectic. The advantages and limitations of this unique approach for the determirution of the eutectic composition are discussed. ThE eutectic composition in phase diagrams is usually determined by thermal analysis of a series of arbitarily selected alloy compositions. The temperatures of the liquidus and eutectic arrests for each alloy are plotted and the eutectic composition is estimated by extrapolation to the entectic temperature of the curve formed by the liquidus arrest temperatures for the series of alloys. Although this approach readily yields the eutectic temperatures, several dekrminations are needed to estimate the eutectic composition, even in a simple system. In a complex ternary system, a great many determinations are often necessary to estimate, even approximately, the ternary eutectic composition. Thus, the conventional method is inherently tedious and time consuming. The application of zone melting provides a relatively efficient method of determining the eutectic composition.&apos; As an illustration, consider the zone melting of an alloy composition C, in the simple eutectic system A-B, shown in Fig. 1, under the ideal conditions of infinitely rapid diffusion in the liquid, no diffusion in the solid, and ease of nucleation of both phases. As the zone moves along the bar, the composition of the zone is enriched by solute rejected during the freezing of the a phase and the zone composition approaches the eutectic composition CE.Once the zone composition attains the lowest melting composition, i.e., the eutectic composition, it remains at this composition as the zone moves along the bar and finally freezes as such at the end of the bar. Chemical analysis of the end of such a zone-melted bar then should yield the eutectic composition CE of the system A-B. A corresponding analysis can be made for a ternary eutectic system. Under the ideal conditions noted above, only one pass of the molten zone is required to yield the eutectic composition. Experimentally, however, a solute-rich layer forms at the solid-liquid interface2 and the composition of the zone does not attain the eutectic composition as rapidly or as uniformly as in the ideal case outlined above. But with agitation of the melt, the ideal conditions can be approximated experimentally. Also, as shown below, zone melting permits a cumulative build-up of the solute at the end of the bar to the eutectic composition. The purpose of this paper is to demonstrate this unique method for determining the eutectic composition. The method is here applied to two systems: first, to the binary Mg-A1 system, in which the composition is well established, and second, to the complex Mg-Al-Zn system in which there is doubt concerning the composition of the ternary eutectic. EXPERIMENTAL PROCEDURE The zone-melting apparatus used in this study is described in detail elsewhere.3 Briefly, the binary alloy rods (5/8 in. in diam and 9 in. long) and the ternary alloy rods (5/8 in. in diam and 6 in. long), with the compositions given in Table I, were zone

Jan 1, 1962

By B. H. Bergstram, C. L. Sollenberger

When glass spheres are crushed by slow compression loading, the outer lune-shaped fragments resulting from the fracture consistently fly outward at high velocity. About 45 pct of the strain energy fed into the sphere-platen system reappears in the form of the kinetic energy possessed by these fragments. These measurements were obtained from high-speed photographs. This kinetic energy can be utilized for addtional comminution if the fragments are allowed to impact against a suitable structure. Comminution theory has advanced considerably in recent years by the study of this unit operation under laboratory conditions. Some of the parameters have been isolated, but the experimental measurements of the pertinent quantities, such as energy, particle size, etc., are still only made prior to and after the conclusion of a fracture sequence. The catastrophic fracture process itself has not been adequately studied from a comminution point of view. It has recently been suggested by Gilvarry that the fragments which result from the free crushing of a single glass sphere by slow compression contain a considerable amount of kinetic energy after fracture. This kinetic energy, if properly directed, possibly can be partially utilized to cause additional fracture. In this paper a hypothesis will be presented which suggests that this kinetic energy is necessarily present and that its dissipation is the process by which a large part of the thermal energy imparted to the crushed product is generated. Evidence supporting the existence of kinetic energy and its utilization for secondary fracture will also be presented. THEORETICAL A previous paper4 has shown that the load-deformation curve of a system composed of an elastic sphere gripped by a pair of parallel platens, can be predicted by a consideration of the theories of Hertz as summarized by Timoshenko.&apos; The deformation A, of one half of the system is given by which states that the deformation is a function of the mutually applied load, P, the radius of the sphere, R; and the respective physical properties of Poisson&apos;s ratio, v, and Young&apos;s modulus of elasticity, Y. The shape of experimental load-deformation curves conform to this relationship. The energy input to the sphere-platen system, can be predicted from the integral of the load acting through the appropriate distance, dA. Since dA can be evaluated in terms of P from the derivative of Eq. 1, this integral can be integrated between limits of 0 and P. The test sphere, however, is loaded at not one but at two points of contact, i.e., at both ends of a diameter, and hence the total energy input, E, is twice the energy input at each end, or The energy input to the system calculated from this equation corresponds to the energy computed from the measured area under the load-deformation curve. Timoshenko, considering the impact of two perfectly elastic spheres, has shown that the inter-penetration distance A is given by - m f (D (^ * ^t w as modified for the special case where one sphere is of infinite radius, i.e., its surface is a plane; where M is the mass of the finite sphere of radius R, and V is the velocity of approach at the start of an impact and also equals the final velocity of separation for perfectly elastic bodies. Because A is also a function of the load and the elastic properties, as shown in Eq. 1, the velocity, V, can also be calculated in terms of the elastic properties and maximum load, P, or

Jan 1, 1961

By A. G. Worthing

Black: Bodies.-In the ordinary conception, a black object is an opaque object that reflects but little of the light that is incident on it. This means naturally that such an object is a good absorber of luminous radiation. The black body; which is so closely connected with high-temperature measurements, represents the limit in blackness of all black objects. It is a body that not only absorbs all visible radiations but also all other radiations in the infra-red and the ultra-violet regions of the spectrum which are incident on it. No substance is known that is completely black; platinum black, one of the nearest if not the nearest representative of the ideal, reflects 1 per cent. or so of ordinary visible radiation. The closest approach to the ideal is a small opening in the wall of a relatively large opaque cavity. Any radiation incident on this black body will be almost completely absorbed if the relative dimensions are properly chosen no matter what the material may be. The great difference between the blackness of such a cavity and of lampblack, for instance, will be apparent to one who makes the simple test. Non-black Bodies.-The field of non-black bodies covers all real bodies. Their characteristics are extremely varied. So far as absorption of radiation-is concerned, these bodies range practically from the almost completely black, platinum-black, and lampblack, which absorb all but a fractional part of 1 per cent. or so of the incident radiation, by an infinite variety of steps to freshly polished silver, which ordinarily absorbs only a few per cent. The exact percentage absorbed depends not only on the nature of the incident radiation, but also on the temperature of the body, the condition of its surface, the angle of incidence, the nature of the surrounding medium, and on certain other less important conditions. As consequences of these varied characteristics, we have not only the differences of color of ordinary objects, but also the changes of color that any one object undergoes on heating or when lighted front various directions. This complexity of the phenomena, in a way, is responsible for the meagerness of knowledge, regarding materials at elevated temperatures. Measurement of High Temperatures.-Excepting in cases where the thermocouple or the gas thermometer are applicable, in which case the temperatures obtained are true temperatures regardless of-the material" studied, high, temperatures are almost always, if not always, determined from measurements of radiation. In fact, determinations of temperature from this latter point of view are often so much more convenient than the thermocouple and especially the gas-thermometer determinations that, in the region where all of these types of measurements may be made, the radiation measurements are often preferred. This is true even though the temperatures usually thus directly determined are not the actual temperatures, a consequence of the sources of the radiation being non-black bodies; in other words, a consequence of being concerned with iron, or glass, or tungsten instead of small openings leading to relatively large-cavities uniformly heated. Coordination of Experimental Results.-In order that data on iron, glass, tungsten, or other non-black bodies obtained in one laboratory, may be, correlated with similar data obtained elsewhere, temperatures must be expressed on a common scale. The true temperature scale is the natural scale for this purpose it is ordinarily the scale to which all other temperatures can be most directly reduced. When the measurements depend on the radiation, a knowledge of emissive powers repre-

Jan 9, 1919