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By A. J. Mortlock

Cobalt and nickel have been diffused at tracer concentrations in gold at several temperatures in the range from approximately 700° to 950°C. The diffusion penetration profiles were determined by a serial sectioning technique in which the gold is first anodized and then the anodic layer is dissolved in acid. In this ulay sections as thin as 250A could be removed reproduci-bly. In all cases, the region close to the specimen surface was characterized by irregular behavior in the sense that the logarithm of concentration was not linear in the square of the penetration distance. In sotne cases, there zuas an indication of the operation of very slow dijfusion in this region, while in others the apparent diffusion coejj'icient was negative. Possible reasons for this anomalous behavior are briefly discussed. In recent years it has been found that the region close to the surface of a metal can sometimes exhibit anomalously slow diffusion characteristics relative to the interior of the metal. One of the best examples of this fact is the work of Styris and omizuka,' who showed that the apparent diffusion coefficient for zinc in the region withi: about 1 p of the free surface of copper was about ,,,, that at deeper penetrations. This result is particularly interesting, because it is free from the possibly complicating effects of low solubility of the diffusing tracer in the solvent metal. In the case of diffusion under conditions of low solubilitjr, interpretaticn of the results in terms of lattice diffusion is difficult because of the enhanced short-circuiting produced by segregation to dislocations.2'3 Measurements by Duhl et 1. suggest that cobalt diffusing in gold may also show a near-surface effect of this type. Once again the solubility is high, so that this result could be of great interest. However, the technique used for analyzing the diffusion penetration zones by Duhl, viz. the counting of residual gamma activity in the specimen following sectioning, appears to have indicated a near-surface effect in a parallel experiment on the self-diffusion of gold reported at the same time. The latter result is known to be spurious, since Kidson5 has demonstrated that self-diffusion in gold does not show this effect. Duhl et 01. also reported some measurements on the diffusion of nickel in gold, but failed to give any data for the near-surface region. As the solubility of nickel in gold is high, such data would also be of special interest. We, therefore, decided to conduct another set of experiments on the diffusion of nickel and cobalt in gold, using a sectioning technique that allows the individual sections to be assayed for solute content and thus gives direct determinations of penetration profiles. Also, by sectioning with an anodizing/stripping tech- nique, very thin layers can be removed and the region close to the surface studied in detail. MATERIALS The gold specimens were supplied as single crystal disks $ in. in diam by a in. high by Monocrystals Co. of Cleveland, Ohio. The gold itself was of spectro-scopic purity, i.e., better than 99.99 pct pure. METHOD Specimen Preparation. One flat end face of each gold crystal was spark planed with a Servomet spark erosion machine set for minimum spark energy. Following this treatment the crystals were preannealed for 2 to 4 days at temperatures of either 400" or 700°C. The three crystals preannealed at 700°C showed signs of recrystallization. The spark-planed end face of each crystal was then coated with the appropriate amount of 63i or 60 radioactive tracer. This deposit was laid down in a simple plating bath containing the as-supplied solution of the radioactive isotope as well as sufficient ammonium oxalate to saturate the solution. Some ammonium oxalate remained undissolved on the floor of the bath for this purpose. During plating further additions of ammonium oxalate were sometimes required to allow the plating to continue satisfactorily, perhaps due to passivation of the undissolved oxalate already present. The thickness of the deposited layer was determined by comparison of the apparent surface activity of the plated specimen with that of a similar specimen having a weighable deposit of the isotope on its end face. Correction for self-absorption of the radiation was made in this calculation. Annealing. The deposited crystals were annealed in a hydrogen atmosphere in sealed silica tubes. During this heat treatment they were supported, active face down, on optically flat silica plates. The temperature was measured with calibrated Pt vs Pt-10 pct Rh thermocouples, and the tabulated values can be taken to be correct to Z°C. All the crystals showed evidence of recrystallization following these heat treatments, suggesting that initially they may not have been good single crystals or had suffered strain during delivery. Concentration Profile Analysis. After annealing, the crystals were sectioned by the anodizing-stripping technique.6 The anodizing involved suspension of the specimen with its cylindrical axis horiz6ntal by a gold wire in a 200-ml beaker containing 1 M Hg304. A cathode in the form of a strip of gold sheet, 2 in. wide and positioned to be in contact with the curved side of the beaker, completely encircled the specimen. An anodizing current of 30 ma, corresponding to a current density of 5 ma per sq cm on the surface of the specimen, was passed for times ranging from 5 to 150 min depending on the thickness of gold to be removed; the solution was stirred continuously during this process. Following this treatment, the specimen

Jan 1, 1969

By Charles Malcolmson

IN the United States, improvements in methods of combustion have made possible the use of the smaller sizes of anthracite. This coal is now being reclaimed from the culm banks accumulated by the miners in the more prodigal years. To-day the freshly mined "slush" is segre¬gated and stored against the time when, through briquetting or some other means, it may be utilized as a commercial fuel. For many years Europe has achieved enviable results in the conservation of her small coal by briquetting. This profitable industry, first placed on a commercial basis in France in 1842, has grown to such magnitude that the "'production during 1913 exceeded 36,000,000 short tons. Briquets produced in Great Britain are used principally for steam purposes and the greater part of the output is either exported or taken by the Admiralty. On the Continent the briquets are sold in all branches of the coal trade. The French railways consume from 16 to 40 per cent. of their fuel in briquet form, and in Germany the lignite briquets, (of which 20,000,000 tons were produced in 1913) are as familiar and interesting to the American traveler as the huge porcelain stoves in which they are burned. It is not strange, therefore, that aggressive and far-sighted promotors heralded this means of converting our ubiquitous coal waste into revenue. To the superficial student the briquetting process seemed so simple as to make success easy. It is for this reason principally that the path of the industry in America has been strewn with failures. The rash enthusiast had either not worked out the mechanical problems involved or had failed to grasp the local conditions under which the briquets must be made and sold. It may be confidently stated, however, that in spite of the many vicissitudes through which it has passed, coal briquetting is now an accomplished economic success in this country, and as a profitable adjunct to the coal industry it has come to stay.

Jan 2, 1915

By James Pollock

SUMMARY THE possibility of colloidal deposition of cinnabar has been neglected. In opalite deposits cinnabar exists in particles within or near the colloidal size range. Colloidal processes have been admitted to be operative in hot springs and low-temperature deposits similar to most cinnabar deposits. Mercuric sulphide sols are stable to elevated temperature and pressure, and in nature probably are chiefly affected by the electrolytes in solution, dilution of colloid, and presence of protective colloids as silica. The stability of mercuric sulphide sols to electrolyte is measured, and shown to be greatly increased by dilution and by the protective action of silica. Mercuric sulphide sols follow the Schulze-Hardy valency rule, therefore the precipitating power of complex mixtures of electrolytes can be computed roughly. The stability of mercuric sulphide sols is shown to be greater than the equivalent precipitating power of the electrolytes in a hot spring depositing mercuric sulphide. It is concluded that finely divided or earthy types of cinnabar are colloidally deposited. POSSIBILITY OF COLLODIAL DEPOSITION While colloidal solution has been suggested as a means of transport for a number of minerals, such as the sulphides of antimony, arsenic, and iron, it has been neglected in connection with mercury. This is surprising because there exists positive evidence that cinnabar is present in certain deposits in particles of colloidal or near colloidal size. Colloidal transport could result from either the rapid dilution or neutralization of alkaline sulphide solution bearing mercury coming in contact with deep ground waters, or from colloidal solution near the original source and subsequent flow to the point of deposition unchanged. That the dilution of a mercuric alkaline sulphide solution will precipitate mercury sulphide in colloidal form has been demonstrated a number of times and is easily confirmed. The dilution hydrolyzes the alkaline sulphide Na2S to the corresponding hydroxide and hydrosulphide NaOH and NaHS, and the diminution of the concentration of alkaline sulphide reduces the solubility. It is not the contention of this writer that colloidal deposition is the mode of transport of mercuric sulphide in all mercury deposits, but that the stability of a mercuric sulphide sol, as demonstrated below, in waters that are similar to those that have deposited mercuric sulphide necessitates consideration of this possibility in many deposits, especially those of the hot-spring and so-called opalite type. EVIDENCE OF COLLOIDAL DEPOSITION Ross1 has shown that most deposits of quicksilver are formed at low temperatures and pressures, and probably by solutions that have relatively simple chemical compositions. In most cases the solutions are probably similar to those observed in hot springs, and in two instances-at Steamboat Springs, Nevada, and Sulphur Bank, California-hot springs have been reported by Becker as actually depositing cinnabar.2 Opalite deposits were believed by early investigators to be surface phenomena

Jan 1, 1944

By K. R. Van Horn

RESIDUAL stresses in metals operate under a cloak of mystery, as they have neither been seen in the laboratory nor detected by means of the microscope. In spite of their phantom-like nature, they frequently exert metallurgical effects that cannot be ignored. In some cases the results have been detrimental, causing rejections or premature failures, but frequently the effects have been highly beneficial to the producer or consumer of metal products. First, however, what is a residual stress? When a metal is plastically deformed by bending, rolling, pressing, or by a phase transformation or precipitation from solid solution, or by a sharp temperature gradient resulting from nonuniform cooling, quenching, or welding, it remains in a state of strain. The strains or strain gradients produced by such operations and retained after all external forces are released are known as residual strains, and the accompanying stresses as internal or residual stresses. Many defects or failures in metal products have been ascribed to residual stresses, sometimes erroneously, because there was no other apparent explanation after the usual metallurgical tools of diagnosis had been applied. For example, during World War 11, the forged aluminum alloy aircraft cylinder head in the reciprocating engine began to replace the cast head with the familiar cooling fins. The fins were machined in the solid forged head by an ingenious milling operation. One plant reported an epidemic of excessive distortion during the delicate high-speed milling. A thorough examination revealed that the composition, heat treatment, mechanical properties, and metallurgical quality of these heads were comparable to those of forgings that machined satisfactorily. It was then claimed that the cause of the machining difficulties was connected with residual stresses resulting from the quenching during the solution heat treatment. An elaborate stress analysis actually demonstrated, however, that the magnitude of residual cooling stresses was lower in the cylinder heads which machined poorly than in those which were satisfactory in this respect. Subsequent tests proved that the machining problems in this case originated from variations in the tools and tool design. Sources of Residual Stresses in Metals Residual stresses are of two origins—mechanical and thermal. Thus, stresses may be produced in a metal by any cold-working process. The distribution and magnitude of these mechanically produced stresses can be calculated in a satisfactory, although approximate, manner for such simple cases as bending, torsion, and expanding of tubes. However, most manufacturing processes are too complex, and the original stress-strain relations in the products are not sufficiently known to permit calculation of the resulting residual stresses. Also, a specific process, such as wire drawing, may vary in complexity or uniformity of working, and large or small residual stresses may result, depending on the conformation of the dies and other features of the working process. Neither substantially unidirectional deformation, such as can be imparted by stretching a metal product having essentially the same mechanical properties throughout the cross section, nor deformation

Jan 1, 1954

By Richard E. Goodman

Rock slope stability assumes different roles in decision making as a mining venture develops and, accordingly, geological investigations vary in thought and in deed according to the project stage. During exploration, stability questions bear on the decision whether or not to mine, because their resolution affects the cost of mining. During the mine lay-out stage, stability is a key factor in deciding how to mine. Finally, during mine operation, stability affects safety and operating costs, and therefore, pit productivity. Among the many considerations influencing stability, rock mass classification and geological environmental factors count heavily. The rock mass behavioral class depends upon the rock character and its degree of fracturation. The loads on the rock are derived from the environmental factors of initial state of stress and the water regime. Of course, stability is also tied to a host of non-geological factors such as the pit geometry, mining style, relative wealth, philosophy of mine operation, and accident history. METHODS OF STABILITY EVALUATION AND CORRESPONDING INVESTIGATORY TOOLS The purposes of the geological investigation are to identify and evaluate the geological factors influencing stability so that the vital questions can be analyzed. The tools selected for stability analysis reflect the stage of development of the mining scheme and therefore the geological investigations, which must furnish data for the analyses and must vary with the project stage. For exploration and mine planning, the methods of resolving stability questions must meet the need to evaluate numerous parameters in limited time; examples of such methods are stereographic projections (1, 2, 3) charted solutions(4) and simple physical models (5, 6). An investigation program that employs geological mapping tools and aids to mapping, such as geophysics, with relatively few rock tests, is in balance with these analytical methods. First data about the water regime are obtained from observed piezometric levels, and the initial state of stress is queried simply through geological inference and experience. In the layout stage more elaborate physical scale models (7) and perhaps finite element models (8, 9, 10, 11, 12), will be relevant to the design process and therefore much more detailed geological investigation is required. The scale of observation of both rock material and joints will be significantly enlarged and mechanical tests of rock and joint strength

Jan 1, 1972

By B. H. Bergstrom, C. L. Stevenson

In any process wherein materials must be pelletized, a crucial period exists during the interval between the manufacture of the green pellets and their subsequent heat treatment. The pellets must possess sufficient strength and plasticity to withstand conveying and sizing. Also, they must be neither excessively brittle nor excessively plastic when placed in a bed on a traveling grate for heat treatment. An acceptable pellet, in the event sufficient forces are applied to cause its fracture, will merely split into two or three large fragments which would not drastically alter the permeability of the pellet bed. However, when brittle pellets are broken, they shatter so that the resultant fine particles either decrease the perimeability of the bed or become entrained in the gas stream and thereby cause dust problems. On the other hand, excessively plastic pellets may not break at all but may merely flatten. This would seriously hamper bed permeability. In the past, pellet evaluation has usually been left to the creative and artistic talents of the balling operators. A multitude of techniques have evolved, of which the most common is the simple compression test. For this test a hand-operated device loads single pellets to fracture, but reliability is strictly operator- dependent. Probably the next most common test is the drop test, which is conducted according to several different procedures. This is an important quantitative test for estimating the amount of handling a pellet will withstand. There are many other tests, such as pinching a pellet between the thumb and index finger, but none are capable of producing reproducible results.

Jan 4, 1962

By T. A. Wilson, S. L. Hoyt

THE plastic deformation of slender single crystals of zinc has been described in some detail in the paper by Mark, Polanyi and Schmid,1 which has become a classic, and also by one of the present authors in a somewhat shorter account.' The study of single-crystal zinc is termed classical because zinc single crystals offer, perhaps, the best material yet available for the study of atomic behavior during deformation and the effect known as "strengthening" in metals. A considerable amount of additional work has also been done on single-crystal zinc, but as it is not closely related to the present paper it will not be considered. Throughout all the former work, the mechanism of plastic deformation first described by Mark, Polanyi and Schmid has been assumed to hold. This may be said to offer the strongest confirmation of its correctness. Even so, the picture of the process has never been as completely portrayed as is desirable. The first object of the present paper is to describe work that has been done in this field, and which is even yet being carried on, in the hope that a more complete picture may be obtained. Mathewson and Phillips' have recently described a new mechanism of the deformation of zinc based on their study of large rectangular crystals. One of their conclusions was that deformation produced twinning with a rotation of some of the basal planes into positions 94° removed from their original position; a position almost the same as that of the prismatic planes before twinning. A second conclusion was that fracture occurred along these basal planes in their new position, and, therefore that fractures previously regarded as prismatic were in reality basal. Such findings are of great significance and they raise a question as to the generality of such behavior. Professor Mathewson's opinion is that even the slender cylindrical single crystals behave in the same manner as his large rectangular crystals when strained by simple tension.

Jan 1, 1928

By N. W. Lord

The process of molten-zone refining is analyzed for long ingots and many zone passages. Formulas are derived which give the resultant impurity distribution in terms of finite series. A comparison with the approximate procedure of Hamming is given. HE physical principles and applications of an extremely physicalprinciple efficient form of metallurgical refinement has been described by Pfann. The purpose of the present paper is to describe a method of analyzing exactly the particular program used which enables the segregation effect to be predicted for any number of molten-zone passages in a long ingot. The method is applied to the particular case of refinement of an ingot whose impurity initially is uniformly distributed throughout its length. A number of molten zones of equal length are passed through the ingot effecting a radical redistribution of impurity. Pfann has indicated an approximate method, due to R. W. Hamming, of calculating the resultant concentration after each successive zone pass for a particular value of the segregation constant defined in his paper. Here a solution will be presented in terms of the number of zone passes and the segregation constant. The expression, though cumbersome, is exact and susceptible to ordinary numerical computation procedures. The results of a similar computation using the procedure of Hamming are presented in a table together with the exact results of the present method. The discrepancy in terms of absolute concentrations is tabulated for the first eight zone-lengths. To establish the notation (which follows that of Pfann1 as closely as possible) and physical basis of the analytical equations, the physical model and principal assumptions may be reviewed. An alloy of two elements, where there is formed a continuous range of solid solutions, usually does not melt as a simple compound. Rather, a temperature is reached where the solid solution is in heterogeneous phase equilibrium with a liquid solution of different composition. The temperature dependence of these equilibrium compositions forms part of the phase diagram. For very small concentrations of a solute B in a solvent A, this usually takes the form of Fig. 1. Sometimes the solidus and liquidus slope upward. This corresponds to a segregation constant (defined below) which is greater than unity. The segregation constant is now defined as k = Cn(x)/CnI(x) [1] where C,,(x) is the impurity concentration in the solid ingot at distance x during the nth passing of a molten zone and Cnl (x) is the impurity concentration of the liquid zone from which the solid at dis- tance x is formed (see Fig. 4 of ref. 1.) C (x) remains the same after passage of the zone. The constant k may be either greater or less than unity in general. Purification in the former case is effected only in a finite ingot and in the portion that is melted last. For k less than unity purification is effected even in an infinite ingot. The method which follows gives, in the former case, the successive increases in impurity concentration and, in the latter case, the successive decreases in concentration. The general case of impurity redistribution will be considered first, and purification will be discussed later on. The analysis rests on the following assumption: The movement of the zone is too rapid to allow appreciable atomic rearrangement in the solid sections and too slow to disturb the uniform impurity distribution in the liquid zone characteristic of equilibrium. Hence, the composition in the solid at the left solidifying interface will be determined by Eq. 1 while the impurity concentration of the liquid zone will be uniform throughout its length. The reasoning which follows closely parallels that of Appendix 11 in Pfann&apos;s paper. It is reviewed here for the case of the nth zone pass in order to make clear the meaning of an operator essential to the present method. Fig. 4 of ref. 1 shows the movement of a molten zone of length 1 in an ingot of total length d. Each Cn(x) can be determined from the condition that the amount of solute added to the zone during an incremental advance, dx, is due to the melting in of a solid portion C(x)dx and the freezing out of kCnl(x), that is d I —r- CnL (x) dx = Cn-1 (x+l)- kCnL (x) dx or, in terms of Cn(x) d k k —— C,(x) +—c.(x) =— Cn-1 (x + l). [2] dx l l This, of course, is derived from the main assumption, the fact that 1 is constant, and that the total impurity content previously present up to x + 1 is constant . A correction has to be made for the region (d — nl) < x < d. This is due to the zone length changing during the passage of the solidifying interface beyond x = d — 1. Since the general solution would be too complicated otherwise, only the region 0 < x < d — nl is considered. The general solution of Eq. 2 is

Jan 1, 1954

By N. S. Stoloff, R. G. Davies

A study has been made of the efject oj different dislocation-precipitate interactions upon the temperature dependence of the flow stress of aged Ni-14 at. pct A1 alloy. It is observed that when the dislocations bow between widely spaced (-20004 coherent Ni3Al particles the flow stress decreases with increasing temperature in the normal way. However, when the dislocations cut closely spaced (-5004 particles the flow stress is independent of temperature from -100 to 600°C, due to a balance between softening of the matrix and an increase in strength of the particles with increasing temperature. The retention of strength at high tempera-tures of commercial nickel-base alloys, which are strengthened by the precipitation of a phase based upon Ni3Al, is thought to be due to the unusual strength properties of Ni3Al. The flow stress of Ni3Al increases continuous1y from -196"C to a maximum at -600"C. It is concluded from a series of thermal-mechanical tests that the sevenfold increase in flow stress over this temperature interval is due to a lattice effect and is not diffusion-controlled. The flow stress of precipitation- or dispersion-hardened materials depends on the resistance to dislocation motion within the matrix and the extra energy required for dislocations to bow between or to cut particles. If the dislocations bow between the particles or if the strength of the cut particles is constant with temperature, then the flow stress of the precipitation-hardened alloy must decrease with increasing temperature due at least to the decrease in elastic modulus of the material. There will be softening also from thermally activated cross-slip or climb, offering an additional degree of freedom for dislocations to avoid particles. For example, in the case of nickel containing a dispersion of thoria,&apos; which most probably deforms by dislocations bowing between particles, the flow stress decreases by about 50 pct between 25" and 650°C. In A1-Cu alloys2 aged to produce the 8" precipitate, dislocations cut the particles, and the flow stress decreases by about 20 pct between -269" and 25°C. However, many commercial high-temperature nickel-base alloys, for example Inconel-X and Udimet-700, exhibit little or no decrease in flow stress with increasing temperature up to about 700°C. A characteristic feature of these alloys is that they are strengthened by the precipitation of a phase based upon Ni3A1. Guard and westbrook4 and flinn&apos; have shown that Ni3Al (and alloys in which a third element such as molybdenum or iron is substituted for part of the aluminum) is unusual in that the hardness and flow stress increase with temperature to a maximum at about 600°C. For the flow stress of a precipitation-hardened alloy to be independent of temperature we propose that the particles must be cut by dislocations moving through the matrix and that the strength of the particle must increase with increasing temperature. Theories of precipitation hardening do not take into account the flow stress of the dispersed particles that are cut during deformation; the only dissipative process usually considered7 is the creation of interface within the particle and between the precipitate and matrix. The purpose of the present investigation has been to study in detail the temperature dependence of the flow stress of a nickel-base alloy strengthened by the precipitation of Ni3Al in two structural conditions such that when deformation occurs it does so by dislocations a) bowing between the particles and b) cutting the particles, respectively. A simple binary Ni-14 at. pct A1 alloy was chosen because considerable information is already available for this system concerning phase equilibria and precipitation reactions and rates.&apos; Dislocation-precipitate interactions in the binary alloy should be similar to those in the more complex commercial alloys. In addition, the mechanical and physical properties of NisAl were studied in detail in the hope of elucidating the mechanism by which the strength increases with increasing temperature up to 600°C. EXPERIMENTAL PROCEDURE For the study of the effect of precipitation of Ni3A1 upon the temperature dependence of the flow stress, an alloy containing 14 at. pct A1 was utilized; a Ni-8 at. pct A1 solid-solution alloy was employed as a comparison material. Vacuum-cast ingots were hot-rolled at 1000°C and cylindrical compression samples, 0.20 in. diam by 0.40 in. high, were prepared from the 1/4-in.-diam rod. Specimens were recrystallized and solution-treated at 1000°C for 1/2 hr and then water-quenched. A preliminary study revealed that, when the Ni-14 at. pct A1 alloy was aged for 1 hr at 700°C, significant precipitation hardening was obtained, and that the structure was free from grain boundary discontinuous precipitation; an overaged condition was produced by annealing the aged specimens at 850°C for 1 hr. To circumvent the difficulties involved in the hot rolling and swaging of Ni3A1, compression samples,

Jan 1, 1965

By H. D. Williams, R. A. Scriven

The distribution of elevation angle of finite plane facets distributed symmetrically about a given axis is derived in terms of the angular distribution of lines which these facets produce in a plane section parallel to the axis. It is assumed that the facets are not markedly elongated in preferential directions. The theory is intended for application to the angular distribution in polycrystalline metals of slip planes and of particular grain boundaries on which certain phenomena such as cavitation can occuv. Illustrative examples are given in closed form and simple numerical techniques are de-ueloped for practical application. The results are applied to the distribution of cavitated boundaries in a copper specimen after fatigue at 400°C and it is found that voids form on the boundaries that exper~enced maximum shear stress. When investigating the distribution of elevation angle between a given axis and planes symmetrically distributed about this axis the angular distribution observed in a plane section parallel to the axis is not necessarily the same as the required distribution. Consequently a technique for processing the results obtained by sectioning methods is required. An example where such a technique would find application is in the problem of intercrystalline void formation during uniaxial tensile creep. Two theories have been proposed to explain this cavitation in terms of the normal and the shear components of stress, respectively. Hull and Rimmer (1959) postulate that the growth of intercrystalline voids is controlled by the rate of supply of vacancies from the grain boundary, the local vacancy concentration being proportional to the normal stress on the boundary. Gifkins (1956) considers that slip arising within a grain causes a ledge to be formed at the grain boundary which is subsequently opened up into a cavity by grain boundary sliding. It might be possible to differentiate between these mechanisms by determining the angular distribution of grain boundaries containing cavities since the former theory predicts a predominance of cavitated facets normal to the stress direction whereas the latter should favor an angle of 45 deg to this direction. In a similar manner an indication may be obtained of the type of mechanism responsible for intercrystalline cavitation during high-temperature fatigue. Davies and Wilshire (1962) have analyzed the slip-plane distribution in a nickel specimen but the problem was not treated in any detail nor was any account taken of the finite extent of the planes being sectioned. Hilliard (1962) has given a very general account of how anisotropy in the microstruciure can be related to measurements taken in one or more plane sections by expressing both the measured and the true angular distributions as expansions in spherical harmonics.* The present analysis is con-

Jan 1, 1965

By H. Udin

G. KUCZYNSKI* and B. H. ALEXANDER*—This paper represents a most noteworthy attempt to evaluate experimentally the surface tension of a solid metal. Because of the great importance of such measurements, any proposed method should receive the closest scrutiny before the results can be considered reliable. In regard to the experimental method, we think that the marking of the gauge length by means of tieing knots in the wire may be the cause of some of the spread in the results. Such a knot may be expected to tighten slightly, and thus increase the gauge length, when placed under stress at high temperature. Although this effect would be very small, amounting at most to only a few times the wire diameter. A fairly tight knot in a wire will decrease the wire length by about ten times the wire diameter, thus only a slight tightening of the knot would cause considerable spread in the results. Upon plotting the stress strain curves from the authors&apos; data, the writers found that there was a fairly consistent tendency towards an S-shaped curve, instead of a straight line. Such an effect could be caused by the tightening of the knots. The writers think, however, that the experimental results are fairly reliable, but that there may be other methods of interpreting them depending upon what mechanism is assumed to be responsible for the shrinkage of the wires. The authors have assumed that the stress due to surface tension results in viscous flow. It should be made clear that it has never been demonstrated that viscous flow can occur in metal crystals even at very high temperatures. The experiments of Chalmers13 on tin, which are so frequently quoted as giving evidence of viscous flow at low stresses are by no means satisfactory. In his experiments, Chalmers found that only the initial rate of flow was approximately proportional to stress. He also found that the rate of flow varied markedly with time which, in his experiments, was less than 2 hr. Inasmuch as there is no proof of viscous flow in metals, and the authors have brought forth no conclusive evidence on this point, it may be worth while to investigate other possible mechanisms of material transport which would account for the shrinkage of the wires. The writers wish to point out that in these experiments the shrinkage of the wires can be adequately explained, according to a self diffusion mechanism. Thus, if we assume a concentration gradient for self diffusion which is a function of the radius of curvature of the wires, and assume that diffusion will occur so that the total surface area is decreased, we find the following expression for the self diffusion coefficient: where k = Boltzmann constant r0 = initial radius of the wire T = absolute temperature ? = surface energy 8 = interatomic spacing t = time e = strain at zero applied stress Eq 19 may be used to evaluate the self diffusion coefficient of copper, using the strain measurements obtained by the authors for zero stress as obtained by extrapolating their curves for 5 rail wires. By inserting a reasonable value for the surface energy (1500 ergs per cm2) we find: -66,000 D = 5 X 10e RT [20] The activation energy is of the correct order of magnitude, but the frequency coefficient is much too high, indicating that surface diffusion may be playing an important role. This discrepancy in the action constant is much smaller than the corresponding discrepancy obtained by the authors for the viscosity coefficient. The writers by no means propose that this proves that the shrinkage of the wires is due to self diffusion but we merely wish to point out that there are explanations other than that given by the authors. In this, as in any kinetic phenomena, it is necessary to study the rate of the process before anything can be said about the mechanism. The determination of surface tension given by the authors is based upon an interpretation of the data which embody the concept of viscous flow. The final proof of this concept will be obtained only after the time relationships confirming the authors&apos; Eq 15 have been conclusively established. The rough linearity of the stress strain curves obtained by the authors for experiments run the same length of time should not be considered as proving that viscous flow is occurring. H. UDIN (authors&apos; reply)—All of the test specimens were annealed at 1000°C for an hour or more before preliminary measurements were made. During this anneal the wires recrystallize, and the greatest part of grain growth takes place. Also, the knots sinter at the cross-over points. This does not in itself eliminate the possibility of end errors, although it greatly decreases their probable magnitude. It is still possible that some extension occurs due to creep in shear at the sintered points. If so, this effect would be quite independent of and superimposed on the normal shrinkage or extension of the wire itself. Within the precision of the experimental results, straight lines satisfy the data as well as do any other simple curves. Until data of greater precision are obtained, it is futile to discuss any possible trends away from linearity. The disagreement between Kuczynski and Alexander&apos;s Eq 19 and our Eq 18 is one of semantics and mathematics, not mechanism of flow, since Eq 18 is based on the self-diffusion concept of viscous flow. It would be interesting to learn how the mathematics leading to Eq 19 deviates from that of Eyring and of

Jan 1, 1950

By F. R. Morral, K. T. Aust

The preferred orientation and earing characteristics of ZS aluminum were studied. An empirical correlation was obtained relating earing behavior and variation of mechanical properties for face-centered cubic metals. Strain-ratio mecsurements for ZS were found to be in good agreement with Hill&apos;s theory of plastic anisotropy. DIRECTIONALITY in sheet metals may be revealed by earing in a cupping test, or by the variation of mechanical properties of tensile specimens taken at different angles to the rolling direction. However, no simple correlation appears to exist between earing and variation in mechanical properties in metals and alloys studied.1-5 Aluminum of commercial purity (known as 2S, with a specified minimum of 99.0 pct Al) cast by the direct casting process was chosen in the present investigation since ears at 45° or 0°, 90° can readily be obtained. Preferred orientation is often the principal cause of uneven metal flow, such as earing, and variation in mechanical properties. Consequently, the preferred orientation characteristics of 2s aluminum were initially studied using both X-ray diffraction and micrographic techniques. The variation of mechanical properties with angle to the rolling direction was next determined in an effort to clarify the apparent lack of correlation of earing behavior with mechanical properties for face-centered cubic metals. Strain-ratio*5,8 measurements were finally conducted to determine first, if the maximum values of the strain ratio occurred at the earing positions, and second, if Hill&apos;s theory of plastic anisotropy7 is applicable to other face-centered cubic metals such as aluminum. Detailed treatments, working, and heat treating are not given in this paper since this study is not concerned with the methods to produce earing, but to correlate earing with other properties and characteristics of the material. The percentage of earing was measured using the formula specified by the x—Y Aluminum Association, -------- X 100 = pct earing, where x is the height of the ear and y is the height of the valley from the bottom of the cup. Preferred Orientation Characteristics of 2S X-ray Studies: Beck and coworkers8 have determined that the rolling texture of 2s after 95 pct cold reduction may be approximately described by four equivalent ideal orientations near (123) [121]. Also, the recrystallization or annealing texture of 2s aluminum consists of four components of the (123) [l21] type, retained from the rolling texture, and of a (100) [001] or cube texture component." Fig. 1 illustrates the typical appearance of deep drawn earing cups with the corresponding X-ray diffraction patterns. The X-ray patterns were taken with copper radiation using the structure-integrating method&apos;" in which the specimen is scanned during the X-ray exposure. The rolling direction was vertical and the rolling plane was perpendicular to the horizontal X-ray beam. It was found that an increase in the retained rolling texture component resulted in a greater 45" ear height, while an increase in the recrystallization texture component (i.e., cube texture) caused greater 0°, 90° earing. X-ray diffraction studies of 2s cold rolled to final thickness followed by a final anneal have shown that the rolling texture, and also the retained component of the rolling texture after annealing, are increased with greater cold-rolling reduction. The preferred orientation characteristics of 2s sheets given an intermediate anneal between cold rolling followed by a final anneal were found to depend on the position of the intermediate anneal during cold rolling. For instance, three identical samples of 2s homogenized ingot, each 1 in. thick, were given the following cold-rolling and annealing treatments: 1—50 pct reduction, intermediate anneal, 96 pct reduction to 0.020 in. and a final anneal; 2—75 pct reduction, intermediate anneal, 92 pct reduction to 0.020 in. and a final anneal; and 3—90 pct reduction, intermediate anneal, 80 pct reduction to 0.020 in. and a final anneal. The intermediate and final annealing treatments consisted of a 70°F per hr heating rate, held 6 hr at 800°F and air cooled. Typical X-ray patterns after each of these treatments are shown in Fig. 2. It was evident that after treatment 1, the retained rolling texture component predominated; after treatment 2, the retained roll-

Jan 1, 1954

By G. L. Fisher, R. Maddin

The rate of self-diffusion in silver single crystals during torsional strain was measured over a wide range of tenperatures and strain rates. The torsional strain was applied in a cyclic manner by reversing the divection of twist aftev a certain fraction of the total strain was reached. Surface roughening was substantially reduced in cyclically strained specimens compared with those strained entirely in one direction. Diffusion coefficients were determined using a special sectioning technique whereby slices could be removed parallel to the surface of a strained torsion specimen. The accuracy of the technique was first determined using roughened specinzens statically diffused to various penetration depths. Simultaneous strain-diffusion experiments were then performed over the temperature range 550&apos; to 800 using strain rates of lo-&apos; to 2.2 x 10&apos; sec-&apos;. The increase in silver self-diffusivity during torsional plastic strain was small. In only one case was the enhancement greater than twice the static value of the diffusion coefficzent. The enhancements increased slightly with decreasing tenzperature and increased with increasing strain rate. A dislocation pipe mechanism of enhancement was found to explain the present results satisfactorily. The magnitude of the enhancements and the tenzperatures at which they were observed suggests that a steady-state dislocation density of 10&apos; to 109 dislocations cm-2 existed during the high-tempevature deformation. The diffusion coefficient in an fcc metal can be increased by 1) an excess concentration of point defects and 2) the rapid movement of diffusing atoms along grain boundaries and dislocations. Plastic deformation may be responsible for enhancements by both of these mechanisms. The results of simultaneous strain-diffusion experiments have caused a controversy over the magnitude of the effect of strain upon diffusion. Experiments reporting large enhancements have been criticized for the manner in which the diffusion coefficient was measured. Several of these experiments have been contradicted by other results obtained in a similar manner. No enhancement was reported by two investigators&apos;&apos;&apos; who performed their experiments at high temperatures where strain is expected to have little effect upon diffusion. A recent theoretical analysis3 indicates that strain enhancement by a vacancy mechanism will be small and exist only at low temperatures and rapid strain rates. It is doubtful whether any experiment has yet proven that strain enhancements can occur by an excess vacancy mechanism. In the present research, experiments were performed at extremes of temperature and strain rate in an attempt to measure enhancement of diffusion by strain. Self-diffusion of silver during torsional deformation was chosen since two separate investigations4j5 indicate that at least a small enhancement exists under these conditions. An accurate method of determining the diffusion coefficient, mechanical sectioning, was employed after a technique was devised to apply it to the roughened surface of a strained torsion specimen. First, the accuracy of the technique was determined for different penetrations (2fi). Then diffusion experiments were performed at temperatures between 550" and 800°C at strain rates of 10"" to 10"" per sec. I) EXPERIMENTAL PROCEDURE Preparation of Specimens. The experimental procedure detailing the growth of crystals, their treatment, and the annealing techniques during straining are contained in earlier publications.496 The dimensions and orientations of the torsion specimens are shown in Figs. 1 and 2. licatiin of Torsional Strain. The torsion procedure was changed from that used previously. The specimens were strained in cycles to reduce the gross distortion and surface roughening inherent in twisting to high strains in one direction. For all strains above 0.30, the total surface strain was obtained as follows: the specimen was twisted to 0.10 strain in a clockwise direction; the direction was reversed; the backlash in the torsion apparatus was taken up; and the specimen was twisted in a counterclockwise direction through the initial starting point to 0.20 surface shear strain in the opposite direction. The strain reversal took no more than 1 min to accomplish. The total accumulated surface shear strain was arbitrarily taken as the sum of the 0.10 strain in the clockwise direction plus 0.20 in the counterclockwise direction. Although cyclic torsional strain was beneficial, surface roughening and specimen distortion were not entirely eliminated. The variation in the diameter at various points on the specimen was often much greater than the depth of the diffusion zone. Since serious errors might result if specimens were sectioned in the usual manner, a technique of lathe sectioning was devised to allow sections to be taken parallel to planes of equal concentration.

Jan 1, 1967

By O. R. Wagner, R. O. Leach, H. W. Wood, C. F. Harpke

PAN AMERICAN PETROLEUM CORP.TULSA, OKLA. CASPER, WYO A field test has been made in which additional oil recovery was obtained from a previously-waterflooded "oil-wet" sandstone reservoir. This recovery improvement was accomplished by adjusting the reservoir wettability through chemical treatment of the flood water. The test was made in the Muddy sand of the West Harrisburg Unit, Neb. The chemical used, sodium hydroxide, was injected as a slug of dilute caustic solution through a water-injection well. The natural wettability of the reservoir and the chemical requirements for reversing wettability were determined in the laboratory from contact-angle studies using field water and oil samples. Laboratory flood tests with a synthetic system had shown that reversing the wettability of an oil-wet consolidated core would lead to improved oil recovery. The field performance indicates that the mechanism by which increased oil retovery is obtained in the field is the same as that observed in the lahoratory. Laboratory studies indicate that higher ultimate recoveries and decreascd water-injection requirements result when the adjusting agent is added early in the life of the flood. However, a previously waterflooded area was intentiorzally chosen for the field test so that unambiguous conclusions could be made about the effects of chemical injection on wettability and the extent of oil-recovery improvernent afforded by wettability reversal. Forces existing at the fluid-solid and fluid-fluid interfaces in a porous medium have an important effect on oil recovery during a water flood. Modifying these interfacial forces in the reservoir to improve oil recovery has been the object of much research. Several papers&apos; &apos; have discussed the use of surfactants to lower the water-oil interfacial tension. This paper describes work concerned with improving oil recovery by modifying the forces at the fluid-solid interfaces— that is, by changing the preferential wettability. An earlier paper: presented evidence to show that some reservoir systems could be changed from preferentially oil-wet to preferentially water-wet by the action of simple chemicals added to the water to increase waterflood oil recovery. The process was attractive for further study because it used only inexpensive chemicals and because it called for a gross "wettability reversal" rather than for a precise adjustment. The present paper is an extension of the earlier work. Laboratory flow tests were made using treated water and oil in a consolidated core to determine the amount of additional oil recovery and the producing performance which might be expected from reversing the wettability of an oil-wet reservoir during a flood. A contact-anglc study using water and oil from the Muddy "J" sand of the Harrisburg field, Banner County, Neb., indicated the reservoir to be preferentially oil-wet and susceptible to wettability reversal through chemical injection. Based on these studies, a field trial of wettability-reversal water flooding was initiated. in the Harrisburg field. The primary purpose of the trial was to determine if wettability-reversal flooding would improve oil recovery in an actual field situation. The field trial was also an important test of the laboratory tecnique used to determine the effect on oil recovery of certain wettability manipulation, as well as a test of the contract-angle method of determining reservoir wetra-bility. The paper is presented in two parts. The first part covers the laboratory experiments leading up to the field trial, and the second part covers the field trial. PART I—LABORATORY STUDY The laboratory experiments consisted of displacement tests using an idealized fluid system and of a contact-angle study with crude and water from the Muddy "J" sand of the West Harrisburg Unit, Banner County, Neb. The displacement tests were designed to determine the effects of a particular wettability manipulation, oil-wet to water-wet, on oil displacement in a water flood. The contact-angle measurements were made to determine the natural wettability of the reservoir and to determine if beneficial wetting changes could be brought about by a chemical addition to the flood water. PROCEDURE DISPLACEMENT TESTS The displacement tests were perfornled in a consolidated sandstone core using a refined oil and water. The wetting properties of this system could

W. S. GRESLEY, Erie, Pa. (communication to the Secretary): A six-entry method of opening coal-mines is, or was a short time ago, practiced in the Connellsville coal-region; but Dr. Chance&apos;s method has a novel aspect; for while in the Connellsville region the main pillars are formed outside of two pairs

Jan 1, 1901

By H. Shaw

GRAVITATIONAL measurements made by means of the Eötvös torsion balance over any area enable a representation to be obtained of the total gravitational effects over the surface of that area arising from the combination of all sources of gravitational disturbance. The investigation of gravitational anomalies occurring in the upper layers of the earth&apos;s crust, in this way, has been attended with considerable success, and, especially in areas in which no undesirable disturbing factors were present, it has been possible to locate geological structures and mineral deposits with remarkable accuracy and also to delineate their confines and to indicate their depth below the surface with a certain amount of precision. Before this can be done successfully, however, it is necessary to determine the gravitational effect arising from all other extraneous .anomalies in order that these may be satisfactorily eliminated. Disturbing features giving rise to these gravitational anomalies may be divided into two classes, according to whether they are situated at or below the surface. The former are determined readily by a detailed leveling of the ground surface, and may be satisfactorily eliminated provided the specific gravity of the terrain material is known, but the latter are generally unknown, and can only be ascertained with difficulty. When, therefore, the observations obtained by means of the Eötvös torsion balance have been corrected for all surface irregularities, known as terrain and topographical effects, there remain residual gravitational values which are due entirely to subterranean conditions. The task of interpreting these results consists in disentangling the various subsurface anomalies, and subsequently in computing and recombining the effects of these various masses in order to verify the interpretation. When the gravitational anomalies are due to large and comparatively simple structures it is a matter of little difficulty to arrive at a satisfactory interpretation of the subterranean conditions, but in more complex areas, where the geological conditions are more complicated and several irregular features exist, the process of disentangling the various constituents of the complex mass arrangement is more difficult and requires the expenditure of considerable time and labor.

Jan 1, 1929

Discussion * of the paper of H. M. Chance, presented at the butte meeting, august, 1913, and printed in bulletin No. 79, July, 1913, pp. 1315 to 1341. George H. Ashley,+ Washington, d. C.:-Mr. Chance&apos;s long practical experience in reporting on coal lands admirably fits him for a discussion of the value of such lands. On behalf of the government geologists, I wish to express my appreciation of Mr. Chance&apos;s friendly, constructive criticism of the government method of valuing coal land in the first part of his paper and, at the same time, to reply to some queries he makes. All admit that coal has no " intrinsic "-monetary value, in the sense that a pound of coal of certain chemical and physical characters is worth " intrinsically " so many cents or fractions of a cent. The term has, however, been found very useful as including those natural factors of coal value, among which are its position and location in the earth, that affect its sale price in contrast with the other cost elements involved in the labor and capital necessary in mining, preparing, transporting, and selling the coal (extrinsic factors). Mr. Chance, while recognizing the " dual origin of value," does not offer any better terms. The survey agrees with Mr. Chance in his definition of coal conservation, that it means the fuller utilization of the heat contents of the coal, and the more complete recovery of the coal from the ground. Coal land withdrawals have not been made to keep such lands off the market, but to prevent their acquisition as non-coal lands before they could be classified so as to be disposed of under the proper law. Nor has the pricing of the more valuable coal lands above the minimum been to raise money for the reclamation fund, to which the money goes, but primarily to discourage the alienation, for holding or speculation, of coal lands not intended or needed for development, and, secondarily, to secure to the people the ?unearned increment," which they are certain in any case to be charged.

Jan 11, 1913

By H. C. Spaulding

Every constructing engineer and designer knows how often it is desirable to provide a speed-adjustment between parts of a machine performing different functions, or between a prime mover and the devices to which it furnishes power, and how bulky and unsatisfactory are most of the methods by which the result is usually accomplished. Of course the step-pulley is the most simple and generally used. It requires, (1) parallelism of shafts; (2) a considerable distance between centers; and (3) a cessation of power during the change from one speed to another. Add to this the necessity for careful design in order to obtain equal belt-tension for all positions; the weight and hulk required for a wide range; and the operative&apos;s positive conviction that better results could be obtained at a speed intermediate between those furnished by two successive steps, and we begin to realize the mechanical shortcomings of this old and familiar friend. The hundred and one other devices, patented and otherwise, for accomplishing similar results, present other objections of varying importance, which need not be discussed here. Without pretending to overcome these entirely, and indeed without claiming absolute novelty, a recent invention of Mr. E. F. Gordon, of Dover, N. H., has seemed to the writer to offer such advantages in flexibility and range of application as to merit a more extended study and use than can be given in his own work, to which it is being applied as rapidly as opportunity permits. It is placed before the members of the Institute, not only to bring out an expression of opinion as to its limitations, but also with the hope that it will thus find opportunities for applications hitherto untried and outside the scope of operation of those at present interested in its development. Simply stated, the device consists of a narrow pulley with a deep V-groove, split by a plane passing through the bottom of the groove, one of the two symmetrical parts so formed being fixed to the shafts, and the second being capable of adjustment so as to bring the

Jan 1, 1893

By Stanley C. Herold

TWENTY-FIVE years ago no distinction was made between water wells and oil wells except in the nature of the fluid produced. Water wells usually showed no decline in their rate of production; when oil wells showed decline something in the manner of handling them was considered wrong. Both water and oil were believed to be subject to the same physical laws in their underground movement toward the wells. Today a sharp distinction is made between them. Whereas water exists alone in the porous formations at depth, oil is usually accompanied by gas. This mixture does not behave as a liquid alone. It is a frothy, seething mass of foam which approaches and enters the wells. Different physical laws come into play. Twenty-five years ago attention was directed entirely to the well itself; today the well is accepted as a mere hole in the ground, a hole to be equipped properly for efficient service, yet without any value whatever unless it is backed up by a sufficiently prolific reservoir. Then, we were concerned with wells alone, 3000 ft. in depth; now commercial wells and their reservoirs are 10.000 ft. deep. Petroleum engineering concepts have necessarily therefore undergone a change in this last quarter century. What are they today?

Jan 1, 1937

By P. D. Southgate

VIBRATION, both ultrasonic and sonic, can affect the course of a variety of metallurgical processes. Reports of work on this subject have appeared at intervals over the last twenty years and a thorough review has been made by Hiedemann,&apos; who gives a full list of references. It has been established that both refinement of structure and outgassing of the melt can be produced in most metals with sufficiently intense vibration. Many of the experiments in this field have been carried out using alloys of direct commercial interest in production- type casting equipment. Here a different approach is adopted, and simple binary alloys which exhibit different types of structure are used to facilitate examination of the effects produced under well-controlled conditions. Results from this kind of experiment should enable the basis of larger scale experiments with similar types of materials to be better substantiated. The alloys selected for this work are: 1) aluminum of 99.2 pct purity, the principal impurity being iron, near 0.4 pct; 2) A1-1.8 pct Fe, which is near eutectic composition; 3) A1-4 pct Fe—the second phase, of composition FeAl3, forms distinct acicular crystals; and 4) A1-12 pct Si—although this is of eutectic composition, the silicon normally appears in the form of large plates. Experimental Method There are three practicable methods by which acoustic vibration can be transferred to liquid metals: a) vibration of the whole of the container; b) electromagnetic induction; and c) insertion of a vibrating probe into the liquid. Method c is chosen here, and a frequency of 8 kc per sec is used. The end of the probe is electrically heated so that the metal near it will be the last to solidify. This ensures that vibration is transmitted directly to the liquid metal without passing through any solidifying and pasty intermediate region, which would attenuate acoustic waves severely. In addition, the heating prevents solid metal adhering to the probe, with consequent detuning. The transducer assembly is shown in Fig. 1. A stack of Permendur laminations 30 cm long acts as a half-wave vibrator and a winding along its length carries polarizing and energizing currents. It is joined by a half-wave coupling bar to a mild steel exponential horn, which tapers from 3.8 to 1.1 cm diam. A stainless steel stub 3 cm in length is welded on the free end. The assembly is supported by a plate located at the node of the coupling bar. Acoustic radiation losses are minimized by allowing the free end of the transducer to protrude above the surface of the cooling water. The exponential horn serves the function of matching the acoustic output impedance of the transducer to the radiation resistance of the probe into the melt. Electrical drive is provided by a 1 kw generator. Measurements of probe vibration amplitude during melt treatment are obtained from a gramophone pick-up with the needle attached to the wide end of the horn. This device is calibrated with a microscope before use. Liquid aluminum is very actively erosive and solution of materials with which the molten metal comes into contactcauses difficulties. Erosion of the probes in particular can be severe since it is greatly accelerated by the vibration. Tests of various acous-

Jan 1, 1958