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By R. L. Bell, T. G. Langdon

A technique was developed- for determining the grain strain, and hence the grain boundary sliding contribution, occurring during the high- temperature creep of a magnesium alloy, from the distortion of a grid photographically printed on the specimen surface. The results were compared with those obtained from measurements of grain shape, both at the surface and interrwlly, and it was concluded that the grain shape technique may substantially underestimate the grain strain and overestimate the sliding contribution due to the tendency for migration to spheroidize the grains. ALTHOUGH a considerable volume of work has been published on the role of grain boundary sliding in high-temperature creep, many of the estimates of Egb (the contribution of grain boundary sliding to the total strain) have been in error due to the use of incorrect formulas or inadequate averaging procedures.' One of the most easy and convenient measurements from which to compute Egb is that of v, the step normal to the surface where a grain boundary is incident. Unfortunately, this parameter is also the one associated with the treatest number of pitfalls. Values of v have been used to calculate Egb from the equation: egb =knrVr [1] where k is a geometrical averaging factor, n is the number of grains per unit length before deformation, v is the average value of v, and the subscript ,r denotes the procedure of averaging along a number of randomly directed lines. If the dependence of sliding on stress were assumed, it would be possible, in principle, to calculate k from the known distribution of angles between boundaries and the surface. This in itself is difficult because the distribution depends on the history of the surface,' but the problem is even further complicated by the fact that v depends on other factors such as the unbalanced pressure from subsurface grains.3 However, the great simplicity of the measurement procedure for v makes it highly desirable that this problem of k determination should be overcome. In the present experiments, this was achieved by the use of an indirect empirical method in which the grain strain, eg, at the surface was determined by the use of a photographically printed grid. The assumption here is that the total strain, et, is simply the sum of that due to grain boundary sliding, egb, and that due to slip or other processes within the grains, eg. SO that: Et = Eg + Egb [2] Thus k is given by: In practice, it is customary to indicate the importance of sliding by expressing it as a percentage of the total creep strain; this quantity is termed y (= 100Egb/Et). The determination of Eg from a printed grid within the grains avoids the difficulties due to boundary migration which should be considered when the grain strain is calculated from measurements of the average grain shape before and after deformation. As first pointed out by Rachinger,4,5 however, this latter technique has the particular advantage that it can also be applied in the interior of a polycrystal. Recently, several workers have produced evidence on a variety of materials6-'' to support the observation, first made by Rachinger on aluminum,4,5 that 7 can be very high, 70 to 100 pct, in the interior, even when the surface value, determined from boundary offsets, is very much lower.10'11 Although there have been criticisms both of the shortcomings of the grain shape technique'' and of the different procedures used to determine y at the surface,' it seemed important to check whether measurements of sliding by grain shape gave values of y which were truly representative of the material. In the present experiments, grain shape measurements were therefore made both at the surface and in the interior for comparison with one another and with the independent measurements of grain strain using the surface grid technique. EXPERIMENTAL TECHNIQUES The material used in this investigation was Magnox AL80, a Mg-0.78 wt pct A1 alloy supplied by Magnesium Elektron Ltd., Manchester. Tensile specimens, about 7 cm in length, were prepared from a 1.27-cm-diam rod, with two parallel longitudinal flat faces each approximately 3 cm in length. The specimens were annealed for 2 hr in an oxygen-free capsule, at temperatures in the range 430° to 540°C, to give varying grain sizes, and, prior to testing, the grain size of each was carefully determined using the linear intercept method. This revealed that the grains were elongated -0.5 to 5 pct in the longitudinal direction. Testing was carried out in Dennison Model T47E machines under constant load at temperatures in the range 150" to 300°C. At temperatures of 200°C and below, tests were conducted in air with the polished flat faces coated with a thin film of silicone oil to prevent oxidation; at higher temperatures, an argon atmosphere was used. To determine v,, each test was interrupted at regular increments of strain and the specimen removed from the machine. At the lower strains, when v, was less than about 1 pm, measurements were taken on a Zeiss Linnik interference microscope;

Jan 1, 1969

By John T. Eash

DURING the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin, 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. SELECTION OF COMPOSITION While the final criterion of the suitability of an alloy for a bearing must 0f course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstructure, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig. I. In addition, the tin bronze contains the hard alpha + delta eutectoid constituent distributed through-

Jan 1, 1945

By Leon Hart

THE nickel-chromium alloys of importance are those containing iron and those free from iron. The most important alloys containing iron, with regard to high tonnage, are the nickel-chromium steels. Straight nickel steel was introduced about the year 1889, but it was not until 1895, when it was found that the addition of chromium greatly increased the FIG. 1.-RESISTIVITY OF NICKEL-CHROMIUM-IRON ALLOYS. strength and resistance to shock, that nickel-chromium steels came into use. The three types of nickel-chromium steels developed at this time were: Type 1, containing 3.50 per -cent. nickel and 1.50 per cent. chromium; type 2, containing 2.00 per cent. nickel and 1.00 per cent. chromium; and type 3, containing 1.50 per cent. nickel and 0.50 per cent. chromium.

Jan 1, 1921

By M. E. Wadsworth, J. S. Cho

The kinetics of silicate adsorption from aqueous colloidal (SO2 . nH2O) silicate sols on thoria (ThO 2) surfaces were determined at 100, 150 and 200°C in an autoclave system. The amount of chemisorbed silica on the thoria surface was determined by means of infrared spectroscopy. First order kinetics were observed in all cases with the anomalous result that the first order rate constant was found to vary with the initial amount of silica added to the system. These results have been correlated quantitatively by means of a strain model of adsorption involving two types of surface silicate bonding, both of which may be readily observed in the infrared spectrum. Initial adsorption occurs rapidly to produce one type of surface silicate followed by a slow transition to a second type of surface bonding, the latter transition representing the slow step in the adsorption process. Initial interest in silicate adsorption on thoria arose from the dispersive effect silica has on finely divided thoria in aqueous suspensions. Spaepen et al studied the equilibrium adsorption of silica on thoria and noted increased adsorption up to approximately 215°C with a notable decrease in adsorption at temperatures above 215°C. Similar results were observed by Cho and Wadsworth2 who identified two types of surface silica by infrared spectroscopy. At temperatures of 100°C and above, rapid initial adsorption occurred producing a surface species with maximum infrared absorbance at 9.4 After extended periods of time, the 9.4 species converted to a more strongly bonded surface silicate with maximum infrared absorbance at 10.3. The latter was very strongly bonded and difficult to remove by desorption in hot distilled water, while the 9.4 species could be removed more readily by similar treatment. The 9.4 and 10.3-p species were distinguishable from free unadsorbed silica which had maximum infrared absorbance at 9.1 The kinetics of the formation of the strongly chemisorbed silica (10.3) on thoria as determined by infrared examination are presented in this study. EXPERIMENTAL PROCEDURE As a source of silicate, Ludox SM (16.36% SiO2) or Ludox HS (30.25% SO2), DU Pont colloidal silica in aqueous suspensions, was added directly to a thoria slurry made up of one liter of distilled water and one gram of thoria. The thoria used was designated D-16-650 and was received from the Chemical Technology Div. of Union Carbide Nuclear Co. It was prepared by firing thorium oxalate at 650°C. The D-16 thoria had a surface area of 32.4 ± 0.6 sq m per g as determined by nitrogen adsorption.* This thoria 'Determined by Unlon Carbide Nuclear Co., ORNL. had a total adsorption capacity for silicate of approximately 19.4 mg of silica per gram of thoria.1 This amounts to approximately one SiO2 molecule for every surface thoria site. In all cases in this study.

Jan 1, 1963

By A. B. Cox, L. W. Wark

In an earlier paper1 measurements of contact angles due to the effect of xanthates on mineral surfaces were reported. The solutions in which these measurements were made differed widely from those of modern flotation circuits. It is intended, however, by introducing, one at a time, the other principal reagents of flotation, to approach gradually the solution composition of flotation liquors. The work now described is an attempt to determine the effect of one of the most important of these reagents—namely, sodium cyanide—on the establishment of air-mineral contact. The work has been carried out for the following companies: Broken Hill South, North Broken Hill, Zinc Corporation, Electrolytic Zinc of Australasia, Mount Lyell Mining and Railway, and Burma Corporation. Since the effect of cyanide is inseparably connected with the alkalinity, the results cited below deal with the mutual effects of alkalis and cyanide. Alkalis alone exert a significant effect on the air-mineral contact but comparatively large amounts are required. Since the addition of a small amount of cyanide greatly decreases the degree of alkalinity necessary for the suppression of contact at surfaces of any of the minerals experimented with (except galena) and since alkalis are rarely used alone in practice, little attention has been paid to cyanide-free solutions. It was shown in the previous paper that, excluding the dixanthogen effect, whenever contact was practicable at all in an ethyl xanthate solution the angle of contact was 60". There is, therefore, less necessity to measure equilibrium contact angles; in fact, the experiments herein described have generally been conducted with a view to determining whether contact is possible and not to measuring the actual value of the contact angle. The separations which have generally to be effected in dealing with complex sulfide ores are: (1) galena from sphalerite, pyrite, etc.; (2) sphalerite from pyrite and/or gangue minerals; (3) copper minerals from pyrite and gangue minerals; (4) pyrite from gangue minerals; (5) chal-

Jan 1, 1935

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By C. K. Rose, J. H. East

Proved oil shale reserves in the Green River formation in Colorado, Utah, and Wyoming dwarf present U. S. petroleum resources. Indications are that the appetite for petroleum products will continue to grow and that this potential source of liquid fuels and related byproducts cannot be disregarded. As a part of its synthetic fuels program, the U. S. Bureau of Mines has opened a mine in the richer beds on the naval oil shale reserves. In addition to supplying material for retorting and refining studies, the development of methods, procedures, and equipment for mining oil shale on a large-scale commercial basis is of the greatest importance.

Oct 1, 1955

By C. D. King

THE advances in basic open-hearth practice which have occurred during the past decade, have been principally in the direction of the physical development of larger units, decreased fuel consumption and increased length of furnace campaigns. However gratifying the economies which have resulted from these improvements are, it must be granted that like advances in chemical, physical-chemical and metallurgical knowledge pertaining to open-hearth practice would have added greatly to these already attained reductions in costs and it is the purpose of this paper to stimulate the discussion and study of these phases of cooperation and their relation to ingot yields. DEFINITION AND CALCULATION OF LOSSES In discussing basic open-hearth yields, the writer refers to the ingot yields obtained in the process of converting pig iron, scrap and ore to steel. In this conversion some scrap is produced. The difference between the total weight of ingots and scrap produced and the original metallic charge, constitutes the loss. Basic open-hearth yields vary considerably, and while some of the divergencies can be explained metal-lurgically because of differences in slag analysis, proportion of pig charges, and character of steel made, there often remain differences that apparently do not readily disclose themselves. In reconciling yields by the usual accepted methods of calculation, one is often forced to evaluate large losses as "unaccounted for." Such a system is prone to accept these large losses as inherent to the operation and not susceptible of appraisement and correction. It is obvious that if the ingot yield, plus the scrap recovered subtracted from 100 per cent. determines the loss, a drop in yield may increase the loss or the scrap, and both contribute to a monetary loss. To be sure, one can subdivide these unaccounted for losses into various components, such as metallics in slag, free Fe in slag, spillage, etc., and thereby reduce the amount of losses considered as "unaccounted for." If empirical methods could indicate with some degree of accuracy all losses, however slight, the undetermined losses become appreciably smaller and resultant calculations will check actual

Jan 1, 1929

CURRENT MATTERS Page Page New York Meeting v Federal Control of Minerals xxxii Meeting of Board of Directors.. ix Naval Consulting Board...' xxxix Reports for Year, 1917: Perkin Medal xl Secretary ix Communication from Albert Treasurer xvii Sauveur xl Committee on Membership... xx Affiliated Student Societies xli Committee on Increase of Membership in Military Service... xli Membership xx Personal xlvii Committee on Publications... xxii Positions Vacant 1 Committee on Library xxiii Engineers Available li Local Section News: Forthcoming Meetings lii Boston xxiv Library liii. Columbia xxv Membership lvii San Francisco xxx Institute Committees lxx Qualifications for Membership.. xxxi Officers and Directors lxxviii.

Jan 2, 1918

By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The role of surface charge in soluble salt flotation, which was developed in Part I, is extended to relate the theory to the specific phenomena of KCI-NaC1 separations. Temperature-collector solubility relationships, metal ion activation, and particle size effects are discussed. The initial paper in this series developed and presented the hypothesis that one of the mechanisms of soluble salt flotation may involve electrical attraction between the collector and mineral surface. This hypothesis was developed from a combination of experimental data and free energy calculations, and details of the logic are presented in this first paper.* The studies have indicated that KC1 has a positive surface charge and NaCl a negative charge. KC1 can therefore be floated with sulfonate ion (RSO;) or with an aqueous polar species such as the aqueous amine chloride, RNH3C1(,,). The chloride end of the RNH3C1(,,) molecular dipole is probably negative and will be attracted to the positive surface of the KC1 particles and absorb (actually probably fit into a vacant chloride site) on the mineral surface. The amine end of the collector molecule would extend into the solution phase and provide the air avid surface required for flotation. NaCl particles are floated by such collectors as aqueous molecules of fatty acid salt, RCOONa(,,), in which the positive inorganic end of the dipole is attracted to the negatively charged surface of the NaCl and, in this case, adsorb and probably fit into a vacant sodium site on the surface. The aminium cation, RNH~, should also be a collector for NaC1. For certain collectors, actual precipitates of the collector must be formed before a sufficient amount of the polar aqueous molecule is present to effect flotation. In a system of this type there is a three-way equilibrium between: Aqeous Molecular Solid Precipitate - A of the Collector (Not Dissociated) . Ionic Species (Dissociated). The controlling equilibrium is probably between the precipitated form of the reagent and the aqueous

Jan 1, 1969

By R. L. Huntington, D. T. MacRoberts, Charles R. Hetherington

Since the equation of continuity governing transient flow of gases through porous media cannot be integrated mathematically into a simple usable expression free from series terms, empirical and approximate equations have been advanced relating cumulative production and future production rates from gas reservoirs with time. In order to check the accuracy of these empirical equations and to obtain an insight into the initial conditions pertinent to the solution of the fundamental equation of continuity, experimental work has been conducted on a vertical 2-in. tube, 91.6 ft. high, packed with unconsolidated Wilcox sand. The results presented in graphical form show the accuracy of the approximate relations. Data from unsteady-flow runs on the 2-in. experimental tube are presented graphically, and are applied to obtain an equation for this specific case, and are offered as an aid in future investigations of this basic equation. The close agreement between equations calculated for steady-state flow and the experiments indicates that the decline of actual gas reservoirs may be treated by an application of these equations without serious error. Introduction The steady-state flow of gas through a porous material—that is, flow wherein the boundary conditions do not vary with time—is subject to analytical solution. Muskat1 has shown that the general differential equation is simply the La Place equation in P2. Direct solutions may be at once obtained. The unsteady state, on the other hand, is not analytically reducible. Since nearly all phenomena of practical interest in gas production involve flow in the unsteady rather than in the steady state, it has been necessary to derive approximate Solutions to the general equation. The validity of such approximations has not hitherto been adequately tested. In the experiments to be described a simple, closed, linear system is substituted for the real complex gas field. The general results, however, are independent of the geometry Of the system' The problem studied is the rate of production, and the accompanying variations in pressure, when one end of a linear porous system is opened to the atmosphere and permitted to produce to exhaustion. An approximate solution to the general differential equation, based upon the assumption of an "infinite series of steady states," is then applied to the results to determine the validity of this method of dealing with actual reservoirs. Theoretical Considerations The fundamental differential equation governing the flow of a gas through a Porous medium can be derived easily from the equation of continuity, Darcy's law, Boyle's law and a statement of the thermo-dynamic nature of the flow. For isothermal flow it is: d2P2/dx2 + d2p2/dy2 + d2p2/dz2 = 2fµ/K dP-dT

Jan 1, 1942

By R. L. Huntington, D. T. MacRoberts, Charles R. Hetherington

Since the equation of continuity governing transient flow of gases through porous media cannot be integrated mathematically into a simple usable expression free from series terms, empirical and approximate equations have been advanced relating cumulative production and future production rates from gas reservoirs with time. In order to check the accuracy of these empirical equations and to obtain an insight into the initial conditions pertinent to the solution of the fundamental equation of continuity, experimental work has been conducted on a vertical 2-in. tube, 91.6 ft. high, packed with unconsolidated Wilcox sand. The results presented in graphical form show the accuracy of the approximate relations. Data from unsteady-flow runs on the 2-in. experimental tube are presented graphically, and are applied to obtain an equation for this specific case, and are offered as an aid in future investigations of this basic equation. The close agreement between equations calculated for steady-state flow and the experiments indicates that the decline of actual gas reservoirs may be treated by an application of these equations without serious error. Introduction The steady-state flow of gas through a porous material—that is, flow wherein the boundary conditions do not vary with time—is subject to analytical solution. Muskat1 has shown that the general differential equation is simply the La Place equation in P2. Direct solutions may be at once obtained. The unsteady state, on the other hand, is not analytically reducible. Since nearly all phenomena of practical interest in gas production involve flow in the unsteady rather than in the steady state, it has been necessary to derive approximate Solutions to the general equation. The validity of such approximations has not hitherto been adequately tested. In the experiments to be described a simple, closed, linear system is substituted for the real complex gas field. The general results, however, are independent of the geometry Of the system' The problem studied is the rate of production, and the accompanying variations in pressure, when one end of a linear porous system is opened to the atmosphere and permitted to produce to exhaustion. An approximate solution to the general differential equation, based upon the assumption of an "infinite series of steady states," is then applied to the results to determine the validity of this method of dealing with actual reservoirs. Theoretical Considerations The fundamental differential equation governing the flow of a gas through a Porous medium can be derived easily from the equation of continuity, Darcy's law, Boyle's law and a statement of the thermo-dynamic nature of the flow. For isothermal flow it is: d2P2/dx2 + d2p2/dy2 + d2p2/dz2 = 2fµ/K dP-dT

Jan 1, 1942

By Charles Stein

The effects of several different prior treatments an the creep behavior of 99.9995 pct aluminum at 260°C and 1000 psi canstant stress are compared with annealed specimens. Quenching from 538oC, irradiation with 2 mev electrons, and tension-compression room temperature fatigue damage were used to change the substructure of the specimens prior to their creep testing. The quenched and the irradiated specimens showed a larger primary and transient stage contribution to the creep curve than those specimens which were only annealed prim to creep testing. The specimen receiving prior fatigue damage at room temperature showed no first stage or transient creep when tested under identical conditions as the above specimens and had an average creep rate seven orders of magnitude lower than that of either the annealed, the quenched or the irradiated creep specimens. In a previous electron transmission microscopy investigationl of the substructure developed during the creep of pure aluminum at 0.57 Tm, it was noted that a large concentration of vacancy loops and dislocation loops were present in and near the subboundaries while the interior of the subgrains contained few of these defects and had a low dislocation density, see Fig. 1. Yim and Grant2 and Hazlett3 have shown that the presence in nickel of a substructure developed by prior cold work effectively reduces the primary and transient contributions to the creep curve. Hultgren,4 McLean,5 Gervais, Norton, and Grant,6 Chang and Grant,7 and others have shown the same effect with the higher stacking fault energy material, aluminum. However, the specific defect responsible for the change in the creep behavior developed by the prior cold work was not established. Specifically, what effectively interfered with dislocation motion in these materials at elevated temperatures? Was it jogs on dislocations produced by their interaction with other dislocations or with vacancy or dipole loops, see Fig. 1, or did the subgrain walls determine the mean free path for glissile dislocations? This would be a realistic possibility only if subgrain boundaries are effective barriers to dislocation motion. The ability of a subgrain boundary to act effectively against glissile dislocations depends on the number and the arrangement of dislocations in the subboundary,8 which in turn is a function of the creep strain.' This paper compares the creep rate of specimens possessing a large vacancy concentration to that of annealed specimens and with specimens having a stable subboundary wall containing Lomer locks produced by prior fatigue damage. EXPERIMENTAL PROCEDURE Vacancy Loops. Aluminum creep specimens, 99.9995 pct pure, were machined from zone refined rod to a 2-in. gage length and a cross-sectional area of 0.025 in. These specimens were annealed at 538oC, 1000°F, for 10 min and quenched into ice water. They were then reheated to the creep test temperature of 260°C, 500°F, and held at this temperature for 18 min to al-low for vacancy condensation and loop formation. The specimens were subsequently creep tested at 1000 psi constant stress at 260°C. The temperature along the gage length was monitored by three Pt-Pt, 13 pct Rh thermocouples, two embedded in the upper and lower shoulders of the specimen and one attached to the mid-point of the gage length- The temperature gradient was held to ± l°C or less throughout the Creep test. Elongations were measured by two LVDT's 'connected in an averaging 'On-figuration, with quartz extension arms placed against the specimen at the extremes of the 2-in. gage length. i K 3J?--' * *H - >^> - ' ^L r 77 . *y J OJL, J Fig. 1—Transmission electron micrograph of pure aluminum strained 8.2 pct at 260°C and 1000 psi constant stress. Note the presence of numerous loops near the light dislocation tangle

Jan 1, 1970

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By J. W. Borough

THE electrical conductivity of pure copper is markedly decreased by small amounts of impurity in solution. The magnitude of this effect has been very carefully determined by numerous investigators who studied a wide variety of impurity elements. Much of this work is summarized in an excellent review by Pawlek and Reichel.' The case of zinc impurity in copper is an exception to the above in that there has been no well-documented study of the effect using high-purity starting materials. The values for the effect of zinc on conductivity, which are usually taken from unpublished work by Skowronki, indicate that zinc in low concentration has no effect whatever in lowering the conductivity of pure copper. This effect, if true, is unusual since it is generally known that even in lowest concentration, impurities exert an effect on conductivity which is proportional to the amount dissolved. It is more reasonable to suspect that in the original work on the effect of zinc some of the zinc was oxidized out of solution during specimen preparation. The following experi- and calculated d-spacings based on the unit cell dimensions of Baenziger et al. Since the single crystal studies of Baenziger et al. were limited to (hk0) and (hk 1) data, it was not possible to Compare all the intensities of the powder and single crystal patterns. However, the strongest reflections of both studies, the (321) reflection, agree very well when the appropriate multiplicity factor is used. Good agreement was also found in a number of other reflections of lesser intensity. Despite the precautions taken in annealing the U6Fe powder, an appreciable amount of UO, was detected in the powder pattern after heat treatment. The powder pattern reported by Groganoand Clews is given in Table I. Except for the 3.15A line, which is the strongest line of UO,, their pattern, as far as it goes, compares favoEably with the data from this study. Gordon and Kaufmann have reported a diffraction powder pattern purported to be U, Fe but it bears very little resemblance to the patterns of Table I. ments were carried out to redetermine the effect of zinc on conductivity using high-purity starting materials and processing conditions capable of producing oxygen-free alloys. Materials used in the experiment were ASR 99.999 pct Cu and Cumingo 99.999 pct Zn. Four 1 lb melts were prepared with identical procedure in argon atmosphere with crucibles made from Speer No. 580 graphite. The compositions were 0.0, 0.1, 0.3 and 1.0 pct Zn. Standard No. 14 wire (0.064 in. diam) was made from these melts as follows. The 1 pct Zn sample was first reduced 94 pct by cold swaging with five annealing treatments of 800o for 10 min in hydrogen between swagings, and then reduced 94 pct to the

Jan 1, 1962

By A. K. Sinha

The market for thermal coal has recently been growing rapidly and it is projected to continue to do so in the foreseeable future. Both the national and international markets often demand high-Btu low-sulfur thermal coal in order to minimize the cost of utilization and meet the environmental restrictions. High quality thermal coal can be prepared to compete in the utility market by desulfurizing the high-Btu midwestern coal and blending it with low-sulfur western coal which is usually low in Btu content. The methods that can be used for optimizing the coal preparation plant operating parameters for physically desulfurizing coal are presented.

Jan 1, 1985

By Wm. Reuben Webster

BRASS is an alloy of copper and zinc. The brasses (using this term to denote all useful proportions of the two constituents) are the most valuable and widely employed of all [ ] nonferrous alloys, because of their high resistance to ordinary corrosive agencies and the very wide range of properties that may be imparted to them by variations in the proportions of the constituents and by variations in mechanical treatment and heat-treatment. Fig. I shows the normal physical properties, as determined by standard tensile tests, of the series when in the annealed condition. Fig. 2 shows the effect of varying amounts of cold-working on an almost pure brass containing 70 per cent copper and 30 per cent zinc. Fig. 3 shows the effect of annealing at various temperatures on the same alloy. This effect is somewhat modi [ ] fled by the degree of cold-working to which a brass has been subjected, as shown by Fig. 4. A fourth test, which is empirical, has been found useful because of its simplicity -the hot hammer test. Samples Y2 in. in diameter and ¾ in. long are placed in a suitable furnace. These are withdrawn one at a time at successively higher tempera¬tures and are subjected to the blow of a drop hammer weighing 50 lb. with a drop of 4 ft. The percentages of' reduction in length of the cylinders are plotted against temperatures and give a comparative measure of plasticity at different temperatures. The results of this test on several

Jan 1, 1942

By E. Posnjak

IT is rather the general belief that acidified solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no. oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by, passing air for 3 hr. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will be proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2. His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 1, 1927

By M. Muskat, H. G. Botset, R. D. Wycoff, M. W. Meres

The subject of the flow of homogeneous fluids—gases alone or gas-free liquids—through porous media may be considered at the present time to be fairly well completed. That is, analytical, graphical, numerical, or experimental methods are now available for obtaining detailed descriptions of the behavior of such homogeneous fluid systems of any reasonable geometry. Thus, satisfactory empirical techniques are now well established for the determination of the permeability of porous media for homogeneous fluids, the numerical magnitude of this permeability uniquely and completely describing a porous medium as a carrier of a homogeneous fluid. Considering this constant as known, the treatment of a wide variety of specific problems involving either the flow of gases or liquids has been carried through to satisfactory conclusions. Beginning with the simple case of strictly radial two-dimensional flow of a liquid or gas into a well under steady-state conditions, generalizations have been developed to apply for systems where the flow is not strictly radial, due either to a lack of uniformity in the reservoir pressures at points distant from the well or deviations from circularity of the external boundary whereby the fluid is being supplied, and finally, to the lack of complete penetration of the well into the producing strata. Satisfactory descriptions are now available for cases where gravity is acting as the driving agent inducing the flow of liquid into the well, either alone or as a supplement to the effect of pressure. The effect of acid treatment on limestone wells has been given a reasonable interpretation on the basis of the fundamental theory of the flow of homogeneous fluids through sands, as have the important features of the problem of water-coning. Then, too, systems in which the outlet of the fluid from the underground reservoir is of a predominantly multiple character may be now considered as in the domain of

Jan 1, 1937

By C. F. Frey, P. J. Ahern, J. F. Wallace

THE high affinity of molten titanium for oxygen and nitrogen has resulted in considerable difficulty in developing a satisfactory melting procedure. It has been found necessary to perform melting operations either in a vacuum or inert atmos-phere, and failure to obtain a satisfactory crucible material has necessitated the use of special melting techniques. These techniques have included cold-mold arc-melting utilizing both consumable and nonconsumable electrodes, skull-melting, drip-melting, and levitation melting.' It has been recognized generally that the melting of both titanium sponge and titanium scrap would be expedited by the use of induction-melting procedures but the lack of a crucible capable of containing molten titanium without objectionable contamination thus far has prevented the use of induction-melting procedures. An extensive investigation: which included the common refractory materials was not successful in developing a satisfactory crucible for induction-melting. Some success in induction-melting has been attained with the use of a graphite crucible material, but in all instances sufficient carbon contamination was encountered to cause an appreciable reduction in the optimum mechanical properties of the titanium or titanium alloys. These investigations"" report an increase in the carbon content from approximately 0.3 to 1.0 pct. A serious reduction in the tensile and forming properties has been observed as a result of this carbon contamination. The development of a satisfactory induction-melting procedure for titanium without undue contamination undoubtedly would have considerable economic significance. Such a process would be particularly useful in melting the large quantities of low-cost scrap now available that can only be reprocessed at considerable expense and difficulty by the more elaborate techniques referred to previously. In addition, the process could provide a satisfactory method of melting and alloying of bri-quetted sponge for forging ingots.

Jan 1, 1959