Search Documents

By P. Hazebroek, C. S. Mathews, E. E. Allen, H. C. Lefkovits

A rigorous study was made of the behavior of reservoirs composed of horizontal layers, unconnected except at the well and filled with a compressible fluid. The report is presented in two parts. Part I deals with the practical implications of the results obtained; Part 11 contains the mathematical derivation of the solution. The main portion of Part I is concerned with application of the results to reservoirs composed of two layers. Relative rates of depletion of the layers are studied, and it is shown that differential depletion between layers exists in the transient stage of the reservoir, which generally is of an order of magnitude longer than the transient stage in a single-layer reservoir. In the transient stage, the more permeable layer is depleted faster than the less permeable. However, the reservoir approaches a steady-state situation where both layers contribute equally to production. Theoretical build-up curves from such reservoirs are presented, and the influence of a skin effect and flow into casing and tubing are also evaluated. The build-up curves are predicted to have, first, the familiar logarithmic straight-line section and, subsequently, a rising and flattened section. The results found are compared with an extension of an approximate theory, and it is found that this simplified theory is applicable over most of the life of the reservoir. Extensions to reservoirs containing more than two layers are indicated, and examples of the performance and build-up curves for three-layered reservoirs are presented. The theoretical results on build-up curves were applied to field examples of such reservoirs, and satisfactory results were obtained. From the build-up curve, the pemeability-thickness product, the wellbore damage and the static pressure are obtained. However, it apparently is not possible to determine the properties of the individual layers from the combined build-up curve. A large number of reservoirs have been found where the producing formation is composed of two or more layers of differing physical characteristics, such as permeability and porosity, and where also the thicknesses of the layers differ. Since in general a differential depletion should exist between the layers of such reservoirs, it would be advantageous to know the amount of the differential depletion under a given production history. It also would be valuable to know the pressure behavior, because it could be undesirable to produce a reservoir in such a manner that the pressure in one of the layers would have fallen below the bubble point of the oil at a time when another layer might still be virtually undepleted. The determination of static pressures in shut-in wells with slow build-up is another feature of importance in layered reservoirs. If the behavior of the reservoir differs appreciably from the predicted behavior of a single-layer reservoir, the type of analysis for build-up curves suggested for single-layer reservoirs is not applicable. Several authors have treated the problem of finding the pressure and production characteristics of multilayer reservoirs. Horner treated the problem of n layers in an infinite field, the layers being connected only at the well. Tempelaar-Lietz2 has presented an approximate treatment of the characteristics of a bounded reservoir composed of two layers of different permeabilities and equal thicknesses. Homer gave no information on differential depletion between layers, and the treatment of Tempelaar-Lietz was not applicable for prediction of pressure build-up behavior. In addition, it was thought that a more rigorous treatment than the one by Tempelaar-Lietz would be valuable in determining the range of validity of this solution. The present study, therefore, was made of a bounded reservoir composed of two or more layers,

By K. Mukherjee

Instantaneous resistance change during martensitic transformation in Fe-30 at. pct Ni alloy has been studied using a low-noise electronic system. The smallest signals recorded in this investigation were of the order of 10 pv. These small signals did not show the initial increase reported by earlier investigators to support a double shear mechanism.&apos; A variety of pulse shapes and sizes was observed during "burst" transformations, and these signals were neither a linear function of the size of martensite plates nor of the volume fraction transformed. Even the smallest signals, presumably from single plates, showed complications resulting from elastic and/or plastic deformation, shock wave propagation, and so forth, which are inherent in the growth process of a martensite plate. The time of formation and interface velocity determined froni this experiment agree very well with the pioneering work of Bunshalz and Mehl.&apos; AN Fe-30 at. pct Ni (c0.005 pct C) alloy was used to study the time of formation of martensite plates. Martensitic transformations, unlike the nucleation and growth processes, are usually characterized by an extremely fast reaction rate. During the transformation, the crystal structure changes and this change is propagated through a finite volume of the parent crystal lattice within a very short time interval. The interface between the two phases probably consists of moving dislocations, and the time of formation of the plate depends on how fast this dislocation interface can move. Knapp and Dehlin~er or Cottrell and Bilby mechanisms, or similar dislocation models, can be used to calculate the time of formation of a martensite plate of a given size. In the past, conventional photographic technique475 as well as electrical resistivity techniques"~-" have been used to measure the time of formation of a martensite plate. The specific resistance of the martensitic phase in Fe-30 at. pct Ni alloy is lower than that of the austenite phase. Therefore if a current is passed through a small austenite sample in series with a large external resistance, then one would observe a voltage change across the sample as martensite is formed. Such dc measurements are shown in Fig. 1. The initial large voltage drop in Fig. 1, at the M, temperature, is due to a "burst" transformation where a large number of plates are formed in a cataclysmic manner within a very short interval of time. Even during the later stages of transformation as shown in Fig. 1, one can observe discontinuous voltage changes due to small bursts. In order to resolve the time scale of such discontinuous stages, the voltage signals are amplified and fed into a highspeed oscilloscope. In this investigation a low-noise amplifier was used for the first stage of amplification. The signal to noise ratio was further improved by the design of a pulse transformer. This transformer was capable of amplifying the signal by a factor of six. Voltage signals were studied over a wide time scale ranging from 2 sec to 0.1 psec. I) EXPERIMENTAL PROCEDURE A) Specimen Preparation. Specimens were cut from induction-melted Fe-30 at. pct Ni (<0.005C) alloy and cold-rolled to 0.2 by 1 mm cross section and an average length of 5 cm. During mechanical shaping, the specimens were strain-annealed at 950°C for 24 hr in vacuum. Finally the finished samples were vacuum-annealed at 1000°C for 6 hr and water-quenched to room temperature. The average grain diameter was 0.02 cm. B) Cooling System. The M, temperature of the alloy was -55°C. Fig. 2 shows the arrangement which was used to cool the specimen at a slow rate. The specimens were mounted inside a i -in.-diam hole in the 2-in.-long section of the copper specimen holder. This cavity was filled with silica gel. A dummy specimen was used under identical conditions for

Jan 1, 1969

By Hans Allenius, R. T. Hukki

This paper describes in quantitative terms the effect of sharpness of classification on the performance of the closed grinding circuit. The analysis is based on a large number of laboratory experiments designed to simulate the two most common industrial closed grinding systems. The experimental results show quantitatively the degree of improvement achievable by more efficient classification. In an earlier paper1 the senior author has presented a trend showing qualitative analysis of mill and classifier performance in tile closed grinding circuit. According to this analysis, the master key to a major improvement appeared to be effective removal of finished fine material from the classifier sands, or in other words, improved sharpness of classification, leading simultaneously to a substantial reduction of the circulating load. One purpose of this paper is to present the results of a quantitative investigation of the closed grinding circuit. Another is to set forth the essential pertinent variables revealed by the quantitative experiments carried out by the junior author. In the two most common systems of closed-circuit grinding, (1) feed to the circuit is introduced into the grinding unit, normally the ball mill, operating in closed circuit with the classifier; or (2) feed to the grinding circuit is introduced into the primary grinding unit, normally the rod mill, discharging into the classifier in closed circuit with the secondary grinding unit, normally the ball mill. In the following discussion, these two systems are analyzed separately in the indicated order. BALL MILL - CLASSIFIER CIRCUIT The Test Apparatus and Procedure: The test appara- tus included: (1) a F 195 mm x 220 mm laboratory ball mill rotated at a speed 77% of the theoretical critical speed, and a 7-kg batch of F 20 mm-F 50 mm steel balls; (2) a conventional 65-mesh test sieve and a Ro-Tap sieve shaker serving as a classifier; and (3) a Permaran instrument manufactured by Outo-kumpu Co. for surface area determinations by the permeability method. As no continuous closed-circuit experiments could be brought about on a laboratory scale, the process was broken down into alternating grinding and sizing steps in such a way that the new feed plus the returning sands always formed a batch of 1000 gm. For each selected grinding period and for each selected sharpness of classification the basic steps were repeated six times. Steady-state conditions were then reached. Crystalline vein quartz was used as a test material. Feed to the process consisted of -10-mesh fraction of this quartz crushed in rolls. This fraction included 15% of-65-mesh material. Experimental Results: The general flowsheet is shown in Fig. 1. Table I gives the essential data obtained representing steady-state conditions under the indicated set of variables. The table is based on 110 grinding experiments, 440 screen analyses and an equal number of specific surface area determinations. Fig. 2 shows the relationship between the cumulative net energy consumption and the cumulative number of mill rotations as evaluated by separate experiments. Note that this relationship is not linear but is instead represented by a slight curve. The data given in Table I are presented in graphical form as follows: Fig. 3 shows the produced -65-mesh material in grams per minute vs. time of grinding in minutes; the sharpnesses of classification at 65 mesh were 100%, 75% and 50%. It is clearly indicated that the highest-capacity figures call for relatively short grinding times and for the sharpest possible classification. Fig. 4 presents the specific surface area on the final -65-mesh product in square centimeters per gm vs. time of grinding in minutes. In conventional mineral dressing processes, a final product characterized

Jan 1, 1969

By W. L. Phillips

Single crystals of aluminum, brass, and copper oriented for (100) and (110) slip were extended at 25°, 400°, and 600°C in simple shear. Aluminum specimens oriented for nonoctahedral slip began to shear at a higher critical resolved shear stress than specimens oriented for octahedral slip. Parabolic stress-strain curves were obtained from zero strain. The initial rate of parabolic hardening was lower for specimens sheared on the (100) plane in a close-packed direction <110>, than for specimens sheared in a nonclose-packed direction <100>. metallographic evidence, however, showed that all slip traces could be explained in terms of (111) <100> slip. All attempts to cause nonoctahedral slip in copper and 70-30 a-brass single crystals were unsuccessful. Instead of shearing, the crystals bent, allowing {111} type planes to come into action. NONOCTAHEDRAL slip in aluminum has been reported under three different conditions: first, as the main mode of slip in tension experiments at elevated temperatures;&apos;-&apos; second, as the main mode of slip in direct shear experiments at room temperat~re; and third, as a minor mode of deformation, i.e., as cross-slip, in tension, shear, and bicrystal experiments at room and elevated temperatures."-l2 However, as far as the author knows, nonoctahedral slip has not been reported in either copper or 70-30 a-brass. The present study was undertaken to determine whether nonoctahedral slip could be obtained in aluminum, brass, or copper at room or elevated temperatures when the shear stress was approximately constant over the cross-section, a maximum at the center, or a maximum at the surface. EXPERIMENTAL PROCEDURE A detailed description of the crystal preparation and shearing apparatus has been given previo~sly. Cylindrical crystals 1/2 in. in diam and 8 in. long were grown from the melt in a temperature-gradient furnace. The aluminum contained 0.001 pct Zn, 0.001 pct S, and 0.001 pct Fe; the 70-30 brass contained 0.015 pct Pb, 0.001 pct Fe, 0.01 pct Ni, 0.02 pct Sn, and 0.005 pct Se; the copper was certified OFHC of 99.98 pct purity. All samples were electropolished prior to testing. The shear apparatus was a modified Bausch type. The strain sensitivity was 4 x lob4 Load was applied by clamping the rods attached to the shear plates in an Instron tensile machine. The rate of loading was 0.02 in. per min. In all cases a 1/8-in. gage length was used. For the tests performed at 400° and 600°C the shear plates, collars, and rods were made of stainless steel. These elevated-temperature tests were performed in an argon atmosphere. A) Aluminum at Room Temperature. Values of a and ß for the various slip planes and slip directions investigated are shown in Table I where a is the complement of the angle between the specimen axis and the slip direction, and ß is the angle between the specimen axis and the normal to the shear plane. The shear stress is a function of a (assuming ß - 0);10 when a is less than 27 deg, the shear stress on the slip plane for which the specimen is oriented has a maximum at the center of the crystal; at a = 27 deg the shear stress is constant across the slip plane; for a greater than 27 deg the shear stress is a minimum at the center. Fig. 1 shows the stress-strain curves for specimens cut from crystals 1, 2, and 5, which were sheared on the (010) plane in the [loll direction at room temperature. These three crystals have shear-stress distributions corresponding to the three dif-

Jan 1, 1962

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

The subjects of this study are two corrosion phenomena familiar to operators of aluminum plants employing Soderberg anodes of the vertical type, namely the sul-fide scale formation observed at the steel contact spikes and the corrosion wear observed at the lower edge of the gas collecting skirts. The causes of these corrosion phenomena are discussed on the basis of observations from practice and measurements on commercial cells as well as on laboratory experiments. It is concluded that the anode spike corrosion is mainly due to the attack by sulfur compounds contained in the anodically evolved gases and that this attack is greatly promoted by cracks and pores in the anode carbon embedding the lower spike ends. The corrosion of the gas collecting skirt is mainly attributed to anodic dissolution of the iron during occasional contacts with the melt. ANODE SPIKE CORROSION The visible result of this corrosion is the formation of a brittle loosely adherent scale on the lower ends of the mild steel spikes maintaining the electric contact to the carbon anode, Fig. 1. The thickness of the scale usually varies from 0.5 to 3 mm, but in some cases scale of about 10 mm thickness has been observed by the writers. During the spike pulling, usually repeated every 3 weeks, part of the scale often loosens and remains in the anode carbon, resulting in contamination of the aluminum with iron. This corrosion has been attributed to reaction of the iron with gaseous sulfur compounds originating from the anode paste materials.&apos;-4 This paste usually consists of 70 pct precalcined petroleum coke with 1.2 to 1.4 pct S and 30 pct coal tar pitch containing 0.5 to 0.7 pct S. During operation the gasification of the anode materials takes place in two ways: First, gases are evolved by the gradual baking of the anode paste added on top of the anode. Due to the sealing effected by the upper semifluid zone of the paste, these gases, containing sulfur compounds from the pitch, are forced downward through pores and cracks in the rigid anode carbon. At the temperatures of the zone of the lower ends of the spikes, 700" to 900°C, the original components of the baking gas must undergo decomposition, similar to that taking place with the production of coal gas, resulting in a gas mixture consisting mainly of H2 and CH4 with small percentages of H2S as the main sulfur compound.5 Second, the anodic reaction results in a mixture of C02 and CO, the total quantity of which is about 15 times that of the baking gas. These anode gases must carry the entire sulfur content of the carbon gasified by the anodic reaction. Henry and Holliday6 have shown that COS is the main sulfurous component of the anode gases from Soderberg cells. Soderberg anodes usually exhibit a network of vertical cracks, frequently traversing from one spike to the next one and to the outside of the block and widening downward to the working face of the anode. In addition the anode carbon, particularly that below the spike ends, is rather porous, as indicated in Fig. 1. It therefore seems probable that the anode gases also may partly penetrate to the spike ends. As the anode is partly immersed in the melt, the static pressure of this must forward this penetration. I) SPIKE SCALE COMPOSITION A great number of freshly extracted spikes from industrial plants were inspected and samples of the scale collected for examination. Before analyzing the samples a thin iron oxide layer, formed by air oxidation of the outside of the red hot scale immediately after spike pulling, was removed. On the average the Fe/S ratio found by these analyses corresponded to I the composition FeSl. oo7. X-ray powder patterns showed no oxide and otherwise agreed with those found by Haraldsen7 for iron sulfide with 50.00 at. Pct

Jan 1, 1970

By J. F. Held

In a study of the influence of cold rolling on mechani cal properties of steel, it was found that the specific rolling procedure influenced crystallographic orientation. Properties developed by several rolling modes were determined and related to crystallographic orientation. Sanzples were cold-rolled various amounts on a laboratory mill. When palm oil was used as a lubricant, the crystallographic orientation was homogeneous throughout the thickness of the samples. Other samples were rolled without lubrication. Variations in intensity of the recrystallization texture components persisted throughout more than 50 pct of the volume of these samples. When the average plastic strain ratio, which is dependent upon crystallogvaphic orientation, was plotted as a function of percent reduction, a maximum was found at 40 pct in the samples which contained the observed texture variation. No maximum was found for the samples with the homogeneous texture distribution. Other mechanical properties, such as tensile strength and yield strength, were not influenced by the variation in crystallopaphic orientation. MECHANICAL properties of steel sheets depend, in general, upon the structural properties of the steel. For example, the Petch equation describes the relationship between yield strength and grain size. Other properties, such as hardness, vary with chemical composition. The plastic strain ratio, or R value, has been found to be dependent upon crystallographic orientation . In the course of investigating the effect of cold rolling on mechanical properties, it was found that a previously reported relationship between percent cold reduction and R value was not always observed. Published data had shown that the optimum cold reduction for best R values is 70 pct for aluminum killed steel.&apos; However, by altering the rolling conditions, the optimum reduction can be shifted to much lower values, or it can be moved to very high values. This paper describes the rolling conditions that lead to shifting of the optimum cold reduction. The effect of rolling conditions on the various structure parameters and the resulting mechanical properties are evaluated. EXPERIMENTAL PROCEDURE Samples of three low-carbon aluminum killed steels were cold-rolled various amounts on a 9-in.-diam 2-high laboratory mill. Hot-mill thermal practice and steel chemistries are listed in Table I. Steel A was rolled with palm oil lubrication and heavy reductions on each pass; i.e., a total reduction of 75 pct was ac- complished with a maximum of five passes. Steel B was rolled without lubrication, and light reductions were given on each pass. After approximately 75 pct reduction, it was necessary to use a small amount of light oil to achieve any additional reduction in thickness. Following cold reduction, the samples were box-annealed at 1300°F for 10 hr. The heating rate between 800" and 1300°F was 50°F per hr, and the cooling rate following the soak period was 50°F per hr. Tensile specimens were machined from the annealed material and these were used to measure yield strength, tensile strength, and the plastic strain ratio (R value). Recrystallization textures were determined by an inverse pole figure technique.*&apos;3 Integrated intensities of the (110), (002), (112), and (222) reflections were recorded for those planes lying parallel to the sheet surface. Examinations were made on both surfaces of each sample, and also at various levels beneath each surface to approximately 0.010 in. depth by etching techniques. RESULTS R Values. The R values obtained in steels A and B are shown as a function of percent cold reduction in Fig. 1. No optimum cold reduction was observed in steel A, rolled with palm oil lubrication. It is likely, however, that an optimum reduction would have occurred had higher reductions than 88 pct been employed. The optimum reduction in steel B occurred at 40 pct. The behavior in both of these steels is quite

Jan 1, 1968

By Thomas C. Wilder

ALTHOUGH there is an abundance of thermodynamic information available in the literature today, no experimental data on the standard molar properties of formation of zinc oxide have ever been reported for the temperature range 419.5" to 908°C. This is the temperature range for which zinc metal is a liquid. so that the formation reaction is: Data have been reported for Reaction [I] where zinc is a solid or a gas. Maier. Parks, and nderson&apos; measured the electromotive force of the cell: in order to obtain the free energy of the reaction: over a limited temperature range. With the known properties of H2O, those of ZnO were calculated. These workers found that t;j of ZnO is -75,930 ± 150 cal per gfw and Mtf is-83,000 300 cal per gfw at 25°C. akolkin made similar measurements to obtain ilF7 and AH; of -75,870 and -82,540 cal per dw respectively at the same temperature. Truesdale and arirlg and Kitchener and 1gnatowicz4 measured the equilibrium of the reactions: respectively, in order to determine Ff of ZnO from the known values of CO, CO2, and H/X The thermodynamic properties of ZnO, presumably taken from the above investigations, are tabulated by Kubaschewski and vans&apos; and Wicks and Block" The latter reference also gives values for the range where zinc is a liquid. These numbers are probably acquired from the known extremities of the range plus Cp data of the components. In the present work the electromotive force of the cell: was measured in order to calculate the properties of ZnO from the well known values of NiO for the temperature range where zinc is a liquid. In Cell [B] the cathode reaction is: and at the anode: The overall reaction is: for which the free energy change is: where is the electromotive force in volts of cell [B] after correction for the Pt-Ta thermocouple. The standard molar free energy of formation of NiO is very well known as a function of temperature. Kiukkola and agner&apos;s data are used in most tabulations. The error is probably less than I00 cal per gfw, The latter authors were the first to use solid mixed oxide electrolytes in galvanic cells. Their work with NiO and other oxides was performed with cells similar to Cell [B] using a variety of reference electrodes of fixed oxygen potential. There may be a small composition range for which either NiO, ZnO or both exist. If nonstoichiometry does exist for these oxides, then the properties described herein are those for the metal saturated compositions. The simple cell design was the same as described elsewheres except that the molten metal electrode was about 125 g of pure zinc including a small (0.25 to 0.50 g) amount of ZnO. The mixture of pure nickel and NiO powders making up the reference electrode was contained in a tube of the ZrOl + CaO electrolyte which was immersed in the molten zinc. A platinum contact was made to the reference electrode; tantalum to the zinc. A refractory cement plug was necessary at the open end of the electrolyte tube in order to prevent zinc vapor from contaminating the reference electrode. Experimental details such as the vessel containing the cell, furnace, temperature control and measurement, and electromotive force determinations of the cell have all been outlined previously. The temperature was varied randomly in the range between the freezing and boiling points of zinc. After each temperature change, time was allowed for the drift at the new temperature to be less than +;"c whereupon a series of three cell readings was taken at least 10

Jan 1, 1970

By R. M. Rose, D. P. Ferriss, J. Wulff

Single crystals of tantalum, tungsten, and the binary alloys thereof were grown by electron-beam zone melting and tested in tension between 77° and 373°K. The ductile-to-brittle transition temperature increased sharply with solute concentration, for both tungsten-rich and tantalum-rich alloys; apparently, the maximum transition temperature exists near the 50 pet concentration. Twinning was observed to be a consequence of cleavage-crack propagation. Cleavage occurred on(100)planes, and extensive tearing and "river markings" were present. The onset of brittleness could not be associated with any change in deformation mode, the yield point phenomenon, or the large rise in yield stress with decreasing temperature. Cleavage was observed to initiate at either the specimen surface, or subgrain boundaries. The observation was made that the grain boundaries of Polycrystalline materials are probably even better as nucleation sites for fracture, and are responsible for brittleness at high temperatures and lower solute concentrations than those of the corresponding single crystals. TUNGSTEN and tantalum, the two high-melting neighbors in the third transition period of the periodic table, present striking contrasts. Although both are bee, tungsten has far higher elastic moduli, and the highest ductile-to-brittle transition (DBT) of all the pure metals.&apos; Tantalum, however, is ductile at liquid helium temperatures. Large strain aging and yield point phenomena are observed in tantalum,2,3 but only to a lesser extent in tungsten.4 Tungsten work-hardens at a high rate,5 whereas this effect is negligible in tantalum.&apos; Since the mutual solid solubility of these two metals is complete,7 and no ordering has yet been reported in the binary system, the possibility of depressing tungsten&apos;s DBT by tantalum additions was considered. Also, tungsten additions to tantalum could produce hard, high-melting alloys which might be ductile at room temperature. Such alloys offered excellent bases for complex alloy development, particularly with regard to the effect of rhenium on Group VI metals.8"10 In addition, there was the opportunity to examine flow and fracture modes in the vicinity of the DBT, with particular emphasis on the correlation between brittleness and fundamental deformation mechanisms. Myers11 has reported that recrystallized alloys with up to 10 pet W in tantalum are ductile at room temperature, but alloys with 20 pct W could not be swaged at temperatures as high as 500°C. The whole spectrum of Ta-W alloys has been surveyed by Braun, Sedlatschek, and Kiefferl2 using sintered powder compacts. In addition to some physical properties they reported a maximum hardness at about 50 at. pet W, dropping to much lower hardness levels for the pure components. They were able to cold work tantalum-base alloys with as much as 30 pet W and to warm work tungsten-base alloys with up to 20 pet Ta by procedures similar to those used for pure tungsten. EXPERIMENTAL In order to study deformation modes and to keep the impurity concentrations at a minimum, electron-beam zone melting was used to prepare single crystals of high purity. The electron-beam zone melting apparatus is similar to that described by Calverley, Davis, and ever" and incorporates a grid control rectifier to maintain control of emission current. Pure metals were refined by making three zone passes at 4 mm per min up the rod. Alloys were prepared by melting together wire of one constituent on a previously melted rod of the major constituent. Subsequently, two zone passes were made in opposite directions to level the composition after the manner suggested by pfann.14 Purification of the starting materials was accomplished by evaporation of the several impurities, and the degree to which this was accomplished is indicated in the chemical analyses of Table I. The uniformity of composition along a zone levelled rod was within the i 1 pet accuracy of the fluorescent X-ray technique used to determine composition. Crystallographic orientation of the

Jan 1, 1962

By Eugene F. Broome, Hugh A. Walls

Self-diffusion coefficients were measured using the modified shear cell technique over a temperature range from 31" to 401°C. These data agree within experimental error with those of Petit and Nachtrieb, which were determined from 30°to 99°C. LIQUID self-diffusion behavior in gallium has been studied previously by Petit and Nachtrieb&apos; using their shear cell technique.&apos; Data were obtained in that investigation over temperatures ranging from 30.6 to 98.7"C, and these comprise the only published data for liquid gallium. In the work reported here, diffusion data were obtained from 30.8 to 400-9.Cusing a shear cell technique different from that of Petit and Nachtrieb. This modified shear cell method and the mathematical analysis for diffusion in a finite capillary geometry have been previously described.3 PROCEDURES AND ANALYSIS The segments of the modified shear cell were fabricated from types 304 and 316 stainless steel. No corrosion problems with gallium were encountered until attempts were made to obtain data at 500°C. The diffusion capillary diameter was 1.59 mm and capillary lengths for the four sets of cell segments used are given in Table I. Gallium with a purity of 99.999 wt pct was obtained from Var-Lac-Oid Chemical Co. The gallium-72 isotope used to measure the self-diffusion coefficients was produced from this inert gallium by irradiation in The University of Texas Reactor Facility, and was checked for radiochemical purity. Following a period of isothermal diffusion controlled to within 0.0l°C, the contents of each capillary section were emptied into a counting planchet, weighed to assure that gallium had not been lost during handling, and the radioactivity determined by windowless gas-flow proportional counting. Great care was taken to obtain a reproducible counting geometry for the samples. Diffusion coefficients were obtained from the solu-tion3 to the diffusion equation for the modified shear cell problem, viz.: in which B2= C2(t)Li + L2)- CSL1-COL2 P* (C0-Cs)(L1+ L2) and L, and L2 are the capillary segment lengths. The step-function initial concentration distribution was expressed as C(x,O) = C, for -L1 = x < 0 and C(x,O) = Co for 0 < x 5 L?. Also, C2(0 = ^- fcix,t)dx Computation of the diffusion coefficients was done numerically as described in our earlier paper.3 Because of the short half-life of gallium-72 (14.1 hr) and the relatively long counting times taken to give a precise value of the diffusion coefficient, it was necessary to account for the radioactive decay both during the actual count and between counts for different samples (before and after diffusion). Thus, the average count rate Cz(t) for a second sample counted from times t3 to t4 can be made consistent with the average rate Co determined for a first sample counted from times t1 to t2 by the relationship: N(e-»i-e-M») , , C2(f) " &-«,)(*-«.-«-»«) [21 in which N is the total number of counts taken and is the decay constant. RESULTS AND DISCUSSION The self-diffusion coefficients determined in this investigation are listed in Table 11. Values of the parameters used to calculate the coefficients are given in the table, as are values of the random counting error &apos; for the concentration ratio pz and the corresponding expected random variation AD in the diffusion coefficient. The quantity is calculable from: &apos;Cg — C2(t)} , „ ,2 .-„¦, M co-csl(ACs)J W in which AC is the error in the individual count rate. The mean values of the diffusion coefficients within each temperature group are also given in Table 11. Such temperature groupings of data are reasonable because of the small variations between the temperature~.~

Jan 1, 1970

By V. Kondic, W. M. Rumball

HUNT and Jackson&apos; have recently suggested that binary eutectics might be classified according to the entropy of fusion of the component phases. Such a classification was in fact proposed2 some time ago by the authors and the purpose of this communication is to present some supporting evidence. As pointed out by Hunt and Jackson&apos; typical metals of low entropy of fusion, ?S, tend to form normal eutectics (using Scheil&apos;s terminology3). Where one phase is metallic (low ?S) and the other nonmetallic (high AS) then anomalous structures are formed. These anomalous structures may either be regular (e.g., Bi-Sn)or irregular (e.g., A1-Si). Finally Hunt and Jackson suggest that where both phases are of high ?S regular faceted structures are formed. In the proposed classification2 the ratio of the entropies of fusion is taken as the quantitative parameter, i.e., ?Sa/?SB = E, where e > 1.0. An extensive literature survey has been carried out2,4 for reliable photomicrographs of eutectic structures. The structures, numbering 151, have been classified into two classes, viz., normal (i.e., lamellar and rodlike) and anomalous. The latter group has been arbitrarily subdivided into regular and irregular anomalous eutectics. Details and sources of the structures are given elsewhere.2,4 In the absence of better thermodynamic data the value of E has been determined for each of the systems making the following assumptions and approximations: l) The entropy of fusion of solid solutions may be calculated additively;5 ii) Inter metallic compounds are treated similarly but with the addition of the following term for fully ordered structures.5 -4.573(Ni lOg10 Nl + N2 log10 N2) where Nl and N2 are the atomic fractions. It might be argued that the entropies of fusion are meaningless as the eutectic phases form at some temperature (T,°K) below their true melting point (Ta or Tb). As AS, = Lo/To if La the latent heat of fusion of a, is assumed independent of temperature, the actual entropy change AS& is given by La/Te. The ratio of entropies of fusion then becomes Fig. 1 shows E&apos; plotted against cumulative totals for normal and anomalous systems from which it is seen that normal eutectics predominate at low values of E&apos;; e.g., some 90 pct of normal systems lie below E&apos; = 1.5 with 65 pct of anomalous systems above this value. Fig. 1 also shows that the regular anomalous structures occur mostly at low values of c&apos; possibly suggesting growth more akin to normal than anomalous growth. The choice of c as a classification parameter was based on nucleation concepts, it being observed that metals widely separated in Sundquist and Mondolfo&apos;s8 nucleation series were anomalous and those close together normal. The basis of these classification views is really outside the intended scope of this communication but it is hoped to explain them fully in the near future.7 Having arrived at this entropy of fusion classification by nucleation considerations it is interesting to note that Hunt and Jackson&apos;s ideas are based on growth considerations. Elsewhere one of the authors4 has shown that an even better classification of the metallographic structures reviewed is obtained from purely conventional heterogeneous nucleation concepts. It has been found that systems having a value of the parameter +b less than 0.28 are almost certainly normal and above this anomalous: V, is the gram atomic volume. This parameter is nevertheless closely related to c and c&apos;, these being an approximation of p. The parameter is also related to the other classification3,8,9 which have met with any success in the past. All these classifications are to be reviewed shortly by the authorsU7 A significant thing about the classifications based on

Jan 1, 1968

By H. D. Outmans

The mechanics of filtration are described by a theoretical-empirical nonlinear diffusion equation which, under certain circumstances, may,be linearized and then solved explicitly. For filtration under static conditions linearization leads to a boundary value problem analogous to a heat flow problem with a known explicit solution. The corresponding solution for static filtration is compared with published experimental data. Under dynamic conditions filtration takes place in three successive stages. During each of these the rate of filtration and/or the thickness of the filter cake are different functions of the filtration time. The proposed mechanism explains the observed high resistance of dynamically deposited filter cakes against erosion and also the connection between filtration rate and viscosity of the drilling fluid. Several of the quantities governing dynamic filtration have no counterpart in the static filtration mechanism. The static filtration rate is, therefore, not a reliable measure for the dynamic rate and vice versa. INTRODUCTION Filtration under simulated borehole conditions, i.e.. either from a static suspension or from a suspension flowing parallel to the filter cake (dynamic filtration), has been the subject of several laboratory studies.1-7 This experimental and theoretical work showed that many aspects of the filtration mechanism cannot be explained by an elementary filtration theory based on the assumption that the filter cake is incompressible. For a more satisfactory theory compressibility should be taken into account. This has been done. at least to some extent, in the filtration theory developed for the chemical industry. Surveying the literature (see Ref. 8 for a bibliography) it becomes apparent that, although several properties of filter cakes deposited from many different suspensions have been measured, including compressibility, the filtration equations are essentially empirical in nature. No attempt has been made, for instance, to develop filtration theory along the lines of consolidation theory.12 This theory, upon which a highly successful development in soil mechanics rests, would appear to be an excellent starting point for a filtration theory since the compressibility concept is an essential part of it. As we will use this theory in the following development it is well to state the four assumptions on which it is based: 1. The fluid flow through a compressible porous medium is governed by Darcy&apos;s law. 2. The rate of change in fluid content of an element of the porous medium is proportional to the rate of change of solid pressure between the particles. 3. The solid particles are incompressible within the range of pressures considered. 4. The total pressure on a surface normal to the line of flow is equal to the sum of the fluid pressure and the pressure between the particles (solid pressure) at that surface. To calculate the rate of filtration and other quantities of interest it is necessary to know the filter cake compressibility and the permeability as a function of the solid pressure. It has not been possible to calculate these functions from theoretical considerations and they will therefore be introduced in this paper as empirical expressions. Both are determined in a compression cell where the cake is subjected to a mechanical load. Permeability and compressibility are measured after the solid pressure has stabilized, i.e., after the excess fluid pressure has been dissipated and the uniform pressure is transmitted entirely by the solids. The permeability and compressibility thus determined are not the same as during filtration in the borehole, under either static or dynamic conditions, because then, due to frictional drag, the solid pressure and hence also the permeability and compressibility vary along a line normal to the direction of the mean flow and can only be defined locally. DERIVATION OF THE FILTRATION EQUATION FOR COMPRESSIBLE FILTER CAKES As the filter cake in the borehole is thin compared to the radius of the hole the filtration may be considered as linear. Taking the x-axis normal to the wall, with its origin at the formation, we have, according to Darcy&apos;s law,

By Orville R. Lyons

CENTRIFUGAL force has been utilized for the dewatering of fine coal for over 50 years by means of machines commonly called centrifugal dryers. In any centrifuge the coal and water are subjected to a spinning action which usually inctedtocreases in intensity as the coal progresses through the machine. This spinning action, or the centrifugal force that it induces, tears water away from coal particles and produces a dewatered coal. The effectiveness of the dewatering action for any particular machine is governed by the size-consist of the coal and the centrifugal force imparted to the water on the coal. Four makes of centrifuge are currently being used to dewater fine bituminous coal in the United States. These include the vertical, basket-screen C.M.I. (Centrifugal and Mechanical Industries) Carpenter, Reineveld, and the horizontal solid-bowl Bird. The C.M.I. and Reineveld centrifuges are similar in construction and are variations of the Elmore centrifuge, varying principally in the slope of the basket, operating speed, size of perforations in the basket, and diameter of the basket. The same operating description suffices for both. These centrifuges are made up of two rotating elements, an outside conical screen frame and an inside solid cone which carries spiral pusher blades. The screen frame is supported by a hollow shaft, and the solid cone by a spindle shaft passing through the hollow shaft. Both the screen frame and the solid cone rotate at high speeds; the solid cone, with its scraping flights, rotating somewhat more slowly than the screen. The wet coal enters the machine at the top, falls on the cone, and is thrown against the screen by centrifugal force. The coal slides down the screen until it meets the upper end of the flights, where it is moved slowly along the flights until discharged at the bottom. The elfluent passes through the sieve basket or screen and discharges into a launder. The Carpenter centrifuge consists of a conical rotating element with a vertical axis, built up of three rows of perforated stainless-steel plates or stainless-steel wedge-wire or round-wire sections cut and rolled to conform to the surface of the cone. Wet material is delivered to a conical hopper inside the centrifuge casing and is distributed in a thin, even layer over the inner surface of the cone by a disk mounted on the rotor shaft. Impacting of the coal against the screen and the centrifugal force exerted as the material moves downwards creates a dewatering effect. The moisture is forced through the coal bed and then through the perforated plates of the basket, collecting in a circular trough built into the centrifuge. The effluent is conducted from the trough through the centrifuge casing by outlet pipes. The dewatered coal is discharged over the inside bottom edge of the rotor. The Bird centrifuge consists of a tank or truncated conical shell, which is revolved at the desired speed by means of a drive sheave. A screw conveyor rotates inside the cone or bowl at a slightly lower speed in the same direction of rotation. The feed entrance, in the center of the large end of the truncated cone, is high enough to allow formation of a pool of slurry. Adjustable effluent-discharge ports are located in the large end of the bowl so the level of the liquid can be regulated. The solids are moved forward by the screw conveyor as fast as deposited and carried above the level of the pool for an interval before leaving the bowl. In the past these four makes of centrifuge could be compared only by indirect means. The author published a rough comparison method in 1949&apos; but

Jan 1, 1952

By M. N. Pathasarathi, P. A. Beck, T. J. Koppenaal

EARLIER work1 indicated that in rolled and annealed copper the volume fraction of the cube-texture component may increase on continued isothermal annealing. Merlini found2 that in rolled copper the well-known increase in the amount of cube-oriented material with increasing annealing temperature3 is concurrent with grain growth, which takes place after recrystallization is complete. It was found that both in copper2 and in aluminum4 the texture resulting from primary recrystallization, even if this is followed by some grain growth, may in general comprise, in addition to the cube-texture component, four symmetrical texture components of the general type (123)[412], i.e., components not very far from the ideal orientations of the rolling texture. The volume fraction of the cube-texture component increases on further annealing at the expense of these four components.&apos; The present work was undertaken to study quantitatively the increase in the volume fraction of the cube-texture component in the course of normal grain growth, under varying conditions. Since the grain-gr3wth behavior of A1-Mn alloys has been already investigated in some detaiL5 an A1 + 0.8 pct Mn alloy was chosen for this work, in which the extent of normal grain growth can be effectively controlled by the inhibiting effect of a dispersed second phase. EXPERIMENTAL PROCEDURE High-purity aluminum of the following composition was used: A1 99.997 pct, Cu 0.0004 pct, Fe 0.0005 pct, and Si 0.001 pct. A high-purity A1-Mn master alloy was prepared by dehydrating manganese chloride at 500°C and reacting it with molten high-purity aluminum at 750°C in a graphite crucible.5 The Mn metal reduced from the salt by the molten aluminum goes into solution in the latter. The master alloy? containing 13 pct Mn, was solidified under conditions suitable for minimizing segregation. An ingot of the final alloy, to be used in the experiments, was per pared by melting high-purity aluminum and the necessary amount of master alloy in a graphite crucible, and by pouring the molten alloy into a graphite mold preheated to 700°C through a box containing graphite baffles designed to intercept most of the aluminum oxide films floating in the melt. The melt was then solidified by placing the mold on a water-cooled copper plate and by keeping the top of the mold hot, in order to minimize piping. The 6 1/2 in. long, 11/4-in.diam ingot consisted largely of a single crystal. Chemical analysis showed that there was little segregation from the bottom (0.83 pct Mn) to the top (0.81 pct Mn). Spectrographic analysis of the ingot showed that the impurity content remained essentially the same as that of the aluminum used. The ingot was processed so as to obtain a uniformly small grain size. without banding. The ini-tial steps of rolling in the form of a flat bar and of annealing, down through a thickness of 0.4 in., are shown in Table I. At this point the bar was cut into four sections, each approximately 3 in. long, which were processed separately as shown in Table If. The table also gives the penultimate grain sizes obtained in each section by annealing prior to the final rolling of 90 pct RA. During the final rolling the strips were reversed end to end between passes. Annealing treatments were given in a salt pot furnace, with the temperature controlled to 1°C. All annealing of section "6s" was carried out above the solvus point to avoid the formation of second-phase precipitate. The penultimate annealing was sufficiently short to give a relatively fine grain size in spite of the high temperature. Section "6L" was processed in a similar manner, except that the penultimate annealing was much longer, so as to allow considerable grain growth. Section "4" was given the two final

Jan 1, 1961

By S. T. Wlodek, John Wulff

Dense, adherent, and ductile coatings of chromium can be applied to Molybdenum by selectively freezing out the chromium solute from a supersaturated copper-or tin-rich liquid alloy. The successful exploitation of this technique depends on the control of variables common to any freezing process. Under the most favorable combimtion of supersaturation, nucleation, and mass-transfey, coatings as thick as 0.004 in. can be obtained. In exploratory experiments it was found that a coating of chromium may be applied to molybdenum by immersing the molybdenum body in a supercooled copper-chromium or tin-chromium melt and selectively freezing out the contained chromium onto the molybdenum body. Supercooling of the liquid metal plating bath can be achieved by cooling, or the maintenance of thermal or concentration gradients in the melt. The technique is similar to conventional dip-plating procedures where the sample is immersed in a molten bath of the pure plating medium, except that in these studies, the plating medium consisted of a dilute solution of chromium in liquid tin or copper. The success of this method requires that the base material to be plated be isomorphous with the coating and insoluble in the plating bath. In addition, the plating bath, while having an appreciable solubility for the coating component, must have negligible solid solubility in the solid plate. Such relationships exist in the molybdenum-chromium, chromium-tin, and chromium-copper systems. Liquid tin and copper are satisfactory as the plating solvent, because although chromium is appreciably soluble in both of these liquid metals, solid inter-solubility is almost negligible, and no compound formation occurs. The same relationships exist between molybdenum and copper or tin except that the solubility of molybdenum in liquid tin or copper is insignificant. It is this combination of solubility relationships, as well as the completely isomorphous nature of the molybdenum-chromium system, which allows the formation of a chromium coating on molybdenum by the selective freezing mechanism. Since the main deterrent to the widespread use of molybdenum for high-temperature structural applications is its poor oxidation resistance, the formation of a dense and ductile chromium coating on molybdenum may well be of commercial significance. In addition, the basic principle of coating formation by selective freezing should be applicable to other metallic or even nonmetallic systems. The precipitation of the solute from a liquid metallic solution, for the formation of a protective coating, has not been previously considered in the literature. Frequently, however, a similar phenomenon has been described in the corrosion of metallic heat exchangers by liquid metals1 wherein temperature gradients in the liquid metal heat-transfer medium result in the formation of layers or deposits of metallic residue2 in the cooler portions of the system. Impregnating techniques using liquid baths have been tried as a plating process. Semchyshen and Barr, for instance, have successfully diffused chromium into molybdenum by immersing the molybdenum specimen in a liquid tin-chromium or copper-chromium alloy. This simple holding technique fails to produce a layer of pure chromium and requires prolonged immersion to allow for the diffusion-activated enrichment of the molybdenum. During the course of this investigation, most of the phase relations published for the copper-chromium4 and molybdenum-chromium4 systems, were found reliable. It was necessary, however, to investigate the solubilities of chromium and molybdenum in liquid tin as well as the solubility of molybdenum in liquid copper. These determinations were made by a simpie weight loss technique on materials of the same purity as used in the plating studies. The results of these solubility studies are given in Tables I and I1 and indicate that although the solubility of molybdenum in liquid

Jan 1, 1961

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman&apos; and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965

By P. E. Arnold, G. S. Ansell

RELAXATION in metals has been studied in detail by many workers in recent years.1-5 These studies have shown that there is an energy-loss peak observed in a metal placed in mechanical resonance at low frequencies which may be correlated with various metallurgical processes. These experiments have been largely used to study single-phase materials. In order to study the effect of a finely dispersed second phase in a metal matrix upon this phenomenon, the relaxation behavior of an aluminum-aluminum oxide SAP-Type alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions was investigated by the use of internal-friction measurements. The alloys studied, designated MD 2100, consist of a matrix of commercial-purity aluminum containing a finely dispersed second phase of aluminum oxide. The aluminum oxide is present in this alloy in the form of fine platelets approximately 130A units thick and several microns on edge. The mean free path betwen dispersed platelets is approximately 0.5 p. The grain size of this alloy is extremely stable at temperatures as high as the melting temperature of the aluminum matrix. In the as-extruded condition the grain diameter is several microns, while in the recrystallized condition it is several millimeters in diameter. The damping characteristics of the alloy samples were determined using a torsional-pendulum device. The internal-friction constant was determined for this alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions over the temperature range from 343" to 923°K at frequencies of 0.9, 1.3, and 1.8 cycles per sec. An internal-friction peak was observed in testing the fine-grained alloys which was not observed for the coarse-grained alloys. This peak, which might be associated with a type of grain-boundary relaxation, was observed at each of the three different test frequencies for the fine-grained sample. The temperature at which the relaxation peak occurred for each of the three different frequencies is shown in Table I. From these data an activation energy of relaxation for each pair of frequencies was determined by comparing the temperature shift of the relaxation peak with frequency between each of the test frequencies, assuming that an Arrhenius-type rate equation is applicable. The activation energy of relaxation determined from these data is also shown in Table I. The mean value of the activation energy was about 6 kcal per mole. The activation energy for the relaxation process determined in this investigation indicates that the relaxation associated with the grain boundaries in this aluminum-aluminum oxide SAP-Type alloy is quite a different process than grain boundary relaxation in single-phase aluminum alloys. In these latter alloys, the activation energy for relaxation has been found to be the activation energy for self-diffusion, approximately 36 kcal per mole1,2 Where the activation energy is the same as the activation energy for self diffusion, it has been proposed that the relaxation phenomena is dependent upon vacancy formation and motion. It is apparent therefore, that, in this aluminum-aluminum oxide SAP-Type alloy, the relaxation must be due to another type of atom transport. It has been shown previously in studies of the high-temperature, low-stress, steady-state creep behavior of as-extruded aluminum SAP-Type alloys, that the activation energy for steady-state creep is one that may be characterized by the nucleation of dislocations from the grain boundaries. It is proposed that the relaxation behavior observed here is due to a similar effect. In this case, the internal-friction peak is a resonance behavior due to the time-dependent nucleation of dislocations from grain boundaries in the sample. A process of this type would have an activation energy which is undoubtedly stress-dependent and of the form Q = Q, + (dQ/du)u

Jan 1, 1962

By S. R. Maloof, W. R. Mitchell, J. A. Mullendore

Preliminary experimental evidence is presented to show that the metallic impurities aluminum, iron, and silicon, and beryllium oxide as found in commercially pure hot-pressed beryllium powder can be reduced to lower Concentrations by Zone -Purification techniques. The reduction in the concentration of aluminum to extremely low levels (10 PPm) is noteworthy, since earlier work demonstrated that aluminum is a major factor contributing to the hot-tearing of beryllium during fusion welding. On the basis of present findings, a method is suggested for producing beryllium metal of improved weldability. EXPERIMENTAL research now being conducted on the purification of beryllium indicates that several of the metallic impurities and beryllium oxide can be reduced to lower concentrations by employing standard horizontal zone-refining techniques. For the preliminary work, commercially-pure hot-pressed beryllium having a purity of 97.84 pct was used. The chemical composition is given in Table I. The hot-pressed beryllium was machined into bars 5/8 by 5/8 by 4 to 6 in. in length. Beryllium-oxide boats which had been conditioned by prior heating in a vacuum of 10"5 mm of Hg at 1100°C for 3 hr were used to hold the beryllium while it was zone melted. The boat with its charge, along with a smaller beryllium-oxide boat containing scrap beryllium to be used for gettering purposes, was loaded into a quartz tube and evacuated to 10-6 mm of Hg. Alter alternately evacuating and flushing three times with purified argon, the furnace tube was backfilled to a pressure of 1/6 atm of A and sealed off by means of a vacuum-tight stopcock. It was then removed from the pumping equipment and mounted on the traveling carriage of the zone-refining apparatus. Heating was accomplished with a 10 kw 450 kc induc- tion heating unit using an induction coil consisting of two turns of 3/16-in. diam copper tubing. Before starting to zone melt, the atmosphere in the furnace tube was gettered by heating the scrap beryllium in the smaller boat to above its melting point and holding at temperature for several minutes. The carriage was then shifted so as to locate one end of the beryllium ingot in the large boat within the induction coil. A molten zone approximately 3/4 to 1 in. was established by loading directly into the ingot. The molten zone was moved very slowly along the length of the ingot. Before each pass was made the procedure for evacuating, flushing, and backfilling, and so forth was repeatedI&apos; Speeds of 1 1/2 and 3 in- per hr were used with up to twelve zone passes. The appearance of a typical zone-refined ingot is shown in Fig. 1. After zone refining, the grains in the ingot appear to be elongated in the direction of zone travel, whilst before, they are essentially equi-axed. A microexamination revealed the presence of a network in the beryllium grains as seen in Fig. 2. Laue spots in back reflection pictures taken of the sample were not sharp, indicating the presence of subgrains in the structure. As can be seen, however, many of the network boundaries cross beryllium grain boundaries. It has been shown by Martin and Moore1 that beryllium solidifies as a bcc structure which then transforms to the hexagonal structure at about 1250oC.It is believed that the observed network is merely the outline of the bcc structure which formed from the melt and are not subgrain boundaries. In order to eliminate surface contaminants, approximately 1/16 of an inch of material was removed from the outer skin of each ingot after zone refining.

Jan 1, 1962

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,&apos; the values obtained were about a third those reported for a 5000 psi surface shear stress.&apos; RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By Michel Elle, John Chipman

The equilibrium of gaseous H20-H2 mixtures with liquid iron-columbium alloys in the range 0.2 to 2.4 pct Cb shows that the activity coefficient of oxygen is strongly diminished by Cb. The oxide in equilibvium with the melt is identified as CbO2. The equi-librium constant at 1600 deg C is [%Cb][fo. % 0]2 = 2.9 x 10-4 where log fo= —0.14 [%Cb]. The deoxidizing power is comparable to that of vanadium, COLUMBIUM (niobium) is finding increasing use as an alloying element in steel. It forms several stable oxides and is removed from the steel bath by oxidizing slags. The specific oxide formed in steel-making is not known although Sazanov snd Shvarts-man,&apos; in their study of its partition between slag and metal, have assumed this to be Cb2O5 It is the purpose of this study to determine its deoxidation equilibrium at 1600°c, the nature of the oxide formed and the interaction between columbium and oxygen in the melt. The investigation was based on the reaction H2 + O=H2O; Kl=ph2o/(pH2[%O]) [1] in which 0 signifies oxygen dissolved in the liquid Fe-Cb alloy. The method and equipment of recent studies2,3 were utilized. In brief, the molten alloy, contained in a small crucible, is held in a controlled mixture of steam, hydrogen, and argon until equilibrium is reached. It is then cooled quickly in a stream of helium and analyzed for columbium and oxygen, the latter by vacuum fusion.4 The solubility of the oxide in liquid iron is determined by visual observation of scum formation on the surface of the melt. Crucibles of MgO proved unsatisfactory because of partial reduction at the metal interface. Pure A12O3 crucibles were heavily blackened by the melt and could not be used at high concentrations of columbium. Silica crucibles were more satisfactory but these introduced some silicon into the melt thus necessitating an uncertain but small correction for its effect on the activities of the other solutes. In silica it was possible to observe the scum formation when the melt became saturated and there was no apparent reaction between scum and crucible. The procedure for saturated melts was as follows. The alloy charge composed of electrolytic iron and columbium grain was melted and held at constant temperature. The gas ratio H2O:H2 was progressively increased by raising the saturator temperature until a point was reached at which a bright film appeared on the surface and covered it completely. This film could be dissolved by raising the temperature of the melt and it reappeared when the temperature was lowered. Under a partial film covering, utilizing bare areas for temperature measurement, the melt was brought to equilibrium with the atmosphere by holding at temperature for about 1 hr as suggested by Dastur.5 INTERACTION IN THE MELT Several experiments were made without columbium to establish a base in silica crucibles. The results are shown in Table I. Except for one run, they agreed well with Floridis1 comparable results in other crucibles. The value of log K1 is taken from Table I as 0.58. This is slightly larger than Floridis&apos; result, probably because of less elaborate safeguards against thermal diffusion. Results obtained in the Fe-Cb-0 series in which no scum formed are shown in Table 11. The equilibrium ratio Kl is defined as ph2o/(ph2[%O]). It is related to the equilibrium constant K1 as follows:

Jan 1, 1962

R. Culver, Colorado School of Mines I appreciated Professor Starfield&apos;s presentation, because his approach to blasting research reflects my feelings that a lot of practical work can be done toward making short-term advances that can be used by the blasting industry. We should not forget this in our attempt to obtain solutions to such idealized problems as a mathematical theory of cratering. The blasting industry would like very much to have the efficiency of the basic blasting processes improved from the range of 20 percent up into the range of 50 percent. And many of these problems should be approached and attacked in the laboratories. Blasting research at the Colorado School of Mines for the past two or three years has been aimed at improving the pre-splitting process, because we feel it will become increasingly important to the construction industry. We have attempted to develop a unified theory of how pre-splitting works; and the more we investigate, the more variables we find. We may never obtain an entirely satisfactory theory of pre-splitting, but we have developed a tentative explanation. One of our first conclusions was that we are making very poor use of the explosive in current pre-splitting practice. But to appreciate this we must first consider how pre-splitting works. A series of parallel boreholes are loaded with low density charges which are detonated simultaneously. (Delayed detonation has been tried, but most people agree that simultaneous detonation is best, and this is what we found.) Stress waves traveling out from each borehole interact with the stress waves from the two adjacent boreholes influencing the direction of the fractures that occur and propagate from each borehole. It has been suggested in private communication with Mr. Wilbur Duvall of the U. S. Bureau of Mines, that the fracture between the adjacent boreholes is a result of the net particle velocities above and below the pre-split plane which tend to set up a net tension along the pre-split plane. Regardless of what the exact mechanism is that causes the fracture to propagate from one borehole to the next, we know that it, in general, relies upon an interaction of the stress waves. However, if there is a large compressive stress normal to the pre-split place, it can practically eliminate any possibility of obtaining the desired pre-split by preventing the desired fractures from getting started. Aside from obtaining a fracture along the pre-split plane, the other major aim of pre-splitting is to minimize the fracturing that occurs around the borehole. We do this by drilling a large hole and putting a small charge in the middle of it. This results in a badly decoupled charge which is very inefficient; most of the energy is used in compressing the air in the borehole. Out of discussions about how pre-splitting works, we decided that perhaps there was some other explosive geometry which would make more efficient use of the explosive, and result in optimizing the pre-splitting process. Starting in the laboratory with small plexiglas blocks, we found that a fully-coupled explosive charge of 5 grains/in. of PETN gave random fractures extending about I in. from the borehole. A 1/4 in. plexiglas plug fit into a 1/4 in. hole in a similar block with the same fully coupled charge gave random fractures extending out only about 1/2 in. due to the energy absorbed in fracturing the plug. If the plug was split longitudinally but otherwise using the same geometry, it was possible to drive a fracture about 2 in. in either direction from the borehole, with an even smaller amount of fracturing around the borehole.

Jan 1, 1967