Search Documents

By Jr. F. M. Perkins.

Capillary forces play a controlling role in water-drive displacement processes both in laboratory experiments and in actual reservoirs, but their quantitative importance may be quite different in the two cases. Because of the importance of conducting laboratory experiments which are representative of field conditions, it is necessary to understand exactly the role of capillary forces in the displacement process. Though a number of experimental investigations related to this subject are contained in the literature, there appears to be a lack of information pertaining to unsteady-state experiments in water-wet media. This experimental study was conducted to obtain additional laboratory data to clarify further the role of capillary forces in both the macroscopic and microscopic flow of oil and water in porous materials. THEORETICAL CONSlDERATlONS The capillary pressure is defined as the difference in pressure between a continuous oil phase and a continuous water phase in a porous material.' The magnitude of this pressure difference depends on the interfacial curvature and the interfacial tension. The interfacial curvature is determined by the geometry of the pore spaces, the wettability of the rock surfaces, and the quantity of cach phase present. Capillary forces are involved in a water-drive displacement process in that they exert a controlling influence on the microscopic fluid distribution which in turn is reflected in the saturation or macroscopic flow behavior. Microscopic Fluid Distribution Because of the microscopic nature of the displacement of oil by water, it is necessary to consider the flow and the fluid distribution in individual pores. On this microscopic scale the capillary Forces, which act over a distance of one or two sand grain diameters, control the distribution of oil and water under static equilibrium conditions. When an external force is applied to the fluids, such as in a water-injection experiment, the applied forces tend to distort the oil-water interfaces. However, in most fine-grained, water-wet sands, the applied pressure difference across one or two grain diameters is usually several orders of magnitude less than the capillary pressure difference. These con-siderations lead to the theory' that even during flow the capillary forces continue to control the microscopic distribution of oil and water within the pores of a porous material for all practical reservoir and laboratory flow rates. This concept of capillary forces controlling the microscopic distribution of fluids has been substantially verified by other investigators3-7 who have found a lack of dependence of relative permeability and residual oil saturation on rate of fluid injection. Macroscopic Distribution The microscopic influence of capillary forces cannot be observed easily and only the effect on the macroscopic or average saturation can be detected. The saturation, of course, is really the point of interest. During a water flood, large differences in saturation at the flood front cause large capillary pressure gradients. This, in turn, causes water to advance ahead of the flood front thereby reducing the capillary pressure gradient in this region. The result is that in homogeneous porous media capillary pressure gradients tend to cause a diffuse displacement front. At low rates in laboratory columns, the front may extend over the entire column length. When the advancing water first reaches the outflow face of a core, the water, which is the wetting phase, cannot be produced because the pressure in the water just inside the core is lower than the pressure in the oil-filled space around the outflow face. This difference in pressure is equal to the capillary pressure for the water saturation existing at the outflow face. Water, therefore, accumulates at the outflow end of the core which causes a reduction in the capillary pressure. Because the capillary pressure does not vanish except at the residual oil saturation,7,8,9 water will not be produced until the residual oil saturation exists at the outflow face. This entire effect,"' which is called the "boundary effect", results in a region of relatively high water saturation near the outflow face. At low rates of injection in a short column, this region of high water saturation may extend over a considerable portion of the column. The influence of capillary forces on the macroscopic flow of oil and water have been described by Leverett.10 For unidirectional, viscous flow in the absence of gravity segregation, the expression in dimensionless form for the fraction of water in the flowing stream, f, is

Jan 1, 1958

By Ray Light, Everett M. White

Numerous articles have been written about the coal miner ; he has been compared with brave men who have gone out to conquer some unknown hazard throughout the ages. Now, however, modern mining is no longer something to be avoided, but a vocation that anyone can be proud of, with remuneration equal to or above that of almost any industry. A concerted effort is being made each day by both the operators of most mines as well as the state and federal inspectors to see that coal mines are as safe or safer than work places in any other industry. However, it is true that mine fires and explosions have occurred in the mining industry since its inception. One of the earliest accurate references to such an occurrence is found in the transactions of the Royal Society of London. In the Colliery Managers' Handbook, 1898, Caleb Pamely writes of an explosion that occurred at Fatfield, England in August 1708, resulting in the deaths of 69 persons. He states: "Three of them, viz, two men and a woman, were blown quite up from the bottom of the shaft, fifty-seven fathoms deep, into the air, to a considerable distance from the mouth of the pit." It is interesting to note that women were employed as miners in England during that period. In the United States, the first record of coal mined was in 1702 by the Jamestown colonists. In 1786, about 20 years after Pittsburgh, PA was first settled, a charter was granted by William Penn to mine coal on the banks of the Monongahela River. Then in 1803, the first important coal company, the Lehigh Coal Co., was established. From this beginning, the mining industry continued to grow in importance and the first state mining law was formulated in 1870. The Pennsylvania state mining law was followed in 1873 by Ohio's, and in 1876 by Maryland's. A mine explosion at Avondale, PA in 1869 stimulated state legislatures to formulate these early laws. In 1907 near the town of Fairmont, WV, there were, within three days, two explosions resulting in a total of 597

Jan 1, 1981

By G. Sachs

According to Tammann,' the explanation of the effect of mechanical deformation in producing changes in the properties of metals is one of the most important problems of physical metallurgy, taking rank with the study of the constitution of alloy systems; and this problem has long attracted the attention of practitioner and scientist alike. Its solution was not advanced materially until Tammann2 set up his translation hypothesis with its crystallographic basis, while other hypotheses, such as the amorphous metal hypothesis of Beilby3 and Rosenhain,4 have been shown by more intensive studies to be less and less satisfactory. The principles of the Tammann translation hypothesis have proved to be useful even up to today and in spite of all of the recent accumulation of experimental data, while the differences of opinion which have arisen relate to the extent to which the hypothesis accounts for the observed changes Ïn properties and to what extent further assumptions are necessary. Stimulated by the proposals of Tammann, there soon developed a lively experimental activity which aimed at the elucidation of the structural or crystallographic changes produced by the mechanical deformation of metals. Parallel movements of crystal "blocks" along definite crystal slip planes had already been observed by Ewing and Rosenhain5 in 1900, in metals which had been moderately deformed but without shedding light on the crystallographic nature of the processes accompanying more severe deformation. The solution of this important problem was not advanced until a much later date, or until the methods of X-ray crystal analysis had become available. Shortly after the discovery of the diffraction of X-ray by crystals, symmetrical diffraction effects were

Jan 1, 1931

By Charles Y. Clayton

The shank, to give good service, should not upset nor should it cause excessive wear on the various parts of the machine. To fulfill these requirements, the steel must have a certain hardness—that is, resistance to deformation. The hardness is expressed in conventional terms, as Brinell or scleroscope number. Before deciding on the hardness that is proper, several factors should be considered; the most important are: type of drill steel used (whether hollow or solid), length of steel, nature of ground, air pressure, and hardness of hammer or anvil block (usually 600 Brinell). These are not all, but they are the most cogent ones. Without doubt, it would be better to use a shank that is too soft than one that is too hard. Most satisfactory service will be obtained from shanks that are just hard enough to resist any tendency to upset. To express the proper hardness in terms of Brinell numbers would mean a great many tests over a long period of time, or a study of drill steels that are being used successfully in the various districts. To obtain some information along this line, the persons making this investigation requested, a number of companies to send to them drill shanks that had been given the usual treatment at that mine. The results of the hardness tests are given in Table 1. The hardness values given in Table 2 are those of shanks known to have been quenched in water and drawn. These results show that where water quenching and drawing are in vogue the hardness is rarely under 400 Brinell.

Jan 1, 1923

By Charles Y. Clayton

The shank, to give good service, should not upset nor should it cause excessive wear on the various parts of the machine. To fulfill these requirements, the steel must have a certain hardness—that is, resistance to deformation. The hardness is expressed in conventional terms, as Brinell or scleroscope number. Before deciding on the hardness that is proper, several factors should be considered; the most important are: type of drill steel used (whether hollow or solid), length of steel, nature of ground, air pressure, and hardness of hammer or anvil block (usually 600 Brinell). These are not all, but they are the most cogent ones. Without doubt, it would be better to use a shank that is too soft than one that is too hard. Most satisfactory service will be obtained from shanks that are just hard enough to resist any tendency to upset. To express the proper hardness in terms of Brinell numbers would mean a great many tests over a long period of time, or a study of drill steels that are being used successfully in the various districts. To obtain some information along this line, the persons making this investigation requested, a number of companies to send to them drill shanks that had been given the usual treatment at that mine. The results of the hardness tests are given in Table 1. The hardness values given in Table 2 are those of shanks known to have been quenched in water and drawn. These results show that where water quenching and drawing are in vogue the hardness is rarely under 400 Brinell.

Jan 1, 1923

By Chung Yu Wang, Guy C. Riddle

There are found in nature upward of II2 minerals containing antimony, but only a few of them, listed in Table I, can be considered as antimony ore-forming minerals. Stibnite (Sb2S3), antimony sulphide or glance, is the principal ore of antimony. The oxide ores—cervantite, kermesite, valentinite, sernarmontite—occur sparingly in nature. Dry methods are generally adopted for the extraction of the metal. Electrometal-lurgical methods have had much attention in America and Germany and have not yet found, on economic grounds, practical or extended application, except in a few places. During recent years, treatment of the poor grades of the ore, especially sulphide, by ore-dressing methods, has commanded some attention and been adopted at a few plants. The impure sulphide of antimony, resulting from the liquation process, is called lLneedle," "liquated" or "crude" anti- mony, and the refined metal itself is called antimony "regulus." The different processes for the treatment of antimony ores are shown in the diagram of Fig. I. Liquation of Crude Antimony The first step in the smelting of antimony is a simple one, the process of LLliquation," which produces crude or needle antimony. Ores containing $ 50 per cent Sb are used in the liquation process for the production of crude. The temperature required for liquation is between 550' and 600°C. Ores to be liquated are broken to about walnut size. If the pieces are larger than this, the low heat used will not penetrate' effectively, and if they are smaller the ore tends to pack too closely for adequate penetration. A packed charge also prevents the free escape of the fused sulphide. Intermittent Liquation in Crucibles The unique type of furnace that is in use in China for smelting is not highly efficient but is simple in construction and operation. The furnace is generally built

Jan 1, 1944

By Andrew Cosgarea, William R. Upthegrove, Morteza Mirshamsi

The capillary-reservoir technique was used with lead-210 and cadmium-115m to determine the self-diffiLsion coefficients of both cadmium and lead in the liquid binary Cd-Pb system. The self-diffusion coefficients of pure cadmium and pure lead were obtained and were compared with the theoretical predictions. Good to excellent agrement between the experimental and predicted values was obtained. The self-diffusion coefficients of cadmium were tneasuved in alloys containing 2.50, 9.13, 17.40, 31.00, 45.00, 69.00, and 97.00 lot pct Cd by determining- the amount of cadniiutn-115m which diffused out of a small-bore capillavy into an infinite reservoir during- a given time peviod. Sinzila7-measurements were made with lead-210 to determine the self-diffusion coefficients of lead in these identical alloys. Diffusivities were determined from measurenzents performed in the temperature interval of 290" to 480°C. The results were correlated with the Ar-vhenius equation, and the maximum variation of the equation parameters (Q and Do) was also inrestigated . THE theory of diffusion in liquids, particularly liquid metals, is relatively undeveloped in contrast to that for the gaseous and solid states. Although the practical application of liquid metals as heat-transfer media has become increasingly important, few liquid-metals systems have been investigated. Experimental data of fundamental significance in this field are not readily obtained, which may explain but not justify the present lack of knowledge. What work has been completed is primarily restricted to liquid diffusion of pure metals; little work has been done in liquid-metal diffusion of binary mixtures. A review of liquid-metal diffusion theory and research is available elsewhere.1-4 In an effort to add to the knowledge of liquid-metal systems and to increase the basic understanding of the diffusion process in liquids, a study of diffusion in the binary-liquid system, Cd-Pb, was undertaken. The capillary-reservoir technique5 was employed to measure the self-diffusion coefficients of cadmium and lead in molten binary alloys. Measurements were made with seven selected compositions and over a temperature range from 290° to 480°C. The experimental apparatus consisted essentially of the following items: constant-temperature bath, diffusion cells, capillaries, capillary-filling device, and a radioactive tracer counting system. EXPERIMENTAL APPARATUS Constant-Temperature Bath. A cylindrical steel vessel, 8 in. in diam and 15 in. deep, surrounded by an insulated heating coil was used with a sodium-potassium nitrate salt mixture heating medium. The bath was maintained slightly below the desired control temperature by the furnace-heating element; and a 250-w heater, actuated by a Bayley proportional temperature controller, was utilized for the final control of the temperature. A constant-speed mixer stirred the salt to insure a uniform temperature within the bath. Four calibrated Chromel-Alumel thermocouples were placed at various positions in the salt bath to verify the absence of temperature gradients. The observed temperature variation during any diffusion run was less than 0.l°C. The entire furnace assembly was mounted on four shock absorbers to exclude building vibrations and the stirrer propeller blades were adjusted so not to induce vibrations within the reservoir. A schematic diagram of the furnace and the constant-temperature bath is shown in Fig. 1. Diffusion Cell. The diffusion cells and associated parts were the same, except for slight modification, as the one used by walls1 in this laboratory, and are shown in detail elsewhere.' A graphite crucible, 4 in. long and 40 mm (1-1/2 in.) ID, enclosed in a 60-mm (2-1/4 in.) Pyrex tube cell about 18 in. long, was used as a container for the melt. The reservoir (molten alloy in the graphite crucible) was usually about 2 to 2-1/2 in. deep. Graphite was used because of its satisfactory nature as a refractory material and the low solubility of carbon in molten Cd-Pb alloy.677 The Pyrex cell was closed at the bottom and fitted at the top (open end) with a 2-in. Dresser coupling. A brass flange was welded to the top of the coupling. The upper part of the diffusion assembly was bolted to this flange with an O-ring seal. The lower part of the diffusion cell was supported in a 3-in. brass cylinder which was open to allow for circulation of salt around the cell. The top assembly consisted of two synchronous motors, a drive shaft, a thermocouple well, and controlled-atmosphere inlets and outlets. One motor was used for rotation of the capillaries at a rate of 1/2 rpm in the reservoir during the diffusion run. The other motor was used for the vertical positioning of the capillaries and the capillary holder by means of a simple screw drive. The capillary holder and drive assembly were lowered into the reservoir for the run and raised after the desired diffusion time at a rate of approximately 0.4 in. per min. Capillary holders were made of graphite. These

Jan 1, 1967

By M. E. Fine, A. A. Henderson

Investigation of the tensile properties of silver based aluminum alloy crystals was undertaken because it appeared attractive for studying strengthening effects due to Suzuki locking with minimum complication. Yield drops were observed in all alloy crystals (1, 2. 3. 4, and 6 at. pct Al) after strain aging at room temperature. No yield drops were found in similarly grown and tested silver crystals. The yield effects are attributed to Suzuki locking but the major portion of the solid solution strengthening to other mechanisms. INVESTIGATION of the tensile properties of single crystds of silver alloyed with aluminum was undertaken because it appeared to be a system in which segregation at stacking faults associated with partial dislocations1 would be the dominant factor in anchoring dislocations. First, silver and aluminum have closely similar atomic sizes and thus solute atom locking of a dislocation due to elastic interactions should be unimportant. Second, while both X-ray2 and thermodynamic3 investigations show short-range ordering in silver-based aluminum alloys, the degree of local order is quite small (X-ray measurements give v = EAB - 1/2(EAA + EBB) = - 0.025 ev and thermodynamic measurements give v r -0.007 ev) and should not be important in strengthening dilute alloys. Third, the stacking fault energy of silver is probably low (as indicated by the profusity of annealing twins) and is very likely diminished further and quite rapidly by aluminum additions since the A1-Ag phase diagram shows a stable hexagonal phase at only 25 at. pct Al. Also, a careful investigation in this laboratory4 has shown that the ratio of twin to normal grain boundaries in recrystallized alloys increases with aluminum content. Thus, with minimum complication from other factors, Ag-A1 alloys seem attractive for studying strengthening effects due to segregation at stacking faults of extended dislocations. EXPERIMENTAL METHOD Single crystals measuring 250 by 5 by 1.5 mm of pure Ag (99.99 pct) and Ag-A1 alloys (A1 of 99.999 pct purity) of nominal compositions* 1, 2, 3, 4, and 6 at. pct were grown in high-purity graphite molds from the melt under a dynamic vacuum (1 x l0-5 mm Hg). The technique consisted of moving a furnace having a hot zone (which melted about 0.5 cm of alloy) over a horizontal, evacuated quartz tube con- taining the mold and alloy at a rate of 3/8 in. per hr. Chemical analysis showed roughly the first inch of the crystal to be solute poor, the last inch solute rich; and the center section uniform in composition within the sensitivity of the analytical method (± 0.2 at. pct Al). The center section of the crystal was cut into five specimens. Gage lengths of reduced cross section, measuring from 1.5 to 2 cm in length, were mechanically introduced by means of jeweler&apos;s files and fine abrasive cloth with the crystal firmly held in polished steel guides. One-third of the cross section was then removed by etching and electro-polishing, the crystals were all subsequently annealed for several days at 850°C in a dynamic vacuum (<1 x 10-5 mm Hg) and furnace cooled to 200°C. The crystal orientations were determined using the usual back-reflection Laue technique. The Laue spots were sharp and of the same size as the incident beam. However, microscopic examination showed the crystals to contain substructures with subgrains of the order of a micron in diameter. The details of this substructure are presently under investigation. Tensile testing was done with a table model Instron using a cross-head speed of 0.002 in. per min. For testing at various temperatures the following media were used: 1) 415oK, hot ethylene glycol; 2) 296ºK, air, acetone, water; 3) 273ºK, ice water; 4) 258ºK, ethylene glycol "ice" in ethylene glycol; 5) 200°K, dry ice in acetone; 6) 77ºK, liquid nitrogen. EXPERIMENTAL RESULTS A) Yield Behavior—A portion of an interrupted stress-strain curve for a 6 at. pct A1 crystal of the indicated orientation tested at room temperature is shown in Fig. 1. Initially, at (a), there is a small, gradual yield drop of about 10 mg per sq mm2. However, on stopping the test, and aging for a few minutes at (b), a sharp yield drop is found. Aging for longer times at (c) and (dl results in larger yield drops (and larger AT&apos;S). At, defined in Fig. 1, is usually larger than the yield drop by about 20 pct; however, this increase in the lower yield is transient since extrapolations of the flow stress curves join as may be seen from Fig. 1. (Both Laue and low-angle scattering photographs revealed no evidence of precipitation in a strain-aged 6 at. pct A1 crystal.)

Jan 1, 1962

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4&apos;5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.&apos;-&apos; EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) &apos;Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970

By C. A. Winkler, V. Hospadaruk

PREVIOUS papers from this laboratory have discussed the effect of chloride ion on the cathode polarization during electrodeposition of copper from copper sulphate-sulphuric acid electrolytes, in the presence and absence of gelatin. The steady state polarization&apos;" was found to decrease sharply and pass through a minimum with increasing chloride ion concentration in the presence of gelatin. The minimum shifted to higher chloride ion concentrations and to higher polarization values with increase in current density or gelatin concentration, while an increase of temperature shifted the minimum toward lower halide concentrations and lower polarizations. Since these observations were made in acid-copper sulphate electrolytes that contained no other addend than gelatin, there was obviously the possibility that they were not applicable to deposition of copper from commercial electrolytes that contain a variety of other substances in relatively small amounts. In particular, it was of interest to determine whether the presence of arsenic, antimony, or bismuth in the electrolyte would materially alter the behavior. Experiments have now been made under a variety of conditions with systems containing these cations, and the results are summarized in the present paper. Experimental Polarization measurements were made at 24.5oC in a Haring cell in the manner described previously.&apos; Electrolytes were made with doubly-distilled water, and contained 125 g per liter of copper sulphate and 100 g per liter sulphuric acid, both of reagent grade Eimer and Amend gelatin from a single stock was used throughout. Chloride ion was introduced as reagent grade sodium chloride, and arsenic, antimony, and bismuth by dissolving the chemically pure metal in hot concentrated sulphuric acid and adding appropriate amounts of the solutions to the electrolyte. Each cathode, of 1/16-in. thick rolled copper, was first etched in 40 pct nitric acid and washed thoroughly with distilled water. The surface was then brought to a standard condition4~9 by electrodeposition from an acid-copper sulphate electrolyte containing no gelatin, at a current density of 3 amp per sq dm for 30 min, followed by deposition at a current density of 2 amp per sq dm for l hr. As in previous studies, the cathode polarization eventually attained a steady-state value (15 to 75 min) such that further change in polarization did not exceed 0.2 mv per min. The polarization values recorded are those for the steady states. "Excess weights" were determined with arsenic and antimony present in the electrolyte, as the difference between the weights of the deposits obtained in the presence of these cations and those obtained in their absence, with the two cells connected in series. When gelatin was present along with the arsenic or antimony, it was also added to the electrolyte in the cell in series. Results and Discussion The results of the study are summarized in Figs. 1 to 6. From Fig. 1, top, it is evident that the presence of arsenic or antimony alone results in an increase of polarization, while bismuth alone causes a decrease. The presence of gelatin (25 mg per liter) rather drastically modifies all three cation effects, as indicated in the lower panels of the same figure. The addition of chloride ion, when no gelatin is present, causes comparable decreases in polarization in the presence of antimony and bismuth, but a relatively larger decrease when the electrolyte contains arsenic. It is interesting to note that the decrease in polarization brought about by addition of chloride when both arsenic and antimony are present parallels the behavior with arsenic alone, while the polarization in the electrolyte containing the cation mixture, without chloride added, corresponds to that for an electrolyte containing only the antimony cation. Similarly, the polarization at zero concentration of chloride in electrolyte containing arsenic and bismuth is that corresponding to an electrolyte containing arsenic alone. From Figs. 3a, 4a and 4b, it is clear that, in the presence of gelatin at a level of 25 mg per liter, the effect of chloride in the presence of arsenic and antimony, or a mixture of the two, becomes quite analogous to that observed in the absence of added cations. When both bismuth and gelatin are present (Fig. 5), the decrease in polarization with increased chloride concentration is virtually absent. This is perhaps a reflection of the large decrease in polarization brought about by the bismuth itself in the presence of gelatin. The shifts of the minimum in the polarization-chloride concentration curves brought about by changes of temperature (Fig. 3b), gelatin concentration (Figs. 3c and 4c) and current density (Fig. 3d) when the metal cations were present are all similar to the corresponding shifts observed in their absence." The approximately linear "excess weightv-anti-mony concentration relation recorded in Fig. 6 would seem to indicate that antimony is codeposited with copper to a considerable extent. On the other hand, only very limited amounts of arsenic appear to be adsorbed or codeposited.

Jan 1, 1954

By Carl J. McHargue

Mechanical twins were produced in electron-beam melted columbium by high-speed impact at room temperature and by slow or fast compression at -196°C. The composition plane of the twins was { 112} and the shear direction was <111>. Notches in the twin bands often corresponded to traces of {110) of the matrix and appeared to be untwinned regions. Markings within the twin bands were interpreted as resulting from {110} slip in the twins. THERE has been much work in recent years concerning plastic deformation by glide, and the dislocation theory relating to glide has reached a relatively high degree of development. On the other hand, there have been fewer studies of deformation by mechanical twinning, and understanding of this process is far from satisfactory. This method of deformation is of interest for at least two reasons. First, it provides a mechanism in addition to glide for the relief of stresses, and, in the bcc and hexagonal close-packed metals may result in significant amounts of plastic flow. Secondly, there is the possibility that twins may act as barriers for dislocation movement, resulting in pile-ups which could nucleate cracks. As might be expected, the bulk of the literature on mechanical twinning in the bcc metals is concerned with iron. A good summary of the work done prior to 1954 is contained in the book by all.&apos; Recently the refractory bcc metals have become increasingly important. Limited studies have shown that tantalum,2,3 molybdenum,4,5 vanadium,6,7 tungsten,&apos; and columbium9-11 deform by mechanical twinning under some conditions. Alloys of molybdenum with rhenium and tungsten with rhenium show extensive deformation by twinning at room temperature.I2-l4 Most of these studies have dealt primarily with mechanical properties at low temperatures or have shown the existence of twins, and there is only a small amount of information concerning the conditions under which they form. The subject of the present paper is the formation of twins under stress in columbium with a consideration of their morphology. EXPERIMENTAL PROCEDURE The material used for these studies was taken from an ingot of columbium which had been melted twice by the electron-be am-method. The analysis of the ingot was (in ppm): B < 1, C = 10, Fe < 100, The cast ingot contained very large grains, and it was possible to obtain single-crystal prisms which measured from ¼ to 3/4 in. on a side. A few experiments were conducted on polycrystalline plate which was prepared by rolling material from the same ingot at room temperature and annealing at 1000 in a dynamic vacuum of 10-6 mm Hg. This gave a plate in which the grains had an average diameter of 3 mm. After the specimens were cut from the ingot, the six faces were metallographically polished and elec-tropolished to remove all traces of cold work. Most of the observations were made on the surfaces of the deformed specirllens without further treatment. Occasionally, etching after deformation was desirable. In these cases, an etchant of the composition 50 parts H2O, 5 parts HNO3 25 parts HF, and 10 parts H2SO4 was found to delineate the twins very well. Unless considerable care was taken to ensure the removal of all disturbed metal left by the mechanical polishing, etching failed to reveal many of the features discussed in this; paper. The specimen&apos;s were deformed either by impact or slow compression at 77°K (liquid-nitrogen coolant), 198°K (dry ice and acetone coolant), and 298°K. The impact load was delivered by a hammer except in one case where the load was delivered by a bullet. Slow compression was carried out on a hydraulic testing machine equipped with a chamber to hold the coolant. EXPERIMENTAL RESULTS It has been generally believed that the conditions favoring the formation of deformation twins are large grains, low temperature, and impact loading. In fact, Barrett and Bakish2 found twins in tantalum only after impact deformation at 77°K, and Adams, Roberts, and Smallman10 observed twins in columbium only at 20 For these reasons, the initial experiments of this study used impact loading. Hammer blows caused many bands resembling twins in single crystals a.t 77" but not at 198°K. Only a few slip lines were observed on any of the single-crystal specimens of this study—essentially all the deformation occurred by twinning. The appearance of the twins on the as-deformed surface is shown in Fig. 1. Although both Figs. 1(a) and l(b) are photomicrographs of twins taken at the same magnification and from the same crystal, they are startlingly different in appearance. Fig. 1(a) was taken from the crystal face approximately perpendicular to the shear direction, whereas Fig. 1(b) was taken from

Jan 1, 1962

By P. H. Brace, N. A. Ziegler

THE study of the relations between gases and metals is one of perennial interest to all who are connected with the production of high-grade metallurgical products. The data reported here are the outcome of work of which the object is to determine the effects of dissolved gases upon the properties of metals and to gain a more detailed knowledge of the reactions between gases and molten metals, particularly iron, under definitely controlled conditions. We have attempted to reduce our margin of error by dealing with relatively large quantities of metal, from 4 to 13 lb. (2 to 6 kg.), and keeping the ratio of refractories to metal as small as practicable. The ingots produced are large enough to provide adequate material for making determinations of magnetic and other physical properties. In choosing the bell-jar type of furnace we were influenced by the results of considerable experimentation along the same general line which indicated that, for the scale on which we were to work, it was important to have the furnace structure independent of the vacuum enclosure. The use of a bell-jar surrounding the entire furnace accomplishes this and also gives great freedom of observation during operation and ready accessibility for the replacements which are necessary after each run. Our choice of analytical method was made in the light of the results secured by H. M. Ryder, who used a method similar in principle for the analysis of very small quantities of gas extracted from strips of metal heated electrically in high vacuum. We have presented some selected preliminary experimental data as being illustrative of the quantity and nature of the gases which occur in iron of different origins, but do not urge any hypothesis at this time. THE FURNACE Our furnace may be described as "a high-frequency induction furnace of the bell-jar type." It is similar in a general way to that described by Cain and Peterson&apos; though we have introduced certain refinements of

Jan 1, 1928

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By T. G. Decker, A. F. Witt, A. M. Gaudin

The historical development of the concept of contact angle hysteresis is reviewed. The measurements of contact angles reported in literature have all been made under static conditions. For the measurement of dynamic advancing and receding contact angles, four methods are described together with an evaluation of their precision. Three of these methods were adapted from devices already used for the measurement of static contact angles. The fourth method uses a new principle and apparatus and is the most accurate. While the relationship between surface tensions and the contact angle was extablished as early as 1805 by T. Young,&apos; it was only in 1890 that the existence of contact angle hysteresis was reported by Lord Rayleigh. His observations, however, remained almost unnoticed. With the invention of froth flotation, the contact angle and its behavior became the subject of investigation. In 1907, L. Sulman and collaborators investigated the cause of discrepancies between recorded values of contact angles. They found that certain variations existed in most cases, but that definite maximum and minimum values of contact angles are obtainable. The difference between the maximum and the minimum contact angle in a given system was termed "hysteresis" by Sulman. First attempts to explain hysteresis were made by E. Edser. In the following years extensive studies of contact angles in various three-phase systems

Jan 1, 1963

By J. W. Furness

Before attempting any discussion of the importance of tariff enactments as applied to exhaustible resources, certain basic factors should be emphasized. First, it must be remembered that minerals differ from organic substances in that they are irreplaceable, and when once taken from the earth&apos;s crust enter into uses which ultimately dissipate them, so . that they cannot be recovered for future use. A second factor entering into the problem is the unequal distribution of the mineral deposits of the world. No industrial nation has within its political confines a sufficient quantity of all the minerals necessary for the maintenance and advancement of present civilization; hence international exchange of these commodities is inevitable. As minerals are essential to modern industry, the supply available to any given nation constitutes a factor which limits its ambition to advance industrially. A nation which has this ambition endeavors to secure not only a supply of minerals sufficient for its current needs, but also sources which will assure it expansion. Should mineral raw materials be withheld from such a nation by enactment, it seems inevitable that every effort will be made to obtain them, and that, should the nation deem itself sufficiently powerful, its ultimate recourse will be force. Thus the importance of tariff enactments, not only from the standpoint of industrial prosperity but from the standpoint of international peace, can be appreciated.

Jan 1, 1932

By James F. Kemp

In earlier gears, the custom prevailed of regarding the anthracite basins as cases of folding with slight development of faulting. Folding is so pronounced and, in the eastern and western Middle Fields, at times so violent, that the inference was a natural one and led to the widespread impression that practically all the disturbances of the seams could be explained in this way. The cross-sections and maps prepared forty or more years ago for the Second Geological Survey of P ennsylvania, by Mr. Ashburner under Prof. J. P. Lesley, exhibit little else than folds.&apos; So far as I can discover faults fail in the charts, except in one small case in the Henry colliery near Plainsville on the outskirts of Wilkes-Barre. Some years ago, while spending a day or two in Wilkes-Barr, under the guidance of R. V. Norris, I looked over some recent and accurate cross-sections of a numbcr of the large collieries and was deeply impressed with the peculiar behavior of some of the seams and the intervening shales. Thus, a seam might present a small, more or less overturned fold, rising 30 to 50 ft. (9 to 15m.) above its general course, and yet the movement would be taken up in the overlying shales, so as hardly to be noticeable in the seams next above or below. These and similar anomalies, especially when shown with the accuracy of engineer&apos;s surveys, possess great scientific and practical interest, bearing as they do, not alone on coal mining, but on theoretical geology and the actual behavior of strata under great compressive stresses. In preparation for the semicentennial meeting of the Institute, an effort was therefore made to secure some of the most interesting sections for presentation to the members. The collection of illustrations here shown is mainly due to Douglas Bunting of the local committee, to whom and to the contributing companies acknowledgments are due. The illustrations are taken from all four of the main basins, but are chiefly from the portions nearest Wilkes-Barre. The first are in the

Jan 1, 1922

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana&apos; good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker&apos;s procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By B. G. Klugh

(New York Meeting, February, 1913.) THE present paper represents a preliminary investigation of the ultimate structure of iron-bearing materials which have been subjected to heat treatment for the purpose of agglormer-ating the fines, or for chemical changes, or for both. Primarily, the object of this inquiry was to determine the relation of the microstructure of each of these materials-to its specific susceptibility to the action in the blast-furnace. It is hoped that this small contribution will serve as a nucleus to a line of research that will throw some light upon the debated questions involved in blast-roasting. Thus far the investigation has been conducted along lines of analogy of known principles, rather than through the applica-tion of any well-defined system of microscopic petrography. This is obviously due to the fact that we are dealing with materials which are the artificial products of a new art, rather than with the natural materials from which the essence of the pure science has been evolved. In the limited tune allowed for this research, it has been conducted upon those materials the chemical content of which allows of their use commercially in the blast-furnace.

Jan 5, 1913

By Charles Goodale

THE principles and theory on which the U. S. mining law of 1872 was based are well understood, and have been discussed at great length by many writers. The papers by Dr. R. W. Raymond1 in the Transactions of the American Institute of Mining Engineers have covered the subject very fully, with explanations of practical results in many adjudicated cases. It is believed that the following instance of the application of the law in recent years will have some weight in a discussion of proposed changes in our mining laws. The litigation between the St. Louis Mining & Milling Co., and the Montana Mining Co., Ltd., a British corporation, over portions of the Drumlummon lode covered more than 20 years, and resulted in a judgment for damages in favor of the St. Louis Co. of such an amount that the Montana Co. declined to pay the judgment, and therefore lost the entire property. The Drumlummon lode claim in the Marysville district, Mont., was located in 1876 by Thomas Cruse. When he staked out his claim, he assumed that the discovery on the Drumlummon vein, and another showing of mineral about 200 ft. distant, were on the same vein, and the center line of the claim was given a course of N. 57&apos;2&apos;E. Development of the Drumlummon vein soon showed that its strike was about N. 15 E., and that the other outcrop was on the North Star lode; so it was inevitable that the Drumlummon vein would cross one or both side lines of the location, and the Montana Co. found it advisable to acquire adjoining claims on both sides of the Drumlummon, in order to avoid possible litigation over apex rights. They bought the Marble Heart, but would not purchase the Hopeful (see Figs. 1 and 2), at the terms proposed for the reason that exploration in the Cruse level had shown the vein to be barren in that region. The owners of the Hopeful were sinking an incline from that claim in 1889, and the Montana Co. enjoined them, contending

Jan 5, 1914

By J. D. Meakin, H. G. F. Wilsdorf

Using a combined decoration and etching technique the dislocation structure of annealed and deformed a brass has been studied. Annealed crystals revealed a low density forest and well-developed subboundaries; lightly deformed crystals contained discrete groups of dislocations. The dislocation density and the number of dislocations in a group were obtained from the micrographs. Using slip-line data, the mean path of a dislocation and the configuration of groups along an active slip plane have been deduced. Observations on secondary and cross-slip are reported. It has been the aim of many investigations to obtain detailed knowledge of the dislocation patterns which are present in metals before and after their deformation. The "decoration" of dislocations with impurity atoms has been considered as one of the promising experimental approaches, and much work has been done to develop this technique for revealing dislocation sites in metals. Following the early work by Castaing,&apos; Castaing and Guinier,&apos; and Lacombe and Berghezan~ on aluminum-rich aluminum-copper alloys, dislocations in this material have been studied extensively by others.+&apos; In these alloys the dislocation sites act as nuclei for the precipitation of the second phase. The main results of the investigations on aluminum with copper are: i) the confirmation of the earlier contention that subboundaries consist of dislocation walls, ii) that many more dislocations are found in slip bands than in regions where less glide had taken place, iii) the observation of individual dislocations, lying nearly parallel to the surface investigated, and iv) that parts of dislocation loops, apparently emitted from a dislocation source, could be made visible. Recently, Jacquet, Weill, and Calvert have succeeded in revealing nearly concentric dislocation loops in quenched A1-4 pct Cu and thus indicated directly the existence of dislocation sources in a fcc metal specimen of normal dimensions. Another decoration method developed by Dash10&apos;11 and applied to silicon crystals makes use of diffusing copper to the dislocations from a surface deposition. The dislocation pattern can then be observed by an infrared technique. His results include evidence for symmetrical and spiral Frank-Read sources, and for arrays of dislocation loops which follow simple crys-tallographic directions. Recently Low and Guard" have studied the dislocation structure of silicon-iron using carbon for the

Jan 1, 1961