Search Documents

By F. Hulsmeir

The increase in drilling activities in Venezuela noted during the latter half of 1932 continued, and 132 wells were completed in 1933 as compared to only 60 completed during 1932. Notwithstanding these new wells, 114 of which were producers, and also the appreciable increase in artificial lifting installations during the year, Venezuelan production was maintained at only a slightly higher level than in 1932, amounting to 120,356,000 bbl. in 1933 as compared to 118,167,000 bbl. in 1932. However, at the end of the year the daily average production of 358,-860 bbl. was 16 per cent higher than that at the end of 1932. Exports from Venezuela recorded an increase of approximately 4 per cent, totaling

Jan 1, 1934

By Richard S. Smith

THAT management and purchasing have developed a more closely-knit working relationship is evidenced by the fact that more and more companies are appointing the heads of their purchasing departments to the position of vice president. This is concrete and dramatic indication that management is utilizing the knowledge and experience gained in this department and working with it at the policy-making level. When the engineering department is at the planning stage of a project, the purchasing department is being asked to sit in on the preliminary discussions . . .today. One result of this cooperation is that drawings and plans will reflect the current situation on material availability and another is that standardization will be incorporated in new construction and equipment.

Jan 1, 1958

ALL critical and strategic materials procurement functions have been transferred from the Defense Minerals Administration, General Service Administration, and the Economic Cooperation Administration and are now centered in a newly formed agency, the Defense Materials Procurement Agency. DWA will report directly to the Director of Defense Mobilization. Mr. Truman stated that he intended to appoint Jess Larson, administrator or General Services to head the new agency (see Trends P. 756). W. C. Schroeder has been named acting director of the Defense Minerals Administration replacing James Boyd. He has been named also to a newly created assistant director position of the Bureau of Mines serving under Mr. Boyd who is director. Schroeder was formerly head of' the Synthetic Liquid Fuels Division of the Bureau of Mines.

Jan 9, 1951

By John V. Beall

There were no easily identifiable tourists. Everybody carried attaché cases and sported the buttoned-down look in dress. They were all there at the Hotel Indonesia to make a deal. But deals don't come quickly over there and those that staved and persevered became bored. They clung to the air conditioning of the Hotel and sought hobbies to while away the weeks-and even months. It is not an easy life but it can pay off fog sonic company. The government officials are neither stupid nor lazy. They are new at their jobs. Many are ex-army men and they know they must learn before they can enter into a contract with confidence. So they take time, and time is on their side.

Jan 1, 1970

By AIME AIME

YALE UNIVERSITY looked like a top-notch school to "Bert" Phillips in spite of the belief that the college in the home town sometimes looks less attractive than a more distant campus. So Bert, a native of New Haven, earned his B.S., M.S., and Ph.D. degrees from Yale. Immediately after Yale days lie served as metallurgist of the Scovill Manufacturing Co., Waterbury, and then went to the Central Research Laboratories of the American Smelting and Refining Co. at Maurer, N. J., where since 1931 he has been superintendent of research. Bert has contributed to metallurgical literature many reports of studies on the constitution and the physical, metallurgy of copper and copper alloys as well as papers on general nonferrous physical metallurgy.

Jan 1, 1938

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By Neils Hansen

The microstructure of dispersion-strengthened aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum oxide has been examined by optical and transmission electron microscopy, and the flow stress has been determined at room temperature and at 400C by tensile testing. Products were examined as recrystallized and as high-temperature extruded, and the microstructures consisted of a fine dispersion of oxide particles in a matrix divided by respectively recrystallized grain boundaries and subgrain boundaries. The flow stress (0.2 pct offset) at room temperature of recrystallized dispersion strengthened aluminum aluminum-oxide products is the superposition of dispersion strengthening and grain boundary strengthening. This superposition has been found to be linear. The flow stress (a) can be related to the grain size (t) by the Petch equation: ing content of oxide and k is a constant independent of the oxide content. For extruded products a similar relation has been found by replacing the grain size by the subgrain size. The k-value is of the same order for the two types of structure, which shows that the subgrain boundaries are as effective slip barriers as grain boundaries. Tensile testing at 400C of re-crystallized and extruded products shows that oxide dispersion strengthening is very effective, whereas the strengthening effect of grain boundaries and subgrain boundaries is small. THE microstructure of dispersion-strengthened products consists of hard particles finely distributed in a metal matrix. The strengthening effect of the dispersed phase has been fairly well established,1 and it has been found that the size and volume fractions of the dispersed particles are important structural parameters. However, in many dispersion-strengthened products which have been worked and heat-treated during manufacture the matrix is divided into well-defined grains or sub-grains, which may also have a strengthening effect. A model of the matrix strengthening in dispersed products worked during manufacture has been proposed,2 introducing the energy of the structure as a strengthening factor, especially at low temperatures. A difficulty in this model is, however, to relate this (stored) energy to the structural parameters directly observable as for instance grain size. The strengthening effect of the matrix grain size after recrystallization has been in- vestigated for nickel-thoria (TD-Nickel) products3 and for copper aluminum-oxide products. Conclusive results were, however, not obtained as the grain size of TD-nickel was constant. 5 to II , after recrystallization at temperatures from 700 to 1200°C and as the copper products containing 5 to 1 wt pct of aluminum oxide could not be recrystallized even after severe cold reduction and heat treatment at 1050C. For aluminum aluminum-oxide products containing from 1 to 5 wt pct of aluminum oxide it has been shown that the tensile strength at room temperature decreases when an extruded product is cold-worked and recrystallized. The matrix in the extruded products is divided into well-defined subgrains of micron size, and as the grain size of the recrystallized products is about two orders of magnitude higher, it is obvious that grain boundary strengthening occurs. Preliminary results8 have indicated that the flow stress containing no grain boundaries, A is a constant and t is the subgrain size. At elevated temperatures the effect of boundaries is more complex; it has been shown11 that recrystallized products having an oxide content of about 3 wt pct are more creep resistant than extruded material in the temperature range 400° to 600°C, whereas on application of a higher strain rate the tensile flow stress (0.2 pct offset) is higher in extruded than in recrystallized aluminum—5 wt pct aluminum oxide products at temperatures from room temperature to 427°C (800), Finally it has been shown12 that the Brinell hardness at 350°C of extruded products having about the same content of aluminum oxide increases with decreasing grain size, determined by X-ray line-width measurements. The present study was undertaken to obtain a quantitative relationship between the tensile strength and the grain size of aluminum aluminum-oxide products in the recrystallized as well as in the extruded state. The tensile testing was performed at room temperature and at 400uC. The grain size of the recrystallized products was varied by changing the degree of cold-work preceding the recrystallization heat treatment. In extruded products grain (or subgrain) size variations were obtained by high-temperature heat treatment after extrusion. EXPERIMENTAL a) Materials. Aluminum aluminum-oxide products have been manufactured by consolidation of aluminum powder covered with a layer of aluminum oxide formed during powder manufacturing. The products examined were manufactured from atomized powder containing

Jan 1, 1970

By R. G. Treuting, W. C. Ellis

The twinned state is characterized by a lattice of coincidence sites. Imperfections are required at stable lateral twin interfaces. Twinned regions can occur with relative ease in the diamond cubic IN recent contributions1,2 on the origin and growth of cubic annealing twins, attention has been directed to the orientation relations between such twinned components and their parent matrix. There are some aspects of twinning which may be illuminated by a more detailed consideration of the twinned state" alone. As an extreme example, the dense twinning in cast ingots of germanium,&apos; as contrasted with the rarity of twins in cast face-centered cubic metals, is yet to be accounted for. It has been this that has led us to the present work, which, it will be noted, uses methods and constructions in many respects similar to those of Kronberg and Wilson.&apos; In the cubic systems, a 70" 32&apos; rotation about a <110> axis is angularly equivalent, as to twinning, to the more usually considered 180" rotation about a <111> axis. Figs. 1 and 2 show a (110) projection of a twinned face-centered cubic lattice and a twinned diamond cubic lattice. In both figures, the two adjacent planes A and B, shown by the larger and smaller circles, are sufficient to represent the entire array. In each case a section of lattice, the original atom sites of which are shown by open circles, has been rotated as indicated through 70" 32&apos; to bring an original. [112] direction into coincidence with the [112] diiection. The latter is the intercept on the (110) projection of the (ill) plane normal thereto, the twinning plane. In the face-centered cubic case the rotation can be performed about an axis passing through an atom-site; the mirror plane then is also a composition plane containing atoms common to both twinned and untwinned lattices. The diamond cubic lattice may be construed as two interpenetrated face-centered lattices. Its (111) planes recur in a sequence of alternately short and long interspacings. Consequently a mirror plane for twinning cannot be a composition plane, but must be the bisector of one of the spacings. When the longer spacing is selected, the closest distance of approach across the mirror plane in the [ill] direc- tion is identical with that in the untwinned structure. In each case periodically recurring (ill) planes (parallel with the twinning plane) are found, on which there is coincidence of atom sites of the pre-twinned and twinned orientations; these are indicated by the cross-hatched circles. In the face-centered lattice there is such coincidence every third (ill) plane; in the diamond cubic lattice, on two adjacent planes in every six. At the twinning interface in the latter, there is on each side of the mirror plane a (ill) plane of atoms common to both twin components. Conceivably, there is little influence on a plane of atoms about to be adhered to such a pair of coincidence planes, whether it be laid down in a normal or in a twinned position with respect to the previously formed structure. Slawson% as attributed the high incidence of twinning in diamond to this boundary state. Further examination shows that the motion of intermediate planes can consist of various pairs of equal and opposite translations, for example of (ill) planes in the [l&apos;;i2) direction, the familiar twinning shear, indicated in the small schematics in the figures. Since the translations form a system of shears of alternating sign between coincidence planes, twinning could take place by such a mechanism over an extended region without extensive shear; in fact, in this case any atom moves but the distance in the [1i2] direction. One alternative construction for the face-centered cubic lattice leading to the same end result is illustrated in Fig. 3. The plane (711) with respect to the pretwinning orientation (the twinning plane of Fig. 1) is given, the twinned region arbitrarily bounded by <110> and <112> directions. The coupled shear is identical to that of Fig. 1. The "rotational" movement about coincidence sites generating the same twinned position could consist as shown of the translation a,/d% for each atom of a group of three in the B layer in a different one of the three <112> directions, and a similar translation of the underlying three atoms in the C layer in either the same or the opposite sense. This is not dissimilar to Kronberg and Wilson&apos;s construction for their 22" rotation of three adjacent (111) planes.

Jan 1, 1952

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF&apos;-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz&apos; to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""&apos;"&apos;"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15&apos;F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.

By W. A. Backofen, D. Lee

Tlze condition of superplasticity or neck-resistanl flow that results front high strain-rate sensitivity has been observed in isothermal tension tests on several titanium alloys and one of zirconium hi general, il was associated with reasonably fine-grain micro-structures being stvained in the transformation range at rates below i - 10 -3 sec-&apos;. The metallographic mean-free path, L, was measured at room temperature after rapid cooling from the temperature of test-ing. The flow stress of Ti-GAL-4V at 950°C was proportional to La at different constanl <; the value of a decreased with increasing. E but at E< 1.5 x 10-4 sec-1 it varied only from 0.9 to 1.25. The findings were interpreted to mean that viscous boundary shear is the rate-controlling process of deformation at high levels of strain rate sensitivity in these materials. Elongation of over 1000 pet could be obtained, but a1 temperatures so high and rates so low that any practical application of the full effect would probably be difficult. As the transformation range was narrowed, by turning from Ti-6AL-4V to Ti-5Al-2.5sn to nomznally pure titanium, the allowable temperature varialion was correspondingly reduced. Superplasticily was not found in Armco iron, presumably because the transformation range was too narrow to allow the developtnenl of a reasonably stable microstructure for isolhermal lesting. THE work represented by this paper grew out of a recent study of texture hardening in a(hcp) titanium and zirconium-alloy sheet,&apos; of which part has now been published.2 It was found that, with heating, the tensile plastic-anisotropy index, R,* was decreased from well above 1 towards 1 as the temperature range for the a(hcp) -ß(bcc) phase change was entered. The clearest example of that trend is illustrated with previously unpublished data in Fig. 1. It might have been thought that such a development resulted simply from introduction of the cubic and therefore plastically less anisotropic phase. However, the accompanying change in the index of tensile strain-rate sensitivity, m = a log a/a log E, was rapidly upwards, to a high of 0.85 in some cases (also illustrated in Fig. 1). At the same time, the total tensile elongation rose to a maximum and the flow strength dropped away as R (and m) approached 1. Taken together, the observations cannot be understood as resulting from the presence of cubic phase, per se. It has been concluded instead that they reflect the largely noncrystallographic deformation which characterizes superplasticity. As demonstrated in other recent work? a necessary condition for super-plasticity is strain-rate sensitivity of flow stress sufficiently high that m is above a lower limit of -0.3. The origin of large m has been traced, in turn, to grain size so small that a substantial amount of viscous deformation is introduced by such processes as Nabarro-Herring diffusional flow4 and/or grain boundary shear.5,6 Because of problems in the processing of titanium and zirconium alloys—problems of high strength, limited ductility, and excessive springback, originating largely in slip resistance-it was natural to wonder if something useful might be done with superplasticity in those materials. Therefore experiments were made for more closely identifying and generally bounding the phenomenon with temperature and strain-rate limits, before attempting to decide about its exploitation. The results are being reported here. EXPERIMENTAL Materials. The two of primary interest were the titanium alloys of nominal composition (in wt pct) 5A1-2.5Sn and 6A1-4V. Others were a 4A1-1/4O2 titanium alloy, titanium of commercial purity (RC-70), Zircaloy-4. and Armco iron. All were received as annealed 3/16 in. thick sheet, except RC-70 which was & in. thick, and tested in that condition. Details of transformation temperature and grain size are given in Table I. The results of dilatometry for the measurement of transformation temperatures were unsatisfactory. Data were finally obtained by metallographic examination of each specimen after test, to determine from the amount of transformed 4 where the specimen had been heated in relation to the critical temperatures. Results were in reasonable agreement with information from the supplier. Strip tensile specimens were of full sheet thickness and taken along the rolling direction, except for those

Jan 1, 1968

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,&apos; only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,&apos; and that the solid solution is quite limited in the MnO-MnS system.&apos; The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1&apos; and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By E. A. Almond

An attempt is made to explain the effect of stress on strain aging by examining the mechanism of yielding for a group of aged dislocations. The experimental results on which the theory is based indicate that a linear relationship develops between the aging stress and the discontinuous yield effect in a low carbon steel THE discontinuous yield effect that occurs in bcc metals after strain aging is usually explained by the interaction of interstitial atoms with individual dislocations. Attempts have been made to interpret the kinetics of strain aging in terms of interstitial segregation to nonrandom groups of dislocations1-3 but apart from Li&apos;s4 work little or no effort has been made to examine the effect of groups of aged dislocations on mechanical properties. It appears likely that such groups can be stabilized if a positive load is maintained on the specimen during aging5 and, furthermore, that the enhanced strain aging effect associated with aging under load might be due to the stability of these aged groups. The effects associated with this latter phenomenon have been described by Almond and Hull, Ref. 5, Figs. 2 and 3, and it is found that the upper yield stress, the lower yield stress, and the yield point elongation are increased by aging under load. The yield point elongation reaches a maximum value but the enhanced effect persists in the upper and lower yield stress values even after extended aging treatments when the general level of the flow stress curve rises. The flow stress, as measured at 8.5 pct total strain, however, is independent of aging stress. Almond and Hull5 showed that it was unlikely that the differences in mechanical properties could be caused by stress enhanced diffusion and they suggested that the effect was in some way associated with the different dislocation distributions that are obtained when specimens are aged with and without an applied stress. At that time no explanation was offered for the strengthening effect produced by stabilized dislocation distributions but additional tests have been performed to establish a quantitative relationship between aging stress and mechanical properties, and also to examine more closely the effect of varying the procedure for applying the aging stress. EXPERIMENTAL The material used was an iron wire containing 0.015 wt pct C, 0.002 wt pct N, and 0.006 wt pct 0. Tensile specimens with a 1 cm gage length and 0.08 cm diam were annealed at 850°C for 1 hr in vacuum to establish a grain diameter of 0.032 mm and then aged at 200°C for 24 hr. After this treatment the amount of carbon left in solution would be less than 10-4 wt pct, and ni- as aging time is increased. It is suggested that this observation, and effects that arise from varying the method of applying the aging stress, can be explained by a strengthening mechanism whereby dislocations are more difficult to move when they are aged in piled-up groups. trogen would be the main cause of strain aging. Tensile tests were performed in a hard beam machine at a constant crosshead speed of 0.02 cm per min and the specimen chamber was immersed in a temperature controlled silicone oil bath at 32" * 0.05"C. RESULTS All specimens were prestrained 5 pct before aging under stress and the results in Figs. 1 to 5 show the effect of aging time and aging stress on the following parameters ?UY = auy — ?F(5); i.e., the difference between the upper yield stress after aging,?uy, and the flow stress after prestraining 5 pct, ?f(5). ?LY = sly —sf(5); the difference between the lower yield stress after aging, ojy, and the flow stress after prestraining 5 pct. s8.5 = the flow stress at 8.5 pct total strain after aging at 5 pct strain. Varying the Loading Procedure. Three variations in the procedure for applying the aging stress were examined; i) After prestraining, the specimen was unloaded to a stress of 18 kg mm-2, aged at that stress, and then tested. ii) After prestraining, the specimen was unloaded to 2 kg mm-" then reloaded to 18 kg mm-&apos;, aged at that stress, and tested. iii) After prestraining, the specimen was unloaded to 18 kg mm-&apos;, aged at that stress, then unloaded to 2 kg mm- before testing. Specimens were unloaded or reloaded by decoupling a clutch in the drive transmission of the tensile machine. This enabled the crosshead to be driven manu-

Jan 1, 1970

By W. B. Gogarty

The reported decreases in water mobility do not seem unusual in view of non-Newtonian fluid properties. Shear stress vs shear rate diagrams have been reported for other solutions of water-soluble polymers. Some of these polymers are similar to the type mentioned by the author. Generally, the shear stress-shear rate is a non-linear function for these solutions. Data for plotting apparent viscosity vs shear rate can be obtained from this function. Apparent viscosity is defined as the ratio of shear stress to shear rate at a given shear rate. When plotted, the apparent viscosity decreases with increasing shear rate. This behavior is typical of a pseudoplastic fluid. For some water-soluble polymer solutions, the apparent viscosity decreases more than 50 times while the shear rate increases 1,000 times. Thus, viscosity of a pseudoplastic fluid only has meaning at a specified shear rate. Results of Fig. 1 could be explained in these terms. Viscosities measured in the Ostwald viscometer represent values at a given shear rate. Some average shear rate is affecting the polymer solutions while flowing through the core. This average value fixes the apparent viscosity as long as the flow rate remains constant. Viscosities measured by the two methods will be equal if shear rates are the same. The results indicate that shear rate in the core is lower (higher apparent viscosity) than in the viscometer. In the paper by Johnson, Bossler and Naumann, the relative permeability is independent of viscosity ratio. Thus, the relative permeability with respect to water flow at residual oil should be independent of the flowing phase viscosity. Polymer solutions will appear as Newtonian fluids The discussion emphasizes the nature of the "resistance factor effect" as discussed in the paper. Repeated anomalies arising in hundreds of experiments led us to the conclusion that non-Newtonian flow is not the only factor. Several of the key anomalies are as follows: 1. Measured viscosities over a range of shear rates from <1 sec-&apos; to 1,000 sec-&apos; do not account for but a minor fraction of the R observed in cores when compared in similar shear-rate ranges. 2. The slope of R vs flow rates in cores is always different from that expected from viscometer shear-rate measurements as shown in Fig. 2. in a core, the level of viscosity being fixed at a given flow rate. With these conditions, the definition of resistance factor R by Eq. 2 is simplified to Since , is constant with rate, R becomes a measure of the apparent viscosity in a core at a given flow rate. Variation in flow rate could easily account for the changes of R shown in Fig. 5. Also, this points to the fallacy of assuming R to be a unique parameter. The constant resistance factors at different flooding velocities appear to be in disagreement with the above discussion. The author furnishes Fig. 2 to support his arguments. As shown, the resistance factors remained substantially constant in the two cores over a considerable range of flooding velocities. However, in the 73-md core, the factor increases at lower rates. This behavior agrees with known characteristics of some pseudoplastic material. These materials act both as Newtonian and as non-Newtonian fluids in different regions of shear rate. Some exhibit first Newtonian, then non-Newtonian, finally, Newtonian character. Others are first non-Newtonian and then Newtonian. This latter type would explain the results with the 73-md core. The Fann-instrument results are not significant since shear rates in the core may be much different than with the viscometer. The higher resistance factor at high rates in the 150-md core is more difficult to explain. The greater resistance at increased flow rates could be attributed to what might be termed temporary bridging. As envisioned, changes in polymer configuration occur at the higher energy associated with the increased flow rate. These changes could cause less effective passage of polymer through the core. Correspondingly, increases in pressure drop will occur. These will be interpreted as higher resistance factors. 3. Most polymer solutions are non-Newtonian and many are more shear-rate sensitive than the polymers in question, yet only a very few polymers demonstrate useful R values. Gogarty&apos;s assumption that viscosities in cores and vis-cometers will be the same if measured at the same shear rate is only valid if non-Newtonian rheology is the only parameter. The experimental evidence does not validate this assumption. The anomalies observed in the equilibrium displacement experiment shown in Fig. 5 are not explained on the basis of varying flow rates since the rates were held constant. M

Jan 1, 1965

By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder&apos;s equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

By Norman B. Pilling

Practical limitations to the usefulness of silicon steels are the hardness and brittleness silicon imparts to iron, making iron-silicon alloys of more than 8 per cent. silicon content unusable except where castings can be employed. In the use of commercial silicon steel, in thin rolled sheets, as in transformer construction, when the silicon content exceeds 4.2 per cent. the sheet is too brittle for satisfactory shaping by punching or similar operations. When such a brittle steel is sheared, it frequently breaks along a haphazard path in advance of the cutting tool. In Fig. 1 is shown a slightly enlarged view of the sheared edge of a 14-mil enameled sheet of nominally 4 per cent. silicon steel. In 5 in. along the sheared edge, only 44 per cent. was actually cut; the rest was torn, with the path of fracture varying widely from the path of travel between the shears. This is probably an extreme case of such brittle-ness, but a shearing or punching test is not necessary to reveal brittle-ness of this order; narrow strips will break when bent between the fingers. In Fig. 2, the proportion of actual cut edge is greater, but secondary fractures branch off at about 30" from the line of shearing in advance of the cut. Deprived of the support of adjacent parts of the sheet, the tips of the angles are bent out of the plane of the sheet by the shears, leaving a peculiar flared effect, like the set of the teeth on a saw. An end-on

Jan 1, 1923

By Norman B. Pilling

Practical limitations to the usefulness of silicon steels are the hardness and brittleness silicon imparts to iron, making iron-silicon alloys of more than 8 per cent. silicon content unusable except where castings can be employed. In the use of commercial silicon steel, in thin rolled sheets, as in transformer construction, when the silicon content exceeds 4.2 per cent. the sheet is too brittle for satisfactory shaping by punching or similar operations. When such a brittle steel is sheared, it frequently breaks along a haphazard path in advance of the cutting tool. In Fig. 1 is shown a slightly enlarged view of the sheared edge of a 14-mil enameled sheet of nominally 4 per cent. silicon steel. In 5 in. along the sheared edge, only 44 per cent. was actually cut; the rest was torn, with the path of fracture varying widely from the path of travel between the shears. This is probably an extreme case of such brittle-ness, but a shearing or punching test is not necessary to reveal brittle-ness of this order; narrow strips will break when bent between the fingers. In Fig. 2, the proportion of actual cut edge is greater, but secondary fractures branch off at about 30" from the line of shearing in advance of the cut. Deprived of the support of adjacent parts of the sheet, the tips of the angles are bent out of the plane of the sheet by the shears, leaving a peculiar flared effect, like the set of the teeth on a saw. An end-on

Jan 1, 1923

By Enrique Hauser

FiRE-damp is a mixture of methane with other inert gases or combustible gases. The inert gases in question are carbonic acid, water vapor, nitrogen, etc. The combustible gases are hydrogen, ethane, etc. The study of the properties of fire-damp, therefore, becomes a study of the properties of methane and the influence on its properties of the different gases we have mentioned. Characteristic Properties of Methane 1. Respirability.—Methane being a paraffin is characterized by its weak chemical affinities. Prom the physiological point of view one could substitute it for nitrogen of the air at least momentarily, without experiencing any difficulty in breathing the mixture consisting of 21 per cent. 02 + 79 per cent. CHI. I have tried this on myself, making the gas exhaled from the lungs burn subsequently in a Bunsen burner.&apos; From the chemical point of view, this weak affinity permits the gas to be burned in certain circumstances with hydrogen and oxide of carbon in an oxygenated mixture, with the result that the last two gases achieve only a fractional combustion. This practice has been utilized with success in the methods of analysis which I have perfected and which I describe later in this paper. 2. Retardation of Flashing Point.—A characteristic property of methane is its retardation of flashing point, noted by Davy in 1816 and studied by Mallard and Le Chatelier in 1883.2 Taffanel and Le Floch have recently confirmed these results.8 Let us recall the nature of this retardation: When a mixture of combustible gases with air or with oxygen is

Jan 1, 1916

By John F. Burst

GENETIC correlations of the various types of Cheltenham fireclays found in Missouri have been the subject of several papers. The correlations usually have been attempted on the basis of stratigraphic and leaching patterns (Wheeler,18 1896; Allen, 1,2 1935 and 1937; McQueen,13 1943). Herold10 (1943), as well as Allen,l,2 has dealt at length with the mineral¬ogy of Missouri fireclays and postulates genetic relationships from min¬eralogical findings. Both researchers cite kaolinite as the primary clay mineral of the Cheltenham formation and suggest that differences in physical proper¬ties are due to clay mineral impurities such as halloysite or illite (not recog¬nized by the name "illite" at the time of Allen&apos;s papers). By ascribing the differences to impurities, it is possible to use weathering as the only major alteration factor. This paper seeks to probe still farther into the clay mineral composition of the Cheltenham formation and to show thereby that the mineralogical differ¬ences that have been found to exist within the "kaolinite" component of the Cheltenham fireclay may alter somewhat the previously held theories of diagenesis. Two Missouri fireclays, which have been rather thoroughly investigated, were chosen for comparison of genetic relationship to clay mineral content. One is a typical plastic fireclay of the middle Cheltenham (McQueen&apos;s classification13) obtained at Mexico, Audrian County, Missouri, from a large open pit operated by the A. P. Green Fire Brick Co. The other-a typical hard flint fireclay-was obtained from a pocket deposit in southwestern Mont¬gomery County, Missouri.

Jan 1, 1952

By Wilbur H. Grant

THE property of the United Comstock Mines Co. lies in the eastern foot-hills of the Sierra Nevada Mountains, in the Washoe mining district of Storey County, Nev. Commencing at the boundary line between Virginia City and Gold Hill, covering all the town of Gold Hill, it extends south to American Flat; the main camp, or the new town of Comstock, the mills, shops, residences of employees, and the main haulage-tunnel portal are located on American Flat. The property extends for about 10,300 ft. along the lode; this covers the southern end of the main Comstock lode, the Knickerbocker branch, and the junction of the Silver City branch with the Comstock lode. Within the property, 5000 ft. of the main Comstock lode is known to have been productive, 1000 ft. of the lode at the northern end of the property is thoroughly developed, and 1000 ft. south of this is partly developed; this leaves about 3000 ft. of the known productive portion that has not been opened up by this company. The northern end of the property, or the Imperial mine, has been intricately developed by five main levels and numerous sublevels. The Yellow Jacket ground to the south has been partly developed by the reopening of three old levels. In addition, the main haulage level is driven from the portal at Comstock for 9250 ft., to the north end of the property; about 5500 ft. of this `is in the foot wall of the lode and parallel to it.

Jan 11, 1922