Search Documents

By L. S. Reid, Irwin Politziner F. M. Townsend

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By L. H. Schwartz, S. K. Lahiri, M. E. Fine, D. Chandra

WHILE the yield stress of solution treated Fe-Cu alloys increases rapidly with aging, a precipitate has only been directly observed in overaged samples.'-" This precipitate is essentially pure fcc copper, the E phase. Hornbogen2 suggested that the initial hardening is due to clustering of copper atoms in a bcc iron matrix. Hornbogen was not able to obtain direct confirmation for such bcc clusters by either X-ray diffraction or electron microscopy; however, he did observe analogous clustering in Fe-Au alloys7 where the scattering factor difference between iron and gold is more favorable than that for iron and copper. Fujii, Nemoto, Suto, and Monma4 recently observed diffuse electron diffraction scattering in a 2.5 pct Cu alloy aged at 500°C: for 30 hr. They suggested that part of the diffuse SCattering was due to a modulated structure of 26 to 42 wavelength parallel to the (110) matrix plane. This disappeared with further aging. However, 30 hr at 500°C is well beyond the peak strengthening in this alloy which occurred at less than I hr at 500oc.4 By transmission electron microscopy they could not distinguish between quenched samples and samples aged to maximum strength. The purpose of the present investigation was to try to obtain further confirming evidence for a precipitation stage preceding the formation of the fcc E phase. Change in Young's modulus was selected for study be- EXPERIMENTAL PROCEDURE The Fe-1.67 at. pct Cu alloy was supplied by the U.S. Steel Corporation in the form of a hot forged rectangular bar. The carbon and nitrogen contents of this alloy were 70 ppm and less than 10 ppm, respectively. The samples for Young's modulus measurements were made by cold swaging to & in. diam and cutting to 2 in. lengths. Tensile test samples 1 in. long were prepared by cold rolling to a thickness of 0.012 in. and then machining to gage dimensions of 0.5 by 0.012 in. For Mijssbauer studies, foils 1 mil thick were prepared by cold rolling. During fabrication the alloy was given intermediate anneals at 845OC followed by quenching. The specimens after preparation were solution treated at 1000°C (y field) or 845°C (a field) for 1 to 2 and 5 to 6 hr, respectively, in a dynamic vacuum of about 2 x lom6 torr. The tensile and modulus specimens were drop-quenched into iced brine through an aluminum foil which vacuum-sealed the bottom of the furnace tube. The MOssbauer foils were drop-quenched into helium gas cooled by passing through N2 (liq) in a copper coil. The grain diameter of the modulus and tensile specimens was between 0.025 and 0.035 mm. The samples were aged from 400" to 500°C in a dynamic vacuum of 2 x 10-6 torr and cooled by pulling into a water-cooled portion of the vacuum system. The dynamic Young's modulus was measured at room temperature using electrostatic excitation and detection of longitudinal vibrations.' Neglecting any length change during the aging, (this is expected to be comparatively small), the fractional change of Young's modulus (?Et)/Eav, is equal to twice the fractional change of the resonant frequency (?ft)/fav . ?ft =ft —fo where fo and ft are the resonant frequencies of a specimen before aging and after aging to time t. The measured f's, approximately 51,000 cps, were corrected to 25°C for any variation in the ambient temperature. The tensile tests reported were carried out at room temperature in an Instron with a 1000 lb full scale load cell. The flow stress reported herein corresponds to a strain of 0.002. The Massbauer spectra were taken in a constant acceleration model AM-1 NSEC spectrometer. The

Jan 1, 1970

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.'-4 Samsonov et al.' reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami's Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

By D. de Fontaine

A convolution procedure is described for obtaining an analytical expression for the composition profiles of solute concentration:; in binary solid solutions. The free energy of solutions containing such compositional inhomogeneities can then be evaluated and the stability of spherically symmetric clusters (G.P. zones, for short) us a function of their radii and central compositions can be studied accordingly. Two characteristic zone radii are defined: the minimum radius (RM) corresponding to the smallest zone for which growth is energetically favored over dissolution, and the critical radius RK) corresponding to zones associated with the minimum work of formation. The values of RM and RK coincide at the two classical limits of nucleation and growth and spinodal decomposition. As the spinodal is approached, however, RM and RK diverge increasingly and it is proposed that the initial] decomposition morphology is governed more closely by the minimum, rather than by the critical radius since the former possesses no singularity within the m eta stable phase boundary. Reversion is briefly discussed in the light of the foregoing and it is shown that a set of reversion temperatures located between the coherent miscibility gap and the coherent spinodal must correspond to a given distribution of low temperature zones. SINCE the early works of Guinier1 and preston,2 the kinetics and morphology of GP zones have been studied extensively, see Ref. 3, for example, for a recent review. Nevertheless, a completely satisfying theoretical treatment of the decomposition of meta-stable or unstable binary solid solutions is still lacking due to the almost unsurmountable mathematical difficulties that one encounters in attempting to solve the pertinent diffusion equation which, in principle, describes the whole process. This equation, first derived by Cahn for the initial stages of spinodal decomposition,4 is a nonlinear partial differential equation of the fourth order in anisotropic space, a general analytical solution of which is completely out of the question. From this equation, some prediction can be made, however, concerning the later stages of spinodal decomposition5 and a recent numerical solution6 of the equation in the case of one- and two-dimensional composition modulations of a solid solution inside the spinodal has led to the following considerations: the sinusoidal morphology7 is to be expected only for solutions of average composition c, located near the center of the coherent miscibility gap.8 For solutions with co closer to the spinodal decomposition, depleted shell zones9 should constitute the first recognizable decomposition product, later evolving to iso- lated, enriched preprecipitates in a uniformly depleted matrix as this must, in all cases, constitute the final metastable morphology, barring, of course, loss of coherency and change in crystal structure. In agreement with the qualitative description of Bonfiglioli and Guinier,l0 it thus appears that the various models discussed by previous authors are, in fact, idealized successive stages of the general decomposition process. Unfortunately, corresponding calculations for a solid solution outside the spinodal are not yet available because of two additional difficulties: it is essential that the diffusion equation be solved in three-dimensional space, and furthermore, one must include in the equation an appropriate "source term" describing the statistics of the creation of composition fluctuations required to trigger the nucleation events. At present, a general treatment of this problem does not appear to be tractable. Nevertheless, by using a modelistic approach, i.e., by selecting a priori certain composition variation profiles and by evaluating their associated free energies, one can draw certain conclusions relative to the stability of these isolated composition modulations or "zones", both outside and inside the spinodal. This is the object of the present investigation. THEORY We shall now describe a standard four-parameter spherically symmetric GP zone, evaluate its free energy according to the Cahn and Hilliard11 formula (Eq. [5], below), and plot the corresponding energy surfaces as a function of zone amplitude and radius as

Jan 1, 1970

By R. F. Blakely, P. E. Potter

Any stratigraphic section or bedding sequence can be synthesized if there is a transition procedure from one lithology or bedding type to another, and if thickness distributions of the different lithologies are known. Stratigraphic sections of a fluvial sandstone body were synthesized with five bedding types: cross-bedding, massive beds, parting lineation, ripple mark and mudstone. The transition procedure from one bedding type to another used dependent, Markovian random processes which have a memory that extends one step backward in the depositional process. As observed in nature, median grain size and sand wave thickness (cross-bedding and ripple mark) decline upward in the synthesized sections as proportions of the different bedding types change. Grain size and permeability were also incorporated into the sections. By changing the transition procedures, bed thickness distributions, rate of upward decline or sand wave height and length, different types of sections can be synthesized, thus making it possible to model many different sedimentation problems. INTRODUCTION This paper describes a general method for synthesizing stratigraphic sections and bedding sequences of sedimentary, metamorphic or igneous origin. Synthetic generation is of interest for several reasons. Close correspondence between real and synthetic sections suggests that the factors used in the synthesizing model may indeed be the correct ones, thus giving the investigator a check on his assumptions. Rapid, inexpensive simulation of many stratigraphic sections permits one to synthesize a rock body (sandstone or carbonate reservoir) or, on a larger scale, the fill of a sedimentary basin. Harbaughl gives an example of mathematical simulation of a carbonate basin. He simulated the basin in the hope that improved prediction would follow better understanding of the depositional processes. From the petroleum engineer's viewpoint it seems reasonable to believe that the synthetic generation of rock properties and their distribution in a reservoir should be relevant in the study of reservoirs. Any stratigraphic section or bedding sequence can be generated provided there is a transition procedure from one lithology or bedding type to another, and provided the thickness distributions of the different units are known. The transition procedure involves random processes that are either independent or dependent. If the depositional process is independent, previous deposition will have no influence on present deposition. However, if it is dependent, past deposition will influence either present or future deposition. Such a dependent depositional process can be thought of as having a memory that extends backward in time through one or more pulses of deposition. A process with a memory can be described by a Markov process. Because the concept of memory or dependence appears to be in accord with our understanding of many depositional processes, Markov processes were used to synthesize the bedding sequences of this study (see Appendix). The above methods are perfectly general and are appropriate for any stratigraphic section or bedding sequence: bedding types in a beach deposit, an evolving carbonate bank or the changing lithologic fill of a thick geosyncline sequence. We chose to synthesize a vertical profile of a fluvial sandstone body because its characteristics were well documented, much was known about fluvial processes and fluvial-deltaic sandstone bodies constitute an important class of petroleum reservoirs. CHARACTERISTICS AND ORIGIN OF FLUVIAL CYCLE The fluvial cycle has been well documented in recent years by Bersier,2 Allen3-5and Visher.6,7 Deposits from fluvial cycles range from 10 to 150 ft or more in thickness and are characterized by a "fining upwards": coarse sandstones with occasional conglomerates grade upward into medium- to fine-grained sandstone, and hence into siltstone and mudstone. The dominant sedimentary structure is inclined bedding: thick cross-beds in the lower half

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION in pure gold has been studied by Sagrubsky,1 McKay,2 Gatos and coworkers,3,4 and Okkerse.5 Sagrubsky used a sectioning technique but reported results far lower than any of the others. The work seems to be carefully done, and it appears that a factor of 60 must have been omitted in his calculations or the units misstated by an equivalent amount. McKay used a surface activity method, and Gatos and Kurtz, following Gatos and Azzam, applied autoradiography to the measurement of activity on an oblique section through the diffusion zone. These two investigations agree well with each other but give results below those reported here. Okkerse employed a very careful sectioning technique. Chemical interdiffusion in Au-Ag alloys has been measured under several concentration conditions. Average values of the diffusion coefficient for the range of 0 to 18 atomic pct Au were obtained by Braune.6 since the diffusion coefficient probably varies markedly over this range, the values may not be too useful. Also, a plot of these data suggests that grain boundary contributions may have been appreciable at the lowest temperature employed. Ebert and Trommsdorf7 give average values for 0 to 9 atomic pct Ag, and Johnson8 reports average values for 45 to 55 atomic pct Au. Johnson also measured silver and gold self-diffusion coefficients in 49.2 atomic pct Au alloys, and self-diffusion in pure silver. The self-diffusion of gold in pure silver has been determined by Jaumot and Sawatsky.10 Other measurements which do not cover a range of temperature or are of low precision are not mentioned in this account since a review by Kubaschewski is available." This contribution reports diffusion coefficients for self-diffusion in gold, self-diffusion of gold in Au-Ag alloys, and chemical diffusion in Au-Ag alloys. Although it had been intended to obtain silver self-diffusion data in the alloys it now appears unlikely that these measurements can be done soon, so a table has been worked out for a self-consistent scheme of diffusion coefficients which should not be too far from the true values. Experimental Details Experiments on pure metals were conducted using fine gold of 99.99+ pct Au and silver of the same purity. Alloys were prepared by melting the two metals together in a graphite crucible in vacuo and allowing the slug to solidify in the crucible. After machining to a cylinder about 0.85 in. diam each slug formed one half of a diffusion couple. Compositions were determined later by analyzing chips taken from the extremities of the diffusion zones. The gold used in the preparation of alloys was sometimes pure gold but was normally either in the form of clean pickled alloy from previous experiments or gold recovered by oxalic acid precipitation from warm aqueous solution. Chips from the various stages of experimentation were dissolved in aqua regia and the solution taken to low bulk, diluted with water, and again taken to low bulk before diluting for the precipitation. This precipitated gold contained a small amount of silver as the only impurity detectable by spectrographic analysis. Disks for use in diffusion couples had opposite plane faces abraded on emery paper as far as zero grit, were annealed for 12 hr at 900°C in argon, and had one face of each disk polished to 000 emery paper. Radioactive gold was plated at about 2 ma per sq cm from a small volume of cyanide solution containing 1 mg of inactive gold as a carrier. Specimens , were freshly abraded on 4/0 emery paper immediately prior to plating. In the case of the active couples disks of a similarly prepared but unplated alloy or pure metal were placed on top and welded to the active disk. With the concentration couples disks of different compositions were welded. Welding was performed after a pressure of 5,000 lb had been applied at

Jan 1, 1958

By A. Gittens

In two recent papers stevens13,14 has compared the methods used by various investigators to calculate the contribution of grain boundary sliding to the total creep strain. In previous work Gittins15 has shown that the strain due to grain boundary sliding Egb may be estimated from the lateral, d, and vertical, v, displacements of a longitudinal marker line as it crosses a grain boundary. He obtained the formula, where nL is the number of grains per unit length measured on the specimens before creep, and \p and ?2 are, respectively, the angle between the grain boundary and the stress axis in the plane of the surface and normal to the surface (see Ref. 13, Fig. 1). The subscript L indicates that observations are made in a longitudinal direction parallel to the stress axis. It was generally found more convenient to measure the grain size of a specimen before creep; this was necessary to characterize the specimen. Stevens13,14 however prefers to define Egb in terms of NL, the number of grains per unit length after creep. Since nL - NL(l + €1) where cr is the total strain, Eq. 1 11 becomes The quantities d and ?, can be determined directly from the marker lines, while v and ?2 are found by sectioning normal to the surface. In the interior when symmetry considerations suggest that v = d and ?1 - ?2 the strain due to grain boundary sliding may be estimated from a suitable internal longitudinal marker line by the equation To determine cgb at the surface using either Eqs. |1| or [2] requires a large number of observations, particularly if many estimates of cgb are required, and also it is impossible to determine the variation of cgh with creep strain on the same specimen because the specimen must be sectioned to determine ?2. Gittins15 found that for a number of materials the sliding vectors d and v were related to each other so that provided one was measured the other could be estimated. Also during creep, grain boundaries tend to migrate to meet the surface at angles close to 90 deg,16 so that the term nL(v/tan?2)L was comparatively small when 4,- 90 deg. By determining the frequency distributions of ?2 on control specimens this term can be estimated without sectioning the creep specimen. In this way an empirical equation based on Eqs. |1| and |2| enables cgb to be determined with reasonable accuracy with fewer observations of the angles and sliding components. For B brass, the relationship between the sliding vectors indicated that ceb = 0.85nLVL . In Table I of Stevens paper this equation is stated to be incorrectly derived. However it should be pointed out that this is an empirical equation derived from Eq. |1|, based on a knowledge of the relationship between d and v and on the frequency distributions of ?1 and ?2 for a particular material under given experimental conditions. It was used only when these relationships were known, to reduce the number of observations required to estimate cb. Therefore the comment "derivation incorrect does not apply. Gittins did in fact make use of Eqs. |1| and 131. Author's Reply I must apologize to Dr. Gittins for the inadvertent misrepresentation of his work. Other slight errors in Table I have been pointed out to me. Langdon (No. 12 Table I), Gifkins (No. 7, Table I), and possibly other workers did not measure the number of boundaries per unit length after creep (A') but the corresponding quantity bejove creep (n). As Dr. Gittins points out, a completely analogous set of equations to those given in the paper can be derived by the same method: using the number of boundaries per unit length before instead of after creep. The basic equations corresponding to Eqs. [2] and 171 of the paper, from which all the others can be derived, are

Jan 1, 1968

By M. Cross

INTRODUCTION The development of refining processes involving gas injection into liquid metals has seen the evolution of a variety of designs [I]. During the last few years or so the top, bottom and side blown processes have, essentially, been combined to produce a series of mixed gas blowing schemes (eg. the LBE [2,3] and LD-OB processes [4,5]). Although, a variety of mixed gas blowing processes have been carefully engineered and recorded operational experience now attests to their effectiveness, optimising their design and operational performance is another matter. Detailed process analysis of such operations is impeded by the complex nature of the physical and chemical processes involved: . fluid flow behaviour of the liquid metal and injected gases, . chemical reactions in the vessel, . mass and heat transfer within the fluid phases in the vessel, . influence of the geometry (eg. location of the tuyeres, etc.), . monitoring the operational performance. By and large, design and operating parameters evolve from a combination of laboratory scale experiments, pilot plant work and, of course, practical engineering experience. Conventionally, the gas-liquid system used to model the industrial process is air-water, for a number of valid reasons including – . visual demonstration plus geometric and (to some extent) dynamic similarity, . the fact that the system demonstrates, at least, qualitatively many of the complex features of gas injection - interaction between the gas and the liquid - the nature of the gas flow behaviour - qualitative indications of mass transfer rates Important experimental contributions to the understanding of gas liquid systems include the work of Brimacombe [6], Wraith [7], T.Robertson [8], D.Robertson [9], Guthrie [10] and Szekely [11] (these references provide starting points to identify the major published work in this area). Although air-water systems have been instrumental in providing a great deal of qualitative insight into the fluid flow behaviour of the processes, reliable quantitative predictions are more problematic. A number of workers (notably Brimacombe and colleagues [6, 12])have demonstrated that different gas-liquid systems can lead to wide variations in behaviour. Other limitations of physical modelling include the assumptions of isothermal flow, scale- up of turbulent flow behaviour and the inability to directly include the effects of chemical reactions. The above limitations in physical modelling, therefore, yield a natural role for mathematical modelling provided that it can be made comprehensive enough whilst remaining cost-effective. The major physical processes involved in gas injection systems may be summarised as . behaviour of the gas envelope structure in moving through the liquid metal . the global movement of the liquid metal . momentum interaction between the liquid metal and the injected gas . heat transfer and mass exchange via the chemical react ions. The behaviour of gas envelopes forming at a tuyere and then moving through the liquid has been investigated thoroughly by a large number of workers. Such models are generally based upon simple physic- al concepts derived from visual observation. An early model by Davidson and Schuler (DS), based upon a force balance between the liquid inertia and a combination of the bouyancy and momentum forces on the envelope, has proved to be a useful tool in predicting bubble volumes at detachment [13]. The DS model has been successfully modified in a number of ways [14-17] to cope with heat transfer and reactive transfer rates, etc. Furthermore, the basic ideas summarised above have also been confirmed on industrial converters by both Guthrie [I8] and Brimacombe [19]. Models have also been developed to predict the behaviour of the "chemical" component of some gas-liquid systems. However, one thing is clear; all gas-liquid reactive systems are governed by the degree to which effective mixing occurs. As such, the processes are dominated by the behaviour of the heat and mass exchange of the two phase fluid flow system. It is the pattern of movement of the turbulent liquid metal plus its interaction with the injected gas which must be predicted reliably, if sufficiently comprehensive comp-

Jan 1, 1984

By J. B. Agan, R. J. Fernandes

This paper utilizes the layered-system approach, modified to include areal sweep efficiency, to determine the miscible-slug size required and to predict the perfort7zance of a miscible-slug process in a highly stratified reservoir having a permeability variation of 0.76. The slug size in each layer was determined from theoretical calculations and laboratory data which showed that, to maintain miscibility in the reservoir, the slug size had to be 8.2 per cent of the floodable hydrocarbon pore volume. Economic considerations, however, such as the value of the miscible product injected, the cost of injection and the cost of reprocessing the miscible product, limited the amount of miscible product which could be injected into the lower-permeability layers. This resulted in subjecting only 60 per cent of the reservoir to a slug size sufficient to maintain miscibility. Utilizing the relationship of producing gas-oil ratio and areal sweep efficiency as a function of pore volume injected (as obtained from data published by Dyes, Caudle and Erickson2), the theoretical performance was determined. This prediction is compared with actual performance to date. Actual performance reflects an increasing percentage of tniscible product in the produced fluid to a particular level, which remains static for a short period and then increases again to a higher level. This performance suggests that the reservoir has performed as a layered system. It is concluded that the layered-system approach can be used to predict performance in a highly stratified reservoir and that economic consideration is a limiting factor in determining the amount of the reservoir which can be miscibly swept. INTRODUCTION The Paloma zone in the Paloma oil field, Kern County, Calif., is comprised of several sand members separated by siltstone, shale and/or cherty sections. Rapid facies changes within the zone indicate that the sediments were deposited in a "near shore" environment. As a result, the Paloma sands have a high permeability variation, and the Paloma zone is comprised of several sand reservoirs. Since one of the sand reservoirs containing crude oil was not receiving the benefits of gas injection, consideration was given to recompleting certain wells to isolate the sand in order to perform a miscible-phase injection project and, thereby, to increase its ultimate oil recovery. Before proceeding with the project, a review of the literature was made to determine the miscible-slug size that would be required to maintain miscibility throughout the displacement process. Although the review showed that considerable information was available for homogeneous systems, insufficient information was available to determine slug-size requirements and to predict performances for a highly stratified reservoir. This paper has been prepared to describe the method used to determine the miscible-slug-size requirement and to predict the performance of the miscible-phase injection project initiated in the Paloma oil field. Although the Paloma project has only been in operation since Aug., 1958, sufficient production history has been obtained so that a comparison can be made with the predicted performance. DESCRIPTION OF RESERVOIR The reservoir in which the miscible-phase project was initiated in the Paloma field is shown on Figs. 1 and 2. Reservoir properties are as follows: average sand thickness, 43 ft; porosity, 19.1 per cent; water saturation, 47.2 per cent: oil viscosity, 0.328 cp; reservoir temperature, 250°F; reservoir pressure, 3,500 psi: gas saturation, 21.2 per cent at time of miscible product injection; and total net hydrocarbon pore volume, 19,993,000 reservoir bbl. LIMITATIONS The method described herein utilizes a layer-system approach, where injection into and production from each layer is assumed to be proportional to the layer's fractional capacity. The effects of increased fluid mobility on injection and production rates, in layers which have had breakthrough, are not reflected in this method. There has been considerable controversy over the slug size necessary to maintain miscibility throughout the displacement process. In this method, the slug-size

By T. L. Loucks, E. T. Guerrero

Pressure drop characteristics in a system composed of two adjacent concentric regions of different permeability were studied. The differential equations for continuity of mass flow in the two regions were solved using the Laplace transformation and the necessary boundary conditions to give the pressure distribution in the composite reservoir, the resulting equation for pressure drop at the inner boundary was evaluated for a variety of composite reservoirs and compared with the results for a uniform reservoir. From this study it was found that under certain conditions the permeability in both zones, as well as the size of the inner zone, can be determined from the pressure drop curve. INTRODUCTION The theory for the pressure distribution and pressure build-up behavior of a well producing a single, slightly compressible fluid from infinite and finite homogeneous reservoirs was presented by Hornerl and Miller, Dyes and Hutchinson.2 Extensions on this original work to provide improved and extended interpretations and better agreement between theory and observed results have been made by Matthews, et a1,3 van Everdingen,4 Gladfelter, et al5 Stegemeierand Matthews,6 Hurst and Guerrero,7 and Perrine.8 More recently Lefkovits, et al,9 studied pressure build-up behavior in bounded reservoirs composed of stratified layers. Houpeurtl0 has suggested various approaches to the general problem of variable permeability and porosity but presented no analytic solutions for particular permeability variations. Albert, Jaisson and Marionll studied the finite composite reservoir and presented numerical solutions to the unsteady-state case and an analytical solution valid only for large times. They also studied the so-called pseudo-steady state for several examples of radial permeability variations. Very similar examples have been treated in the unsteady state with application to pressure build-up by Loucks in an unpublished manuscript. More recently Hurst12 has presented the complete point-sink solution (valid for all times) for the infinite composite reservoir. He applied these solutions to interference between oil fields along with an even more elegant application of his explicit solution to the material-balance equation including water influx. Mortada 13 approaches the same application by avoiding the point-source limitation but gives the solution for the aquifer region which is valid only for large times. Hopkinson, Natanson and Temple14 have treated both the finite and infinite composite reservoir obtaining the pressure distribution for the inner zone valid for large times. This paper presents a theoretical study of the pressure distribution in an infinite composite reservoir composed of two adjacent concentric regions of different permeability. The object was to determine the manner in which pressure drop at the inner boundary of a composite reservoir depends upon time, the permeability of each zone and the size of the inner zone. Expressions for the pressure distribution in both zones are developed which take into account the radius of the sink and are valid for small times as well as large times. It was felt that an understanding of the pressure drop behavior in various composite reservoirs would be of assistance in the interpretation of some pressure build-up curves which do not behave according to the theory derived for uniform systems. Often the region surrounding the wellbore is either more permeable or less permeable than the reservoir because of the various drilling and completion practices. The effects of reduced permeability due to drilling-fluid invasion and of increased permeability due to fracturing or acidizing need to be more carefully defined. Therefore, an equation for the pressure drop in a composite reservoir was developed, and the effects of both the permeability in each zone and the size of the inner zone were studied. STATEMENT AND SOLUTION OF PROBLEM BOUNDARY CONDITIONS AND ASSUMPTIONS The physical system studied was a composite

By H. D. Kessler, R. J. Van Thyne

Phase diagrams of the titanium-rich portion of the ternary systems from 0 to 10 wt pct Al and 0 to 1 wt pct 0, N, and C were determined. Micrographic analysis of annealed high purity arc melted alloys was the principal method of investigation and was supplemented by X-ray diffraction. TITANIUM-ALUMINUM alloys exhibit excellent properties, particularly for elevated temperature use. For this reason, the Materials Laboratory, Wright Air Development Center, sponsored an investigation of the effect of the interstitially soluble contaminants, oxygen! nitrogen, and carbon, on the Ti-A1 system. Using high purity arc melted alloys and micrographic analysis of annealed samples as the chief method of investigation, titanium-rich partial phase diagrams were determined for the ternary systems. Experimental Procedure Materials: The titanium used in the preparation of the alloys was iodide crystal bar (99.9+ pct pure) produced by the New Jersey Zinc Co. and Foote Mineral Co. The aluminum was obtained from the Aluminum Co. of America in the form of sheet. The given analysis was: Si, 0.0006 pct; Fe, 0.0005; Cu, 0.0022; Mg, 0.0003; Ca, <0.0006; Na, <0.0005; and Al, 99.99. High purity titanium dioxide purchased from the National Lead Co. was used in the preparation of the oxygen-bearing alloys. The spectrographic analysis of this material was as follows: SiO,, 0.07 pct; Fe,O,,, 0.002; A1,0,, <0.001; Sb,O,, <0.002; SnO,,, <0.001; Mg, <::0.001; Cb, <0.01; Cu, 0.0004; Pb, 0.002; Mn, <0.00005; W, <0.01; V, <0.002; Cr, <0.002; Ni, <0.001; and Mo, <0.002. Special spectroscopic graphite rod purchased from the National Carbon Co. was used in the preparation of the Ti-A1-C alloys. Alloy Preparation: Alloy ingots weighing 10 grams were melted in a nonconsumable tungsten electrode arc melting furnace using water-cooled copper hearths and a helium atmosphere. The arc was struck on a tungsten stud in the copper block to minimize contamination from the electrode. Details of the techniques have been reported.&apos;, &apos; Each ingot was inverted and remelted a minimum of four times to insure homogeneity, without opening the furnace. Remelting small control ingots of iodide titanium under similar conditions resulted in no measurable hardness increase, indicating contamination-free melting conditions were used. The alloy charges and resultant ingots were weighed to the nearest milligram. Only small weight losses were obtained upon melting, indicating that the actual compositions were very close to the nominal compositions. Check analyses substantiated this. Oxygen and nitrogen were added during ingot preparation as master alloys. An oxygen master alloy containing 25 wt pct 0 was prepared by melting iodide titanium and pressed titanium dioxide (40 pct 0) powder. The Ti-25 pct 0 alloy is more easily handled during weighing and charging than the pressed TiO, powder. Chemical analysis indicated that titanium-nitride received from an outside source contained large amounts of impurities (2.7 pct Ca). Therefore, a master alloy containing approximately 12 pct N was prepared by melting nitrided sponge titanium. As the sponge melted with difficulty, the alloy was diluted by addition of titanium to lower the melting point. The chemical analysis of the final alloy was 6.69 pct N. Both master alloys are friable and were used as —8 +16 mesh lumps resulting from crushing the ingots. NIelting the Ti-A1-0 and Ti-A1-N compositions five times produced homogeneous ingots. The preparation of homogeneous carbon-bearing alloys caused considerable difficulty. Alloys containing less than 1 pct C were prepared using spectrographic graphite rod, 1/8 in. diameter by 1/8 in. long. However, the graphite did not dissolve even with long melting times and many remelts. The ?/s in. pieces of graphite were used rather than powder because the low density powder is troublesome in arc melting.

Jan 1, 1955

By A. S. Michaels, M. C. Porter, A. Stancell

Previous laboratory studies have demonstrated that the injection of small quantities of reverse wetting agents during water displacement can increase oil recovery from unconsolidated porous media.9 In the present investigation, an attempt has been made to determine more fully the effects of reverse wetting treatments and to clarify the mechanism by which increased oil recovery is effected. Water-oil displacements were performed in beds of 140-200 mesh silica sand. Hexylamine slugs (injected after 0.25 pore volume of water throughput), when adequate in size and concentration, were effective in promoting additional oil recovery. Their effectiveness increased with the quantity of amine injected. However, slugs of sufficient size and concentration to stimulate oil production at water flow rates of 34 ft/day did not do so at 4 ft/day. Visual studies in a glass grid micromodel have shown that the stimulation of oil production, via ayueous hexylamine, is a result of transient changes in the oil wettability of the pore walls. if the amine slug is of sufficient size and concentration to induce significant changes in the adhesion-tension, large continuous oil masses will be formed. if the superficial water velocity is high enough to result in rapid desorption of the amine, a favorable "wettobility gradient" may be established across the masses; under such conditions, high oil mobility is observed, and increased oil recovery results. INTRODUCTION It is generally agreed that the efficiency of oil displacement by water in porous media is limited in part by capillary forces which cause the retention of isolated masses of oil — resulting in the so-called "irreducible minimum oil saturation". Recent estimates10 indicate that there are about 220 billion bbl of petroleum in United States reservoirs which are not economically recoverable with present techniques (such as water flooding). This amounts to almost five times the known recoverable reserves. It has been recognized for some time that a suitable alteration in the water-oil interfacial tension and/or the contact angle, as measured between the water-oil interface and the solid surface, should result in better displacement efficiency. Surface active agents can be used as interfacial tension depressants to accomplish this objective,1,2,7 but unfortunately, the additional oil recovery is seldom commensurate with the treatment cost. In contrast to interfacial tension depressants, the effect of contact angle alterations on water-oil displacements has received relatively little attention in the literature. It is known that the wettability affects the displacement process.3,4,11 Displacements in water-wet systems generally result in lower residual oil saturations than those in oil-wet systems. The effect of "&apos;transient" wettability alterations concurrent with the displacement process have been investigated by Wagner, Leach and coworkers,4,11 wherein it has been demonstrated that the establishment of water-wet conditions during water flooding of oil-wet, oil-saturated porous media is accompanied by significant increase in oil displacement efficiency. Michaels and Timminss studied the effects of transient contact angle alterations resulting from chromatographic transport of reverse wetting agents through unconsolidated sand. It was demonstrated that chromatographic transport of short-chain (C4 through C8) primary aliphatic amines can improve oil recovery and that the recovery increases with the quantity of amine injected (i.e., with either the amine concentration or the volume of the slug injected). Circumstantial evidence indicated that the increased displacement efficiency resulted primarily from transient changes in wettability of the porous medium. In the Present investigation. additional information has been obtained on the effects of reverse wetting treatments and the mechanism by which increased oil recovery is accomplished. Hexylamine slugs of varying size and concentration were chromato-

Jan 1, 1965

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper .to, discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in. brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: 1-gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2-liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3-glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4-crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that carried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant, contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.1 At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1-aqueous solution, a much more expansible liquid, and a gas; 2-aqueous solution, salt crystals, and a gas; and 3-the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20° and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.2-6 Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid. carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.7,8 Hartley (1876, 1877),9,10 Hawes (1881),11 Wright (1881),12 Johnsen (1920),13 and Holden (1925)14

Jan 1, 1952

By J. A. Stachura

Continuous mining machinery provides the coal industry with one way to compete for a larger share of the total energy market. Various types of machines are discussed and some of the problems with continuous miners, encountered by operators, are reviewed. Equipment manufacturers are working with mine personnel to provide solutions for problems that arise. While coal production over the past 25 or 30 years has been on a horizontal plane, coal&apos;s share of the total energy market has declined. To participate more effectively in this total energy market, it is necessary to produce coal more efficiently. It is the obligation of all management, employes, and mining departments to gear the deep mining industry to the rapid progress and changing of today&apos;s modern industry. This can be accomplished in the near future with the selection of the proper type of continuous miner best suited to each operator&apos;s individual situation. In most mining operations there is tremendous incentive to undertake the continuous mining program. It can reduce the size of the mine greatly by permitting a minimum of working places; it makes pillar recovery work more efficient from the standpoint of overall cost, amount of coal recovered, and safety. The work force can be reduced materially permitting closer and more efficient supervision. It simplifies maintenance because equipment can be more readily standardized. The trend of the coal market favors the use of continuous mining machines. Although there appears to be a general feeling that continuous mining is still a relatively new program and will be slow in replacing conventional mechanical equipment, the fact is that tremendous strides have been made since the first machines were installed in 1948. This program is advancing at approximately the same rate that mobile loading machines replaced hand loading. From 1948 to 1955 there were approximately 450 continuous mining machines in service. In October 1959, a survey revealed that there were more than 700 continuous mining machines in service. Many operators have expressed a desire to undertake this program, but they feel that they could not do so at this time because of one or more of the following reasons: 1) the thickness of their coal seams, 2) seam characteristics, 3) soft bottoms, 4) bad roof conditions, 5) size consist, 6) insufficient flexibility in machines, 7) difficult ventilation problems, and 8) high maintenance costs. With the realization on coal about the same today as it was in 1948, or slightly less and since coal is still failing to participate to a greater degree in the total energy market, it is not surprising that the coal industry is desperately exploring more economical methods for deep mining. The manufacturers are aware that the coal industry is willing to invest in continuous miners if the equipment is built for maximum flexibility, will produce higher tons per man, and assure long life between overhaul programs. CONTINUOUS MINING MACHINES Before discussing details regarding the selection of a continuous miner, let us have a preview of some of the continuous mining machines which are available to the coal industry today. Jeffrey Manufacturing Co.: The machine shown is the Jeffrey 76 A.M. Colmol. This is their most widely used miner, and has been particularly successful in central Pennsylvania and in high-wall mining in western Kentucky. One of the outstanding features of this auger-type miner is its portability. The entire mining range can be changed from its lowest point to the maximum height without stopping the mining operation. Jeffrey 76 B.M. Colmol: This machine is similar to the 76 A.M. model; however, it is built bigger and stronger for a mining range of 50 1/2 to 72 in. This is the model that is now available (Fig. 2). Jeffrey has added two arms to the top row, omitted the odd arm in the bottom row, thus permitting a 50 pct larger throat opening. This eliminates one

Jan 1, 1961

By Richards R. Vandervoot

T HE creep behavior of many polycrystalline metals at moderate stresses can be described by the empirical relationship: where Em is the minimum creep rate, A is a constant, a is the applied stress, E is the average elastic modulus at the test temperature, and D is the self-diffusion coefficient.&apos; This equation is generally applicable for strain rates of less than around 10-5 per sec and temperatures greater than about one-half the melting point in absolute units. Under these conditions atomic mobility plays an important role in the deformation process, and steady-state creep occurs when a dynamic equilibrium is reached between the generation and recovery of dislocation substructure. Although several theoretical mechanisms have been proposed to explain the creep of polycrystalline solids,2"4 the dislocation climb model2 is in accord with most experimental observations. The majority of creep data used to develop Eq. [1] came from metals with either the fcc or hcp crystal structures. However, on the basis of results for a and 7 iron as well as those for a and a thallium, Sherby concluded that the high-temperature deformation behavior of close-packed metals and bcc metals is probably the same.&apos; The greater creep resistance of fcc and hcp metals and alloys on a relative temperature scale was attributed to lower diffusivities in the close-packed structures. To further compare the creep properties of fcc, hcp, and bcc metals, creep data for all six bcc refractory metals were analyzed according to Eq. [I]. The results are shown in Fig. 1. The sources of information for the quantities used to prepare this figure are listed in Table I, except for high-temperature elastic moduli. The latter data were obtained from Refs. 28 and 29. The dashed lines in the figure represent the range and breadth of data analyzed by Sherby for fcc and hcp metals. In general, the deformation behavior of all of the refractory metals, ex- cept possibly that of tungsten, can be represented by Eq. [1]. This correlation is strong evidence of the similarity that exists between creep of pure close-packed metals and creep of pure bcc metals. At (Em/D) < 108, the results of Flagella and Tarr on tungsten (W-1 in Fig. 1) agree with the five-power stress law, while those of Green (W-5 in Fig. 1) show a seven-power stress dependence. Where (Em/D) > 108, the stress exponents for other data on tungsten were in the range 10 to 15. It is possible that the creep rate dependence on stress in this region is not a power law but exponential (i.e., Em - eßo). However, it was not feasible to differentiate between these two cases because of the steep slope and scatter in the data. Note the inflection point in the curve for the data of Flagella and Tarr (W-1 in Fig. 1). The slope of the line changes from 5 to around 10 at Em/D = 108. The breakdown of the fifty-power stress law at high stresses is not uncommon in other metals, and this phenomenon may result from nonequilibrium conditions in the material such as excess lattice vacancies produced by rapid straining.30 The mechanical strength of a polycrystalline metal is related to its microstructure. Attempts to establish the influence of grain size on the creep rate of metals and alloys have led to a wide variety of results. For example, the following effects have been observed: creep rate decreases as grain size increases;31&apos;32 creep rate decreases as grain size decreases;&apos;,33 creep rate is a minimum at some critical grain size and increases with either an increase or decrease in

Jan 1, 1969

By G. Derge, R. E. Grace

Diffusivity of bismuth in liquid Pb-Bi alloys has been measured by the capillary reservoir method as a function of temperature and composition. Fair agreement between theory and experiment is found for the measured diffusion coefficients and activation energies of diffusivity and viscosity in dilute lead alloys. The measured diffusion coefficients in the high bismuth alloys describe mass transport in special concentration gradients. THE study of diffusion in liquid metals has been restricted largely to the amalgams over small ranges of temperature and composition. In contrast to this, diffusion and transport of ions and molecules in aqueous and organic solvents have been studied extensively for the past 50 years. The general difficulty of measuring diffusion coefficients in both gases and liquids at high temperatures has been that of eliminating convection currents. Measuring techniques based on freezing and sectioning after the diffusion period1 are not particularly satisfactory because of the volume changes and segregation which occur during freezing. The most promising technique which is currently being developed for liquid metals is the capillary reservoir method. This eliminates convection currents from the diffusion zone and requires measurements only of the length and initial and final compositions of the alloy within the capillary. Anderson and Saddington&apos; have measured the diffusion coefficient of tungstate anions in aqueous Na,W04; Wane4&apos; and Hoffman- ave studied structure and self-diffusion in water and self-diffusion in mercury, respectively, by similar techniques. Selection of the Pb-Bi system for initial study was made for several reasons: I—It afforded a low temperature system for development of techniques which would be suitable for high temperature measurements in liquid iron. This research on diffusion in liquid iron is now in progress as a part of a general program on the rates and mechanisms of slag-metal reactions. 2—Activity data on liquid Pb-Bi alloys of all compositions are available from the emf meas- urements of Strickler and Seltz.9 3—Some data are available on the diffusion of bismuth into solid lead. The measurements on solid alloys were made by von Hevesy and Seith7 for the concentration range of 0 to 2 pct Bi. An appropriate solution to Fick&apos;s law (unsteady state) for the capillary reservoir has been found by considering the mass flow which passes through a unit area of surface on a slab of infinite thickness as a function of time. This is the first application of this solution to diffusion measurements, although a similar solution is available for identical boundary conditions.&apos; By analogy with heat conduction, the problem reduces to a perfectly insulated infinite slab at temperature C,, one surface of which is quenched to C, for all times, t. Heat is permitted to flow from quenched surface of the slab to an infinite supply of coolant at C.&apos; (see Appendix). For the corresponding solution for diffusion in liquids, these terms become Where Cu is the initial concentration of component A" in entire capillary at t - 0, C, is the final con- In this case. component A is bismuth, and C, = 0. centration of component A in entire capillary at t = t, C, is the concentration of component A in bath for all t, 1 is the length of the capillary in centimeters, t is the time of diffusion period in seconds, and D is the diffusion coefficient in square centimeters per second. By comparison with solutions to Fick&apos;s law used in the solid state, this solution for liquids is similar to the Grube solution for solids, where the change in D with chemical composition is not taken into consideration. Difficulty is to be expected if large concentration gradients are employed and if the concentration gradients extend over an appreciable length of the capillary.

Jan 1, 1956

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami&apos;s reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."&apos; A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. &apos; J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff&apos; have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953