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By H. Herman, M. E. Fine

Kinetics of reversion and reformation of GP I were studied resistometrically in Al-1.7 at. pct Cu. The reversion process is over in roughly 1/2 minute at 205 "C irrespective of the amount of primary aging. After reversion the occurrence of an incubation time before reaging begins has been substantiated. The reaging kinetics is drastically accelerated by plastic deformation to the specimen. An incubation time is observed only if the specimen is aged before reversion. The incubation time and the effect of plastic deformation indicate that nucleation of GP I is heterogeneous. Simple clusters of copper atoms apparently do not act as nuclei for GP I. AFTER quenching aluminum-rich copper from the solid solution range, Guinier-Preston zones of the first kind, GP I, form very rapidly at room temperature. The rate, largely controlled by the concentration of vacancies, is initially most rapid1 (that is, at the time of the first measurement: 1/2 min) and decreases with time. The nucleation is thought to be athermal. If after aging for several days the GP I is dissolved by reversion at 205°C, according to measurement of Young's modulus an incubation period is observed before GP I begins to form on subsequent aging.2 Yet if the reversion is carried out immediately after quenching, both resistivity3 and modulus changes2 show no incubation effect. The zones which form after reversion have the same structure as those which form after the quench.4 Because of entropy considerations and also the short diffusion time, the solid solution after reversion, 2 min at 205°C, is probably more highly clustered than at the original solution treating temperature, 520" to 550°C. It appears most reasonable to associate with nucleation the incubation time observed on reaging after reversion. A simple cluster of copper atoms, many of which are presumed to be present after reversion, is then not a sufficient nucleus for GP I; a GP I nucleus must contain something in addition to a cluster of copper atoms. The purpose of the present note is to give some additional experimental information concerning the incubation time and rates of reaging after reversion. The existence of the incubation time has been verified by measurement of another property, the electrical resistivity. Acceleration of reaging after reversion by plastic deformation has also been investigated. In acl.dition, the kinetics of the reversion process itself was studied. EXPERIMENTAL Electrical resistance was measured by the poten-tiometric four probe method. The 1.7 at. pct Cu alloy was furnished by the Aluminum Co. of America in the form of 1/2 in. rod. The major impurities reported by Alcoa were Fe (0.002 wt pct), Si (0.003 wt pct), and Mg (0.001 wt pct). Specimens for measuremenl of resistance were prepared by rolling to 0.010 in., cutting 2 by 0.2 in. pieces, rolling the middle pclrtions of these to 0.005 in., and splitting the 0.010 in. sections up to the reduced central section to form current and potential leads. Aluminum extension wires insulated with ceramic tubes were spot welded to the leads. The specimen was supported by the lead wires. The whole specimen assembly was annealed at 500" C in an air furnace for more than 12 hr and then aged at room temperature. This was done to assure quick and complete resolution during subsequent solution treatments. These were carried out in Houghton's "430 Temper Salt" at 520'C for 1 hr. Unless otherwise specified, quenching was accomplished by quickly transferring the specimen from a salt pot to 25°C water. Aging was carried out in a 3 liter dewar of distilled water, rotated and stirred. The temperature was controlled to +0.01°C with a thermomercurial regulator in conjunction with a transistorized relay

Jan 1, 1962

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By C. E. Birchenall, G. Derge

IN studying the kinetics of slag-metal reactions, it has become increasingly apparent that a complete knowledge of all aspects of interface phenomena will be required to clarify these processes adequately. A part of the data required for all oxidizing slags used in the refining of impure iron to steel is the rate of exchange of iron between the slag and metal phases. The simplest equilibrium of this type is that between liquid iron and iron silicate slag when both phases are equilibrated with the silica crucible containing them. In this study, the exchange of iron between the two liquid phases has been measured by using radioactive Fe as tracer. The observed high exchange rate indicates the ease with which such interfaces may be crossed in refining processes. The experiments required for this study involved relatively minor and normal modifications of well established techniques. Melting was accomplished by induction heating in heavy walled, fused silica, rotating crucibles." Rotation was used to minimize dilution of the slag by crucible erosion. The melting stock was ingot iron. Slags were prefused in iron crucibles using chemically pure grade oxide reagents. The special conditions applying to the active iron additions will be described for individual experiments. Suitable precautions were observed with regard to protection against radiation hazards.' Identification of Activity This particular study was initiated several years ago, but held in abeyance because the radioactive iron available at that time contained a foreign activity which concentrated in the slag so as to mask the iron activity and render the results unin-terpretable. With the benefit of experiences from other studies, radioiron of suitable purity can now be prepared. As received from the Isotope Div. of A.E.C., the unit appears to contain Fe + Fe50 and a high activity cobalt. The cobalt and iron are separated by repeated ether extractions, and the purified iron stored for sufficient time for the Fe'7 44 day half-life) to decay to negligible activity, leaving only Fe as the active isotope. This was confirmed by the absorption curves for slag and metal samples from heat No. 1. In Fig. 1 the experimentally measured points for the absorption curves of slag and metal are fitted by the calculated slope of 5.8 mg per sq cm in aluminum, which corresponds to the Mn K doublet emission resulting from the capture of an orbital electron of Fe" by the nucleus. This shows that the radioactive species are the same in both slag and metal and identifies it as Fe55 Description of Individual Heats For the first heat, the radioactive iron was contained in the prefused slag. The active Fe55 had been precipitated with carrier and was added as Fe2O3 during fusion in the iron crucible. The charge of 500 grams of ingot iron was melted, the protective iron sleeve added, rotation started, and a prefused, inactive slag was added to allow the system to approach equilibrium. After about 5 min at temperature, the wash slag was skimmed and the active slag added. Initial slag and metal samples were taken as soon as the slag was molten. Additional samples were taken at indicated intervals thereafter. Slag samples were dipped with a small iron spoon and metal samples were sucked into 1/4 in. ID silica tubes. The slag and metal samples were pulverized and mounted for radioactive counting. The slag samples were analyzed chemically for FeO. Temperature was read after the last slag sample by immersion of a Pt-Pt-Rh thermocouple protected by a fused silica sheath. Since no significant variation of rate with temperature was observed

Jan 1, 1954

By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick's second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method' are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5' could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5' or Ag'lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5' and 0.6 N HNO3 solution for the A"'), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5' atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969

By Leonard B. Lipson

Boyer, Morgan and Muskat,' with improvements by Morgan, McDowell, and Doty,l and Laird and Putnam,' have described a scheme for the determination of fluid saturatic in porous media by measuring the x-ray linear absorbing power of particular fluids in the media. This method is one of several which depend on the linear absorbing power of the fluids in the porous medium. Other examples of linear absorption methods involve measurement of dielectric constant, gamma ray absorption, and ultrasonic attenuation. It is the purpose of this note to demonstrate by theortical considerations that the absorption versus saturation curve for a linear absorption method is not necessarily a single valued function of the saturation. Such non-unique behavior must be considered and evaluated before suitable saturation determinations can be made by a linear absorption method. To illustrate the discussion, examples will be given only for the simplest cases of combinations of two different dielectrics. The dielectric constant method was chosen for illustration because it was thought to demonstrate most graphically the point in question. According to Argue and Maass,4 the resultant dielectric constant of a combination of two different dielectrics depends on the orientation of the dielectrics in the electric field of the test condenser used to measure the dielectric constant. One ease involves alternate slabs of dielectrics E1 and E2 perpendicular to the electric field of the test condenser, as shown in Fig. 1A. For this case: l/'E, = A/E, + B/E,.......(1) where E,,, is the dielectric constant of the combination, A is the ratio of the path length through dielectric E, to the distance between the plates of the condenser (assuming the dielectrics have the same cross sectional area as the condenser), and B is the ratio of the path length through dielectric E2 to the distance between the plates of the condenser. It will be noted that the constants A and B are numerically equal to the fractional "saturation" of the region between the test plates of the condenser by the two dielectrics E1 and E2, respectively. Another case involves alternate columns of the two dielectrics parallel to the electric field and forming a continuous path between the condenser plates, as shown in Fig. 1B. For this case: E., = AE1 + BE2.........(2) where E., is the dielectric constant of the combination, A is the ratio of the cross sectional area of dielectric E, to the cross sectional area of the condenser plates (assuming the lengths of the dielectrics equal the distance between the condenser plates) and B is the ratio of the cross sectional area of dielectric E2 to the cross sectional area of the condenser plates. As before the constants A and B are the effective "saturation" of the condenser by the two dielectrics. Still another case is described by Lichtenecker5 where dielectric E2 is shown in the form of small particles distributed at random in dielectric E1. This is shown in Fig. 1C. For this case: log Em = A log E1 + B log E2.....(3) where Em is the dielectric constant of the combination. A is the ratio of the volume of dielectric E1 to the volume of the condenser, i.e., the effective "saturation" of the condenser by dielectric E,. B is the ratio of the volume of dielectric E2 to the volume of the condenser, i.e., "saturation" of dielectric El. Equations (l), (2) and (3) are plotted in Fig. 2 for E1 = 2.5 (oil) and E2 = 80 (water). Equations (1) and (2) may he thought of as representing the limiting cases of the configuration of two fluids which might be expected to exist in a porous medium. Equation (3),

Jan 1, 1951

By Nicholas J. Grant, Rolf Nordheim, Thomas B. King

Constant-load creep-rupture tests were conducted in an argon atmosphere at temperatures of 1600 to 2200°F on two heats of iron containing about 0.06 and 0.09 pct P in solid solution. The tests were conducted in the as-cast condition. Stresses were selected to give strain rates approaching those encountered in the hot working of steel, and within the limits of the creep-rupture test apparatus, namely. from about 0.001 to 50 pct per sec. FOR generations, rolling and forging practices have been developed largely by empirical methods, based on prior experience. While largely successful, difficulties are frequently encountered when new or different alloy compositions are tried for the first time. There is need to know the relationships which exist among temperature, strain rate, composition, and other variables on the deformation and fracture characteristics of steels. It has been shown for aluminum and several high-temperature alloys that the deformation and fracture characteristics follow rather well-defined laws and patterns which are closely related to the effects of strain rate, temperature, and composition.1"3 As the melting temperature of aluminum or its alloys was approached, it was possible to study the interplay of work-hardening factors and recovery or recrystal-lization, the latter resulting in improved ductility and increased resistance to intercrystalline fracture. In particular, the effects of composition are very poorly known. Within the meaning of "composition" should be included impurity elements, such as sulfur, phosphorous, lead, copper, and many others, as well as those elements which are added for alloying purposes in iron. The role of multiphase structures, in contrast to solid solutions, should also be studied in much greater detail. high strain rate creep-rupture tests would provide information regarding the deformation and fracture characteristics of metals at hot-working temperatures. It was also desired to establish the stresses which are necessary to accomplish the desired deformation, and to relate these to the strain rate and temperature. Secondly, it was the purpose of this particular study to determine the effects of phosphorus, within solid solution limits, on the deformation and fracture characteristics of iron at hot-working temperatures. EXPERIMENTAL PROCEDURE Two phosphorus levels were selected, one corresponding to the upper limit normally found for commercial steels, and one substantially higher than this, but within the region of solid solubility at the test temperatures chosen for this investigation. Twenty-pound heats were prepared by induction melting electrolytic iron in air in a magnesia lined furnace. After deoxidation with about 0.2 pct Al, ferro-phosphorus was added, and the heats were then poured into prefired silica molds. The purpose of using silica molds was to obtain a slow cooling rate during solidification to produce a relatively coarse grain size, producing a structure subject to some segregation and therefore more nearly characteristic of ingot structures. The major part of the casting assembly provided a large shrinkage head in order to produce sound castings and to promote slow cooling of the specimens. The primary austenitic grain size varied from ASTM No. 2 to No. 00. The composition of the heats, including a low phorphorus melt, used for comparison purposes, is shown in Table I. It will be noted that the oxygen content of the phosphorus containing heats is relatively high, in spite of the deoxidation practice, a condition which is difficult to control in small melts. Creep-rupture tests were nevertheless undertaken when it was noted that this quantity of oxygen did not appear to give results any different from those from a heat containing 0.01 pct 0, low phosphorus and comparable carbon Content;4 see Table 11.

Jan 1, 1961

By T. A. Read, M. W. Burkart

The crystal geometry of the cubic-tetragonal interface after partial transformation of an indium-thallium alloy single crystal is described and a general theory is presented. The effects of applied stresses on this transformation are interpreted and the latent heat of transformation is obtained from observations of transformation under stress. A DIFFUSIONLESS phase transformation between face-centered cubic and face-centered tetragonal structures has been reported for the indium-thallium system by Bowles, Barrett, and Guttman1, 2 The transformation takes place at approximately 105 "C at 18 atomic pct Tl and 25°C at 23 pct Tl. In their study, Bowles, Barrett, and Guttman used poly-crystalline samples whereas in the present study single crystals were used to eliminate the transformation constraints imposed by adjoining grains. The use of single crystals made possible a comprehensive study of the effect of stress on the transformation. In the course of the work, it was possible to formulate a new method of analyzing dif-fusionless transformations (presented in this paper) which permits calculation of the geometry of the interphase interface from a knowledge of the crystal structures of the initial and final phases. The specimens were prepared from chemically pure thallium and 99.97 pct In which were weighed out to produce 3 to 4 grams of alloy of the desired concentration. The metal was placed in clean fused silica tubing, then melted, degassed and sealed under vacuum. (To obtain single crystals, it was found that both degassing and extreme cleanliness were essential.) Single-crystal specimens were grown by a modified Bridgman technique.8 pecimens were removed from the tube by dissolving the quartz in concentrated hydrofluoric acid which attacks the specimen very slowly. The specimen then was polished mechanically to produce four flat surfaces, electropolished, and annealed at 140°C for 48 hr. The electropolishing solution used was that described by Bowles, Barrett, and Guttman and the polishing was carried out on both the high and low temperature phases of the alloy. The high temperature polishing was done at 110°C with a stainless steel cathode. Visual Observation of the Transformation in Single Crystals A visual study of the transformation was made on specimens which had been electropolished in the high temperature phase. The specimens were supported on the stage of a metallograph by an electrically heated holder which contained an opening for observing the specimen. Visual evidence of transformation was found in the presence of an interface which separated the two phases. The interface plane defines the boundary of the phase undergoing transformation and manifests itself by the sharp change in angle between the surface of the specimen and the incident light at the juncture of the two phases. On slow cooling, well-annealed specimens transformed from the face-centered cubic structure to the face-centered tetragonal structure by the motion of a single plane interface which traversed the specimen from one end to the other. Upon heating, the interface moved back in the reverse direction. The interface could be started, stopped, or reversed at will. A temperature hysteresis of about 31/2oC was observed in the reversal of the interface. Holding an interface stationary caused it to disappear completely in most cases, whereas in other instances the interface became less distinct depending upon its orientation. The interface could be made to reappear by changing the temperature of the specimen. The low temperature tetragonal structure exhibits only the fine markings or subbands reported by Bowles, Barrett, and Guttman and is illustrated in Fig. 1. These subbands are twin-related. Back-reflection Laue patterns show the breakup of the cubic spots into pairs of spots corresponding to the twin orientations of the tetragonal phase.

Jan 1, 1954

By Peter M. Fozzard

The San Bartolomt silver deposit was discovered by a United Nations team of geologists working with a counter- part team of staff of the Ecuadorian Government's General Directorate of Geology and Mines (DGGM). The Phase I project over five areas of operation during which this discovery was made was financed through a United Nations Development Program contribution of $860,000 and an Ecuadorian Government participation of about $680,000 equivalent. Existence of mineralization at San Bartolomé was first recognized in 1966 when a reconnaissance geochemical stream-sediment program was carried out over a 10 500 km2 (4,054 sq mile) area centered around the city of Cuenca in southern Ecuador. Over the course of this project more than 10,000 samples of stream-sediment, soil, and rock materials were collected. Average costs per sample were $10.00, as follows: collection, $5; sample preparation, $1.60; assay work, $3.40. Initially in the program (1965-1966) sediments were collected along all motorable roads and tracks. Routine analyses, originally by colorimetry and later by AAS, were for Cu, Pb, Zn and occasionally As, Ni, and Co. Discovery geochemical samples from the San Bartolomé drainage area were among the first to be taken in 1965. As luck would have it, the road along which this traverse was taken passes only some 100 m (328 ft) downstream from the mineralized suboutcrop. The relevant two streams sampled are of inconsequential size, some 1 m (3.3 ft) in width, with a limited flow volume throughout the year. Original anomalies were recognized through cold-extractable Cu/Zn analyses. The pH of all river waters was also recorded at sample sites. Resampling the discovery sediments when AAS became available showed total extractable values of between 150 ppm-300 ppm Zn, 550 ppm Pb, and 10 ppm Ag. In 1967 the first followup was by rough-and-ready means. Dithizone field-kits (THM) were used to rapidly test soils from the surrounding area. The area has no outcrop. This work allowed the definition of an area of interest of some 2 km (1.2 miles) x 500 m (1640 ft). Six approximately 1 km (0.6 mile) to 1.5 km (0.9 miles) lines spaced at approximate 250 m (820 ft) intervals were established and used for IP surveys and soil sampling at 50 m (164 ft) intervals. Where one of the lines crossed the westernmost geochemical discovery creek a first-priority geophysical anomaly coincided with a major Zn/Pb (and later Ag) soil anomaly. A pit was sunk and encountered mineralized vein material at a depth of 1.5 m (5 ft). This lucky glory hole confirmed the geochemical discovery and prompted systematic followup. Immediately, costeaning of the west bank of the discovery creek, the Quebrada Ocashuaico, was carried out and exposed weathered and leached mineralization. Nearly 100 mineralized veinlets ranging in thickness from 0.5 cm (0.2 in.) to 8 cm (3 in.) were exposed across the 180 m (59 1 ft) costean. Sixty mineralized veinlets were determined over a 90 m (295 ft) wide zone. Sampling delineated minable widths averaging between 0.16 and 0.31 kg/t (5 and 10 oz per st) Ag with associated copper (very sporadic) lead and zinc. Over the period 1968- 1972 a considerable amount of detailed work was completed: detailed IP, EM Turam, magnetic and mise-a-la-masse geophysics, very detailed soil- sampling, trenching, drilling and glory-hole drifting, and cross-cutting. Numerous problems were encountered: the area was found to be a most difficult geoelectrical target; zero outcrop; pyrite (nonargentiferous zones) associated with faulting; mineralized groundwater; extensive clay development; loss of diamond drill-core, and no two-dimensional surface information. As the program developed the complexity of the structure was slowly unravelled, using a degree of good guesswork. Apart from photogeological and ground geological mapping at various scales, the following

Jan 1, 1985

By David Cornell

Back pressure test data on natural gas wells are short time test data of unsteady state nature. Performance curves from which unsteady state effects have been eliminated, called stabilized performance curves, are necessary for understanding the behavior of gas wells and for scheduling gas fields for periods up to 20 years. A calculation procedure has been developed whereby three day, seven day, 30 day, or other duration stabilized performance curves may be calculated from back pressure test data. Such curves are essential for correct gas deliverability calculations and gas field scheduling. I NTRODUCTION The manner in which a back pressure test is made will affect the slope of the back pressure curve because the radius of drainage changes with the length of time that the well is allowed to flow. The reciprocal of the slope of the back pressure curve is defined as n in Equation 1 and varies from 0.5 to 1.0. If the flow is viscous and the radius of drainage constant, n will have a value of 1.0. Because of turbulence in the formation near the wellbore, the pressure drop is usually greater than the viscous flow pressure drop and the exponent n is frequently less than 1.0. In addition, since the radius of drainage moves away from the well-bore during the test, the gas flows a greater and greater distance as the test proceeds, with a resulting increased pressure drop at the high flow rates, and, again, n for the test tends to be less than 1.O. The effect of the changes in the radius of drainage may be calculated and the results used in preparing stabilized performance curves for fixed values of the radius of drainage. Such curves can be made for a defi- nite time period, such as three day, seven day, or 30 day stabilized performance curves. These cukes will show the effect of turbulence near the wellbore and can be used to predict the performance of the gas well at any flow rate or for any production period. In order to discuss the importance of the radius of drainage quantitatively, it should be defined. Muskat" defines the radius of drainage as follows: "... the radius of drainage gives the distance from the well to which the approximately steady state condition has been established ... it being assumed that no gas is removed from any point until the radius of drainage has passed that uoint." An eauivalent definition of the radius of drainage is that radius at which the extrapolated portion of the steady state portion of the pressure gradient gives a pressure equal to the shut-in reservoir pressure. This definition is also implied in the back pressure equation. The radius of drainage is, then, the distance into the reservoir from which the gas appears to originate at any time. It is, however, only a useful concept and does not actually exist. Fig. 1 illustrates the definition of the radius of drainage. At the end of each flow period the radius of drainage may depend on three factors: (1) the duration of each flow period; (2) the rate of gas production; and (3) the rate and duration of the previous flow periods. In general, back pressure tests are conducted with various lengths of production time and at various flow rates. Each individual back pressure test, therefore, requires an individual analysis. The calculations of the change in the radius of drainage have been made, however, for the case of equal flow periods for all four production rates and several sets of increasing flow rates. Fig. 2 illustrates the results of such calculations made by the method of Cornell and Katz2 for the case of 8, = 50,000 and the flow rate increasing in the ratio 1.0:2.0:3.0:4.0 for each flow period. The increase in the radius of drainage during the test is apparent.

Jan 1, 1956

By Heribert Wiedemeier, Ali Khan

The tetnperature-conposition phase diagram of the syste,n MnS-CdS has been investigated over a range fro)n 600° to 1000° C. The small degree of solid solution on the MnS rich slde cornpared to the large CdS rich single-plzase region could be esplained by the difference in strzrctures of the cotnponents and the relative sizes of the metal ions. The change in lattice parameter as a function of cot)zposition is linear atzd jollous Vegavd's rule within experittzental limits of error. Mns and CdS have gained considerable attention in recent years because of their interesting solid state properties. In order to investigate such properties and thermodynamic quantities of mixed compositions of transition metal chalcogenides, it is necessary to establish their phase diagrams. Two earlier publications are concerned with the MnS-CdS system. Schnaase' found complete miscibility when MnS and CdS were co-precipitated in aqueous solutions at room temperature. However, there is evidence that the mixed crystals were not stable over the entire range of composition. roger's' investigation of the ternary system ZnS-CdS-MnS at 900" C indicates a solution of 48 mole pct MnS in CdS. During the course of this work which covers a temperature range from 600" to 100O° C, emphasis has been placed on the use of high-purity materials and well-defined modifications of starting products. EXPERIMENTAL Starting Materials. The stable green modification of MnS with NaCl structure was prepared by direct fusion of the elements and by chemical transport reaction. Stoichiometric amounts of manganese of 99.99+ pct purity and of sulfur of 99.999 pct purity from Gallard-Schlesinger Corp. were sealed in an evacuated quartz tube at a pressure of 10"5 mm Hg and annealed for 48 to 60 hr at 800°C. The quartz tubes used throughout this work were outgassed under high vacuum at a temperature of 90OU to 1000° C for 12 to 18 hr. For the synthesis of MnS by chemical transport3 stoichiometric ratios of elemental manganese and sulfur and small amounts of iodine were sealed under vacuum in a quartz tube, which was placed in the temperature gradient, 900/800-C, of a two zone furnace. Single crystals of MnS in form of platelets and octahedra were deposited at the cooler end of the tube. The manganese content was determined by EDTA titratin. A typical result of several analyses was 63.05 pct Mn which agreed well with the computed value, 63.14 pct. Commercially available CdS of 99.9+ pct purity, a mixture of the cubic and hexagonal forms, was converted into the hexagonal high-temperature modification by annealing CdS under vacuum in quartz tubes at 700° C for about 36 hr. As a second method, cadmium sulfide was transported in a temperature gradient, 70O° /650" C, with in vacuo sublimed iodine from the hot to the cooler zone of the tube. Large sized crystals in form of hexagonal columns and some platelets were obtained. An average result of the cadmium analysis by EDTA titration4 was 77.93 pct in good agreement with the computed value, 77.81 pct. Only the NaCl modification of MnS and the wurtzite modification of CdS were used for the solid solutions. Preparation of Solid Solutions. Finely powdered MnS and CdS samples were thoroughly mixed in molar ratios and compressed into pellets of about 6 mm diam and 2 mm in height at a pressure of approximately 13,500 atm.

Jan 1, 1969

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By Irwin R. Higgins

CONTENTS A. Introduction B. System Description C. Uranium Pilot Plant Programs D. Summary INTRODUCTION The Chem-Seps Continuous Countercurrent Ion Exchange (CCIX) contactor was first conceived of in 1951 at the Oak Ridge National Laboratory. In the 27 years that have passed, there has been a steady stream of pilot plant process development studies on a variety of processes far too numerous to mention. These have been in the area of water and waste treatment, chemical processing, ore leach treatment, and many others. Many successful production systems have been installed and operated in a variety of applications. A few of these are described herein together with a description of the system and its operational characteristics. SYSTEM DESCRIPTION Chem-Seps Continuous Countercurrent Ion Exchange* is a single loop in which various sections are separated by valves to isolate the sections performing different functions simultaneously. (Refer to Figure 1). To explain the working of a typical unit, let us use a simple configuration used in water softening or demineralization. The resin is moved in small increments by the hydraulic ram action. All solution flows are countercurrent to the flow of resin. The contaminants are removed in the process cycle and the resin is moved in the pulse cycle. A controller in the effluent stream from the treatment section senses the proper limit permissible in the effluent. In the process cycle, the influent enters through a set of distributors, moves downward and leaves through a set of collectors. Simultaneously the regenerant enters through valve RE and leaves through valve WA. The rinse enters through valve RI and its duration is controlled by an interface controller. In the process cycle, valves B, C, and D are closed, isolating all the sections. The duration of the process cycle is 4-10 minutes depending on the contaminants to be removed and is controlled either by a timer if the contaminants are fixed, or a controller in the effluent stream, if the contaminants fluctuate at short intervals. Valve A is open and resin is dropped to the pulse section simultaneously with the removal of contaminants in the treatment section, regeneration of loaded resin in the strip section, and rinsing of regenerated resin in the rinse section. As the resin drops through the valve A, it is backwashed to remove the suspended solids or resin fines. Removal of these fine particles is important to avoid the unnecessary pressure drop in the bed and plugging of the distributors. At the end of process cycle, all flows going into the unit and out of unit are automatically shut off. The valve A closes and valves B, C, and D open in proper sequence. A slug of water enters through valve PU, a predetermined incremental volume of resin moves into the regeneration section, an equal volume of regenerated and rinsed resin enters the bottom of the treatment section, and an equal volume of the loaded resin leaves the top of the treatment section and goes into the resin reservoir section. (The resin movement is plug flow with the Reynold's number being in the laminar region of the curve, and no fluidization occurs during the pulse cycle.) The total time required for proper sequencing of valves and the movement of resin is 20-30 seconds. At the end of this period, the valves B, C, and D close and valve A opens. The solution valves open and normal steady state operation begins. All valves are interlocked and properly sequenced. The resin movement is precisely controlled by sonic devices. Special Features of Chem-Seps CIIX "Downflow"*: The raw feed in the treatment section moves downward and the resin moves upward in the treatment section. The "downflow" of feed overcomes the handicap encountered in "upflow" systems. The "upflow" of feed requires a certain minimum flux during process cycle to lift the bed and keep it

Jan 1, 1979

By A. G. Guy

In a special type of electrodiffusion experiment the entire specimen is at constant temperature. The vacancies are then created at one end of the specimen and flow to the other end where they are destroyed. The energy required to operate the corresponding sources and sinks results in a super saturation of vacancies at one end of the specimen and an under -saturation at the other end. This gradient in vacancy concentration produces a chemical-diffusion flux, J(D), of vacancies in addition to the flux, J(E), caused by the electric current. Using the experimental data of Ch. Herzig,5 it is shown that a super saturation of 1 pct can cause J(D) to be about 25 pct of J(E), and thus account for the anomalous behavior of short specimens. THERE are advantages in a phenomenological treatment as contrasted to an atomistic one. For example, there are many reactions involving the element copper that are quantitatively and usefully understood from a phenomenological viewpoint, even though electron theory is not yet able to predict whether copper should be fcc or cph.' Similarly, the lack of a complete atomic theory of vacancies need not prevent the development of a treatment based on thermodynamics and chemical kinetics. In the following discussion, models will be used for the vacancies and for the mechanisms by which they move or are created or destroyed, but the phenomenological treatments are not dependent on the details of these models. The important product of a phenomenological analysis is an equation that describes the relation among the measurable quantities determining the behavior of the system. Based on such an equation, experiments can be performed to study these quantities in detail. Eventually atomic theory will supply an adequate theoretical base for the phenomena in question. A chemical species whose chemical potential was invariant during reactions in binary and ternary systems of varying composition would indeed be an anomaly. Yet this is the role that has frequently been assigned to the vacancies in pure metals, in dilute solutions, and even in ordinary alloys. The weight of available evidence supports the view that supersatu-rations of vacancies are on the order of 1 pct in usual diffusion processes.' Although it may seem strange that such a small deviation from equilibrium could significantly affect the thermodynamic properties of the vacancies, it is well known that the driving force for an ordinary chemical reaction is the departure of the components from their equilibrium state. Similarly, the reaction of vacancies that results in the formation of pores in various types of diffusion3 can reasonably be attributed to the supersaturation of vacancies. In the present paper, it will be shown that small degrees of supersaturation can significantly affect the kinetics of the diffusion process itself. ISOTHERMAL ELECTRODIFFUSION Two different experimental techniques are convenient for studying the behavior of vacancies in a pure metal in the presence of an electric field. Gilder and Lazarus4 studied self-electrodiffusion in a gold specimen in which only the central portion was at high temperatures. In this case the significant vacancy sources operate inside the specimen in the presence of a temperature gradient. In the laboratory of Th. Heumann a method has been devised for studying self-electrodiffusion at constant temperature.5 In principle, there is then no effect of thermodiffusion. It will now be shown why in this case the significant ATungsten disks \^^ ^^ ^Gold disks^^ ^^"T>.... "TTZA ? Up Iy'7 markers ///// ////// initial plane p I y/y/y of joining \I 7//// V7//A_________I_________V//// -I 0 +I Distance from center of specimen (a) -— Direction of flow of electrons —Direction of flw of vacancies %yy} Matano I z~irkendall /%W, vy/A inlerfacej "interface ///// -} HfiK- +/ 0 Distance from center of specimen (6) Fig. 1—-Schematic illustration of the essential features of isothermal self-electrodiffusion. (a) Initial condition of specimen. (b) Condition of specimen after electrodiffusion.

Jan 1, 1970

By R. D. Pehlke, W. M. Small

The effect of added alloying elements on the solubility of nitrogen in a liquid alloy of 74 wt pct Fe. 18 wt pct Cr, and 8 wt pct Ni has been studied. At 1600°C and 1 atm nitrogen pressure, aluminum, chromium, columbium, manganese, molybdenum, tantalum, and vanadium increase the solubility of nitrogen in the liquid 18 Cr-8 Ni alloy, whereas additions of cobalt, copper, nickel, silicon, tin, and tungsten decrease the solubility. Interaction parameters based on a constant ratio of iron, chromium , and nickel have been used to quantitatively define the changes in nitrogen solubility. INVESTIGATIONS on the solubility of nitrogen in liquid iron have usually treated the pure metal, and often the influence of a single added element. Pehlke and Elliott1 carried out a comprehensive study on the influence of alloying elements on nitrogen solubility in liquid iron, and compared their results with previous studies. Turnock and pehlke2 have recently reported a study on the solubility of nitrogen in multicomponent liquid iron alloys. The original interaction parameter proposed by wagner3 was successfully employed in these studies. The need for obtaining information on the gas solubility in more complex alloys is indicated by the increasingly significant role played by dissolved gases in the processing of iron-based materials. The commercial stainless steels, for example, represent an area where data on nitrogen solubilities are required as a function of composition, temperature, and gas pressure. The nitrogen solubility in liquid Fe-Cr-Ni alloys has been studied by Humbert and Elliott.4 Their investigation covered the entire ternary system, and attempted to use data from binary alloys to predict nitrogen contents in liquid ternary alloys. Langenberg,5 using a method developed by Morris and buehl,6 calculated the nitrogen solubilities in multicomponent iron alloys from data available on binary iron alloys at 1600°C. Nelson,7 using a regular-solution model, extended this prediction to include the effect of temperature. Chipman and corrigan8 and Turnock and pehlke2 also employed empirical methods to calculate nitrogen solubilities in liquid multicomponent iron alloys. In order to provide a basis for predicting nitrogen solubility in liquid stainless steels, and to extend the data available for thermochemically modeling systems of this type, the following investigation was carried out. The study involved measupements of nitrogen solubility in a nondilute alloy and examination of the influence of a small addition of an alloying element on the nitrogen solubility. The study was focused on a very narrow range Of composition in the vicinity of 18 wt pct Cr-8 wt pct Ni (herein referred to as 18-8) with special emphasis on the change of.nitrogen solubility with the addition of a fourth metallic element. EXPERIMENTAL PROCEDURE A Sieverts' apparatus, described previously,1,2 was used in this investigation. The charge materials were contained in a recrystallized alumina crucible and inductively melted. Additions were dropped from a glass side-arm. All materials were hydrogen-refined and vacuum-treated to eliminate or minimize the oxygen content. The source and purity of materials is given in Table I. The initial metallic charge was heated to approximately 1000°C and held under vacuum for 30 to 45 min as a means for removing hydrogen and adsorbed gases. Argon was used as the calibrating gas to determine the "hot volume". The average hot volume of the system was approximately 50 cu cm STP and a few experimental runs were made using a reaction bulb with a hot volume of 80 cu cm. The temperature range studied was from 1550° to 1700°C and the temperature was measured optically. THEORETICAL PRINCIPLES General Discussion. Nitrogen dissolves in liquid iron alloys according to the reaction: 1/2N2(g) = N (wt pct in solution) [l] The equilibrium constant, K1, for this reaction is written as:

Jan 1, 1969

By T. J. Koppenaal

The surface slip line structure has been investigated by optical microscopy during the easy glide deformation of Cu-A1 single crystals as a function of composition, testing temperature and prior thermal treatment. The slip line structure in alloys of 2.5 or less at. pct Al is similar to pure copper, while alloys of 5 or more at. pct Al show slip tracings typical of a brass. Cross slip is observed in the "a-brass type" crystals and the amount of this type of slip increases rapidly with aluminum content. The cross slip tendency in 14 at. pct Al crystals is signicantly higher when tested at 150°C as compared to 4.2" and 77°K. In addition, cross slip is more pronounced in this alloy in the furnace cooled condition than when quenched from 450°C. The cross slip behavior is analyzed in terms of existing models for this type of deformation. In two previous investigations, reports of yield points1 and solid solution strengthening2 in Cu-A1 single crystals have been given. This paper enlarges upon the brief description of the slip line structure discussed in these reports. Since the easy glide slip line pattern of copper changes markedly with the addition of -30 pct Zn (-brass),3 a study of slip lines as a function of solute additions in Cu solid solutions should help to explain some of these differences. In addition to composition variables, slip lines have also been studied as a function of testing temperature and prior thermal treatment. PROCEDURE The slip line observations were made on single crystals of 0.5 to 14 at. pct Al using a light microscope. Details concerning the preparation and basic testing procedure are given elsewhere.' Prior to testing, each crystal was homogenized at 900°C for 24 hrs, furnace cooled, and electrolytically polished in a 60 pct phosphoric acid solution. The strain rate was-5 X 10 sec-I in each case. Unless otherwise stated, all observations reported upon here were made during the early stages of easy glide. RESULTS AND DISCUSSION The maximum magnification generally used was 1000X, and slip lines could be resolved down to about 105 cm (1000A). This resolution is appreciably less than obtainable with electron microscopy replica techniques where the replication can resolve slip lines down to about 40 A. Thus, while many qualitative features could be studied, the type of quantitative data obtainable with an electron microscopy replica study could not be made. Crystals containing 0.5 and 2.5 at. pct Al deform much like pure copper exhibiting a high density of fine slip lines that cover the entire gage length of the specimens. Fig. 1 shows the surface slip line pattern in a 2.5 at. pct A1 extended 0.01 shear strain at room temperature. Crystals having 5 to 14 at. pct A1 showed appreciably coarser slip lines that were generally concentrated at one end of the gage length. During easy glide these coarse slip lines propagate along the gage length in a manner similar to that observed in a-brass single crystals by Piercy, Cahn, and cottrel14 and refered to by them as a Lüders band propagation. Fig. 2 shows a typical area of these coarse slips in a 14 at. pct A1 crystal after a room temperature shear strain of 0.01. Two slip systems were apparently active. Using a method described by Cullity, the angles, between the specimen axis and the normals of the primary and secondary slip planes were determined to be 50 and 84 deg, respectively. 'From the Laue photograph, was 52, 81, 66, and 30 deg for the primary, cross, conjugate, and fourth slip planes, respectively. The secondary active plane in Fig. 2 is thus established as the cross slip plane, and the operative slip system is evidently the cross slip system, e.g., slip

Jan 1, 1963

By Leonard L. Melton, Calvin D. Saunders

The design and performance of many operations common to the petroleum industry depend upon the unique properties of a class of materials known as non-Newtonian fluids. The art of measuring and describing these properties, called rheology, has fallen far behind the field applica-tion of these fluids in this industry. Empirical methods are still employed although theoretically sound methods of analysis are now available. This paper illustrates a completely general method of analysis of the rheological properties of non-Newtonian fluids which id independent of the type of viscometer employed and also the rheological type of fluid encountered except those of a thixo-tropic or rheopectic nature. Values of the rheological properties of a fluid obtained using this method of analysis are based upon an absolute scale of measurement, eliminating the necessity of employ-jng arbitrary concepts of the flow properties of non-Newtonian fluids, The fundamental nature of this method of analysis is further demonstrated by evaluating the precision with which measurements have been made of these rheological properties by employing a dimensionless criteric: —the Fanning friction factor-Reynolds number correlation. INTRODUCTION Non-Newtonian fluids are not new in the petroleum industry. Particular properties of non-Newtonian materials have been recognized and used to advantage in drilling fluids and have found excellent application in the hydraulic fracturing process.'.' While usage of these fluids is not new in this industry, the art of measuring and describing their rheological properties is still in its infancy. This is reflected in the accepted method of evaluating drilling fluids, API RP 29, (1950), which recommends a one point "viscosity" measurement. These shortcomings are recognized by various groups in the industry and more adequate methods have been prposed.3,4 The efforts Of these people are to be commended; but, at the same time, the limitations of their method of analysis and viscometer must be appreciated. This method Of analysis is applicable Only to Bingham plastic fluids as is pointed out early in their articles. The consistency of a Bingham plastic fluid must also lie within the range of the viscometer which is also well defined by the author. It is believed that the apparent simplicity of this method of analysis and the utility Of Operation Of their viscometer will soon make the terms non-Newtonian fluid and Bingham plastic fluid synonymous as used in this industry; a tendency which has already been encountered. Application of this method of analysis to a non-Newtonian fluid other than a Bingham plastic can lead to erroneous results. The field of rheology has long been hampered by the adherence to arbitrary concepts of Of of the flow properties Of non-Newtonian fluids. This has resulted in the design and operation of viscometers so as to fulfill these concepts rather than following the more logical method of analyzing experimental data so as to yield a fundamental truth. completely Bingham proposed the concept Of plastic flow and yield asu rement. data presented by Buckingham could hardly be interpreted so as to substantiate this theory; but rather succeeded in establishing the fact that compliance with this flow concept could never be realized in the capillary tube vis-cometer.5 Bingham, in reply, sug-gested "Rather than complicate our formula, it would seem to me a much better plan to so change the conditions of flow that the formula will be linear... Reiner0 stated .This plan has been followed by me in collaboration with Miss Riwlin. . . . From the present paper (Reiner and Riwlin, 1929) it will be seen that it is possible to choose the conditions of flow so that the formula based on Bingham's law of plastic flow remains linear. This is realized in the rotation viscometer," Thus, a viscometer, with design and operation based on the Reiner and Riwlin equation for plastic flow, is restricted to a specific range of flow

Jan 1, 1958

By R. G. Knickerbocker, W. E. Brown, G. J. Vahrenkamp, M. M. Fine

THE results of a research and development laboratory and pilot-plant mineral-dressing investigation by the Bureau of Mines of the complex copper-lead-cobalt-nickel ores of southeast Missouri are reported in this paper. This investigation, in cooperation with the National Lead Co., showed that separate concentrates of lead, copper, and cobalt-nickel could be made by fine grinding and flotation. An industrial plant built subsequently by the St. Louis Smelting and Refining Div. near Fredericktown, Madison County, Mo., produced such concentrates during the war years. Present commercial production at the mill is limited to lead and copper concentrates, but research to permit economic utilization of the cobalt and nickel values is continuing. The complex sulphide deposits near Frederick-town in Madison County, Mo., have an operating history that dates back to the years preceding the Civil War. Perhaps these operations can best be summarized in terms of output which are given by Tyler: "Previous to 1900, the Mine la Motte Co. shipped cobalt ore to Swansea and in 1903 produced 120,000 pounds of oxide in a Missouri plant. Another cobalt refinery erected in 1906 by the North America Lead Co. at Fredericktown, Mo., operated intermittently until 1910. In 1909 it produced 83,384 pounds of cobalt oxide, 328,403 pounds of nickel, 8,314 tons of nickel-cobalt concentrates, 600 tons of copper concentrates, and 1,353 tons of lead concentrates. This plant was purchased at a forced sale in 1915 by the Missouri Cobalt Co., which produced a certain amount of oxide in 1918 and in 1920 recovered 102,410 pounds of cobalt oxide and cobalt hydrate, valued at $262,810." According to Buehler,2 "The ore, which consists of a complex mixture of the sulphides of cobalt, nickel, copper, lead, and iron, occurs at the contact of the pre-Cambrian porphyry and the overlying Lamotte sandstone and Bonneterre dolomite." The source of most of the cobalt and nickel is siegenite, a member of the linnaetite series of minerals. Its composition is variable, and although the chemical formula may be given as (CoNi),S,, it usually contains both iron and copper. The siegenite is characterized in this instance by an intimate association with chalcopyrite, and to a lesser extent with iron sulphides. Galena, on the other hand, while dis- seminated throughout the ore, is not closely bound to other constituents. Gangue is composed essentially of dolomite and quartz. Petrographic examination showed that fair liberation of sulphides and gangue could be attained at — 100 mesh. Complete liberation of micronsize inclusions, particularly of sulphides in each other would not have been possible at —400 mesh. Beneficiation Studies Many samples of the southeast Missouri ore were tested, but most of the work was confined to five samples of churn drill cuttings weighing 15 tons. The samples were reportedly representative of five sections of the deposit and were tested individually and as a composite. Only the results of the tests on the composite, which contained 1.28 pct lead, 2.03 pct copper, 1.06 pct nickel, 0.87 pct cobalt, 3.57 pct iron, 15.4 pct lime, and 23.9 pct silica, are presented in this report. In view of the rather complex and intimate association in the mineralogical composition of the ore, flotation was the logical choice in the selection of a beneficiation process. Other mineral dressing unit operations were considered as an adjunct to flotation, but none were beneficial. Many tests were made on these samples to determine the flotation characteristics of the mineral siegenite. As a result of this work, it was noted the siegenite was intermediate in floatability between chalcopyrite and galena on one extreme and iron sulphides on the other. The difference in floatability between siegenite and the iron sulphides was not very great and, in general, the same reagents that depressed pyrite and marcasite would also, in slightly larger quantities, depress siegenite. This tendency for siegenite

Jan 1, 1952

By V. M. Dobrynin

Experimental data demonstrate that physical properties of porous rocks change under pressure. In this paper an assumption is made and proved that under pressure the changes of physical properties such as porosity, density, permeability, resistivity and velocity of elastic waves are controlled to a large extent by the pore compressibility of rocks. It is also shown that the pore compressibility of rocks can be determined, within the range of pressures from 0 to 20,000 psi, by knowing the maximum pore compressibility and the magnitude of the pressure. Mathematical equations were developed which permit one to define changes in physical properties of porous rocks under pressure. These equations were verified by experimental data obtained from the study of sandstones. INTRODUCTION In studying the behavior of porous rocks under pressure in the field of petroleum technology, the most interesting aspect is the observation of those properties which characterize the rocks as possible reservoirs — for example, porosity, permeability, resistivity, density and the velocity of elastic waves. The literature dealing with this problem mainly contains data concerning the study of only one or at most two of these parameters, but not of the group as a whole. An attempt is made in this paper to find general equations involving each of these parameters, which will permit the study of the behavior of rocks under pressure. All experimental data used here were obtained from the investigation of consolidated sandstones. EXPERIMENTAL In addition to the use of published experimental data, an experiment was carried out which studied the main physical properties of sandstones under pressure. Two homogeneous quartz sandstones were chosen for this purpose: (1) the Torpedo sandstone from Kansas, and (2) the Medina sandstone from Ohio. The porosity of the Torpedo sandstone was 20.2 per cent, and that of the Medina 8.7 per cent. Permeabilities were 45 md and less than 1 md, respectively. Each sandstone contained about 5 per cent clay minerals, consisting mostly of kaolinite and chlorite, which were distributed quite evenly throughout the samples. One cylindrical sample 2 in. in diameter and 5 in. in length was cut from each sandstone and then saturated in a vacuum with a 3N solution of NaC1. This high concentration was used in order to obtain true formation factors and to decrease the swelling of the clay minerals. The methods of mounting the samples and measuring the changes in porosity and resistivity were practically the same as those described by Fatt and Mann.1,2 Changes of resistivity under pressure were studied for sandstones with 100 per cent water saturation, and for sandstones with the irreducible water saturation. The irreducible saturation was obtained by enclosing the saturated rock samples in relatively fine silicate powder so as to remove the water by capillary action. This procedure is described by Orkin and Kuchinski.3 Changes of permeability with pressure were determined at room temperature using nitrogen as the flowing medium. In studying the effects of pressure, one series of measurements was made using an internal pore pressure Pi equal to the atmospheric pressure, while the overburden pressure Pe ranged from 0 to 20,000 psi. A second series of measurements was used over the same range of overburden pressure, but with an internal pore pressure of 1,800 psi. When the results were compared on the basis of net overburden pressure (Pe — 0.85 Pi ), there was practically no difference for these two sandstones. The origin of the factor 0.85 in the expression for net overburden pressure is given by Brandt,4 Fatt5 and Geertsma.6 The relatively large bulk volumes of the sample (about 15 cu in.) made it possible to observe a

By Larry J. Tucker

INTRODUCTION The orebody at Pea Ridge strikes NE-SW and dips at about 800 to the SE. The ore and surrounding rocks are Pre-Cambrian in age. These rocks are usually very competent. Locally strong jointing has caused problems and toward the hangingwall dikes have caused particular problems during or after the open stoping phase of production. About 396 m of sediments lie over the ore. The shape and mineral content of the orebody has been fairly consistent so far with production areas lying from the 1375 to the 2475 levels. The deeper limits of the ore- body haven't been found yet. The ore is high grade magnetite with a strike length of over 600 m and a maximum width of over 180 m on some levels at the center of the orebody. Production at Pea Ridge for the first three years of operation came from two types of open stopes. The original stopes were recovered with horizontal production rings being drilled and blasted from vertical raises. Later a more typical sublevel stoping method using vertical production rings from one or more drilling sub- levels was used. There were a number of reasons for the selection of open stoping as the initial production method at Pea Ridge. First, it was judged that the ore was not of a block cave quality. After fifteen years of production, this assumption can be verified. There was some concern during the planning days for the potential for high flow rates of water into the mine from aquifers in the sediments lying over the orebody. Dewatering wells from surface and underground were put in as a precaution and nothing came of this potential problem. Open stoping and its resulting pillar structure put off this problem by supporting the sediments a few years longer. For a moderate investment in level development some production from open stoping was quickly realized. The first open stopes were brought in on what was then the bottom mine production level (2275), near the shaft pillar and situated on the footwall. This production practice of stoping on the heels of development from shaft pillar westward and from footwall to hangingwall continued through the open stope phases of production at Pea Ridge for many years. From the standpoint of mine efficiency and pillar stability, this would not seem to be a recommended mining practice. 74 570 w electric slushers, using 1.37 m dippers, pulled the open stope ore out into 18 ton bottom dump cars. Ordinarily five of these cars made up a train, which was pulled to the dump area by a trolley powered electric locomotive. Open stoping had the disadvantage that 100% of the recoverable portions of the orebody had to be developed in order to recover 33% of the ore. 67% of the ore was left behind in a large pillar system. For many years we had no planned method for recovery of these pillars. Mining methods are of course, limited by the existing technology. Advancing technology, coupled with the limited production capabilities of open stoping, low efficiencies and high relative cost early in the history of the operation recommended that other mining methods be looked at. In Sweden, considerable practical experience, coupled with a large amount of theoretical work had become available on sublevel caving. To Pea Ridge it offered the apparent benefits of: 1) The flexibility of diesel powered trackless haulage. 2) The efficiency of two machines to one operator on longhole drilling. 3) A multilevel production picture with a large number of drawpoints for ore recovery. 4) 100% recovery of the mineable portion of the orebody in one production pass, with no pillar recovery problems left behind. This paper outlines the experiments and experiences which Pea Ridge has gone through with sublevel caving from 1967 to this date.

Jan 1, 1981

By J. O. Brittain, E. Lautenschlager

Yield point measurements were made on polycrys-talline specimens of a iron deformed various amounts at 770, 1950, or 273°K, aged, and redeformed at 77: 195°, or 273°K. When the prestrain temperature is lower than that subsequent to aging, the yield point return is suppressed relative to specimens deformed at the same temperature both before and after aging. The degree of suppression is a function of both the magnitude of prestrain at the lower temperature and the difference between the deformation temperatures before and after aging. It is proposed that the suppression is caused by the formation of dislocation barriers during the initial low-temperature deformation. The aging kinetics of polycrystalline a-iron wires deformed at 77o or 303oK were studied at 44 " and 64 "C using internal friction measurements. No change was noted as a result of the difference in prestrain temperature. IN an earlier investigation1 it was observed that the return of the yield point was suppressed when a poly-crystalline specimen of a iron was plastically deformed at 77oK, aged at room temperature, and subsequently tested at room temperature. In order to investigate this observation, a research program was undertaken to measure the effect of prestrain temperature on the strain aging of a iron.' According to Thomas and Leak,3 return of the yield point and internal friction are similar measures of strain aging since both are dependent on solute atoms leaving the solid solution. The decrease in internal friction as a function of aging time is indicative of the removal of solute atoms from the solution, while the return of the yield point as a function of aging time gives the rate of arrival of solute atoms at the dislocations. According to Cottrell and Bilby,4 the solute atoms create an "atmosphere" which locks the dislocations and causes a return of the yield point upon restraining. In this experiment, both methods of measuring strain aging were employed in order to have two independent measurements of the strain aging phenomenon. In a previous study,5 the strain aging kinetics of a similar lot of a iron were measured for specimens which were prestrained and tested at the same temperature over the range of 77" to 273°K. Although some differences were found in the correlation of the two methods employed for measuring strain aging, the kinetics of strain aging were unaffected by the change of prestrain and test temperature. In another study,6 dislocation line tension and the density of the solute atmosphere were found to contribute to the return of the yield point when ingot iron specimens were prestrained at 303°K and tested at a lower temperature, namely 77°K. This paper is concerned with changes in strain aging kinetics produced by pre-straining at 77" to 303°K and testing at either the prestrain temperature or at higher temperatures up to 273°K. EXPERIMENTAL PROCEDURE The polycrystalline a iron specimens used in both the tensile and internal friction tests were 0.033-in. diam ingot iron wires, wet hydrogen treated and re-carburized. A more detailed procedure for processing a 3/16 in. ingot iron rod (nominal wt. pet composition: Fe - 0.013; C - 0.0125; Mn - 0.023; Si -0.005; P - 0.0023; S - 0.11; Cu - 0.004 N) to 0.033 in. diam specimens containing approximately 0.020 wt pet C and no detectable nitrogen with a grain diameter of 0.033 to 0.040 mm is given elsewhere.5 Immediately prior to testing, specimens were solution treated for 15 min at 700o ± 2°C in a static vacuum of less than 50 ?. of Hg and rapidly quenched into an ice-water bath while still enclosed in a 3 mm quartz vial. The internal friction specimens had 8-in. gage lengths and the tensile specimens had 2-in. gage lengths. The wires used as tensile specimens were first run as internal

Jan 1, 1962