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By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,' based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.' This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- '. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.', ' Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,' are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952

By G. A. Chadwick, D. Jaffrey

The morpho1ogies and orientation relationships of the phases in the Sn-Zn and A1-A13Ni eutectic systems were examined by electron microscopy and X-ray diffraction techniques. In each alloy the "transition" from the lamellar to the fibrous morphology was found to be one of scale, not of type. The minor phase in both systems exhibited certain well developed facets which were not affected by changes in the ingot solidification rate. The crystallographic relationships displayed by the pairs of phases in both systems were also insensitive to the growth rate. In the Sn-Zn alloy, the unique relationship of: growth direction - II [1201 Sn - II [01101 Zn and ribbon interface plane 11 (101) Sn 11 (7012) Zn was determined. The Al-Al3Ni alloy phases did not possess any particular orientation relationship, though the Al3Ni phase invariably grew in the [010] direction and exhibited the same set of facet planes. These results are discussed in relation to current eutectic growth theories and explanations of the "lamellar to fibrous transition". THE lamellar to fibrous transition that occurs in many eutectic alloys has been the subject of considerable speculation and experimental study. In some alloys it can be induced solely by an increase in the solidification rate,'-3 whereas in others the transition supposedly occurs only if the lamellae are forced to grow out of the overall ingot growth direction.4-6 he cause of this latter type of transition has been attributed to deviations of the lamellae from their low energy habit planes;4'5'7 fibers are produced because the sustaining force for lamellar growth (a low energy boundary) is destroyed. Implicit in these explanations is the assumption that fibers are circular in cross-section and completely lacking in low energy inter-phase interfaces. The "natural" growth rate dependent transition has been studied less thoroughly although Tiller8 has attempted a theoretical explanation of it. Tiller's arguments are not completely satisfactory9 but his suggestion that the relative undercoolings of the solid/liquid interface for lamellar and fibrous morphologies are growth rate dependent cannot be totally discounted; it is possible, for instance, that the relative interfacial undercoolings could alter and produce the observed morphology change if the orientation relationships between the phases and the associated interphase bound- ary energies were sensitive to growth rate. Salkind et al." have reported finding a change in the orientation relationships in the A1-A13Ni system accompanying the lamellar to fibrous transition, but contradictory evidence has also been reported for this3'" and another system,12 so the position remains unclear. In an attempt to clarify matters a study was made of the "lamellar to fibrous" transition in the Sn-Zn and A1-A13Ni eutectic systems; the morphologies of these two selected systems are quite similar when viewed by optical microscopy. In the present research the morphologies and morphology changes were investigated by electron microscopy. The orientation relationships existing between the eutectic phases were also determined for both morphologies in both eutectic systems. EXPERIMENTAL PROCEDURE The materials and method of alloy preparation and ingot solidification for the Sn-Zn system have been reported previously.2 In this investigation nine horizontally grown ingots of the highest purity (99.9997 pct) were used. The temperature gradient in the melt was not intentionally varied and was approximately 10°C per cm. Seven growth rates between 1.3 cm per hr and 20 cm per hr were imposed. The A1-A13Ni alloys were prepared from "Spec. Pure" nickel and 99.995 pct aluminum by melting the components in an open alumina crucible and casting the melt into the cold graphite mold. Six ingots of the Al-Al3Ni alloy were unidirectionally solidified at growth rates from 1 cm per hr to 12 cm per hr under high purity argon. A typical ingot was 20 cm long, 1 cm wide, and 0.75 cm to 1.5 cm thick. Samples taken from the bars at positions 12 cm from the nucleation end were examined by conventional orthogonal-section metallo-graphic techniques. When required, samples were mounted for X-ray diffraction analysis using the Laue back-reflection technique with a finely focussed X-ray source. The surfaces of the A1-A13Ni specimens were prepared by mechanically polishing them down to the 1 µ diamond pad stage followed by an electropolish in 80/20 methanol/perchloric acid solution at 0°C and 20 to 30 v. The Sn-Zn specimens were repeatedly polished on an alumina pad and etched in hot dilute (2 pct) nitric acid until the diffraction spots were found to be sharp. Thin films of the alloys were prepared for observation in an electron microscope by spark machining thin discs (0.03 to 0.04 in. thick) from longitudinal and lateral sections of the bars and elec-trolytically thinning them via a jet polishing technique. For the A1-A13Ni eutectic alloy, an 80/20 mixture of ethanol/perchloric acid at 40 v and 20°C was found to be satisfactory. A solution of 70/20/10 methanol/perchloric acid/butylcellosolve at 25 v and 20°C was used on the Sn-Zn alloy. For the former alloy the jet nozzles (cathodes) and the disc clamps were of aluminum;

Jan 1, 1970

By C. T. Butler, W. W. Kay, R. D. Boddorff, R. L Ash

DRILLING and blasting in anthracite open-pit mines is a continuous problem to contractors and explosive engineers because of the diverse conditions caused by the nature of the geological formations, the extensive mining of the portions of coal beds near the surface, and the proximity of many strip pits to populated areas. Pennsylvania anthracite occurs in four separate long and narrow fields totaling only 480 sq miles. The coal measures are rock strata and coal beds that are considerably folded and faulted. The crests of the anticlines are eroded extensively. The beds outcrop on the mountain sides and dip under the valleys. At first only the upper portions of the syn-clines could be stripped. Now stripping to increasingly greater depths is economically possible, as is indicated by the fact that the proportion of freshly mined anthracite produced by strip mining has increased from 3.7 pct of the total tonnage in 1930 to 29.6 pct in 1950. Much of the rock overlying the deeper beds now being stripped is so extensively broken that considerable difficulty is experienced in drilling satisfactory blast holes and in using explosives in such manner as to insure a uniformly broken material easily removed by the excavating machinery. Such breaking of rock strata has occurred because the bed now being stripped has been mined extensively in former years by underground methods, and tops of gangways and chambers have subsequently failed. Draglines are used to uncover coal where the overburden can be moved with little or no re-handling. These machines range in size from those having a 2 cu yd capacity bucket on a 60-ft boom to those handling a 25 cu yd bucket on a 200-ft boom. Draglines are also used to strip to the bottom of the coal basins if the depth and the distance between the crops are not too great. For this type of operation blast holes are drilled full depth to the bed. These holes are commonly 30 to 90 ft deep; however, in exceptional cases, holes may be as shallow as 12 ft or as deep as 130 ft. Drilling is normally done for blasts of 12,000 to 60,000 cu yd of overburden, 30,000 cu yd being considered an average blast if vibration is not the controlling factor. Where the stripping of wide basins or the exposure of a moderately pitching vein makes the use of draglines impractical, dipper front shovels equipped with 4 to 6 cu yd buckets load into trucks. Overburden is removed in benches of 25 to 30 ft with blast holes drilled 4 or 5 ft deeper than the planned floor of the bench. For shovels under 5 cu yd bucket capacity the volume blasted varies from 8000 to 12,000 cu yd, whereas a volume of 30,000 to 50,000 cu yd of overburden is frequently blasted at one time for the larger shovels where vibration is not an important factor. During the past decade the churn drill, generally the Model 42-T Bucyrus-Erie blast hole drill equipped for drilling 9-in. diam holes, has become the most common blast hole drilling machine. Electricity powers half the churn drills in use and is preferred on the large strippings where electric shovels are operated and the working area is concentrated. On these operations the cost of additional electricity for the drills is less than the cost of fuel to operate diesel units because of the existing large demand load of the excavating equipment. Moreover, electric motors start more easily in cold weather and generally are less expensive to maintain. Diesel driven units are employed where a higher degree of mobility is required. The average drilling speed is 8 ft per hr, although in softer rocks a rate of 15 ft per hr is attained. Where rock is hard and strata is badly broken, drill speeds may be less than 2 ft per hr. Low drilling production results under these circumstances when loose material falling from the upper portion of the drill holes causes drill stems to be jammed. Rock formations vary so greatly in the region that a 9-in. diam churn drill bit may become dull after drilling only 2 ft or may drill satisfactorily for 56 ft; however, an average of 35 ft is usual in sandstone of medium hardness. Dull bits are hoisted to flat bed trucks by the sand line of the drill and are usually sharpened in the contractor's bit shop adjacent to the job. Care is generally taken to cover the thread end of the bit with a cap. To facilitate handling of bits around the drill, a heavy thread protector having an eye top is becoming more popular than the flat-top rubber or metal cap furnished with new bits. The 9-in. diam blast holes for a 25 to 30 ft bench are normally on 18x18 ft to 20x20 ft spacings, depending on the character of the overburden, although in broken ground 15x18 ft centers may be used to obtain better breakage and a more even bottom for the bench. The patterns of holes for shots

Jan 1, 1953

By R. D. Boddorff, R. L. Ash, C. T. Butler, W. W. Kay

DRILLING and blasting in anthracite open-pit mines is a continuous problem to contractors and explosive engineers because of the diverse conditions caused by the nature of the geological formations, the extensive mining of the portions of coal beds near the surface, and the proximity of many strip pits to populated areas. Pennsylvania anthracite occurs in four separate long and narrow fields totaling only 480 sq miles. The coal measures are rock strata and coal beds that are considerably folded and faulted. The crests of the anticlines are eroded extensively. The beds outcrop on the mountain sides and dip under the valleys. At first only the upper portions of the syn-clines could be stripped. Now stripping to increasingly greater depths is economically possible, as is indicated by the fact that the proportion of freshly mined anthracite produced by strip mining has increased from 3.7 pct of the total tonnage in 1930 to 29.6 pct in 1950. Much of the rock overlying the deeper beds now being stripped is so extensively broken that considerable difficulty is experienced in drilling satisfactory blast holes and in using explosives in such manner as to insure a uniformly broken material easily removed by the excavating machinery. Such breaking of rock strata has occurred because the bed now being stripped has been mined extensively in former years by underground methods, and tops of gangways and chambers have subsequently failed. Draglines are used to uncover coal where the overburden can be moved with little or no re-handling. These machines range in size from those having a 2 cu yd capacity bucket on a 60-ft boom to those handling a 25 cu yd bucket on a 200-ft boom. Draglines are also used to strip to the bottom of the coal basins if the depth and the distance between the crops are not too great. For this type of operation blast holes are drilled full depth to the bed. These holes are commonly 30 to 90 ft deep; however, in exceptional cases, holes may be as shallow as 12 ft or as deep as 130 ft. Drilling is normally done for blasts of 12,000 to 60,000 cu yd of overburden, 30,000 cu yd being considered an average blast if vibration is not the controlling factor. Where the stripping of wide basins or the exposure of a moderately pitching vein makes the use of draglines impractical, dipper front shovels equipped with 4 to 6 cu yd buckets load into trucks. Overburden is removed in benches of 25 to 30 ft with blast holes drilled 4 or 5 ft deeper than the planned floor of the bench. For shovels under 5 cu yd bucket capacity the volume blasted varies from 8000 to 12,000 cu yd, whereas a volume of 30,000 to 50,000 cu yd of overburden is frequently blasted at one time for the larger shovels where vibration is not an important factor. During the past decade the churn drill, generally the Model 42-T Bucyrus-Erie blast hole drill equipped for drilling 9-in. diam holes, has become the most common blast hole drilling machine. Electricity powers half the churn drills in use and is preferred on the large strippings where electric shovels are operated and the working area is concentrated. On these operations the cost of additional electricity for the drills is less than the cost of fuel to operate diesel units because of the existing large demand load of the excavating equipment. Moreover, electric motors start more easily in cold weather and generally are less expensive to maintain. Diesel driven units are employed where a higher degree of mobility is required. The average drilling speed is 8 ft per hr, although in softer rocks a rate of 15 ft per hr is attained. Where rock is hard and strata is badly broken, drill speeds may be less than 2 ft per hr. Low drilling production results under these circumstances when loose material falling from the upper portion of the drill holes causes drill stems to be jammed. Rock formations vary so greatly in the region that a 9-in. diam churn drill bit may become dull after drilling only 2 ft or may drill satisfactorily for 56 ft; however, an average of 35 ft is usual in sandstone of medium hardness. Dull bits are hoisted to flat bed trucks by the sand line of the drill and are usually sharpened in the contractor's bit shop adjacent to the job. Care is generally taken to cover the thread end of the bit with a cap. To facilitate handling of bits around the drill, a heavy thread protector having an eye top is becoming more popular than the flat-top rubber or metal cap furnished with new bits. The 9-in. diam blast holes for a 25 to 30 ft bench are normally on 18x18 ft to 20x20 ft spacings, depending on the character of the overburden, although in broken ground 15x18 ft centers may be used to obtain better breakage and a more even bottom for the bench. The patterns of holes for shots

Jan 1, 1953

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman' have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By J. B. Hess, C. S. Barrett

TO reach equilibrium between different phases in cobalt-rich alloys requires prohibitively long annealing cobalt-richalloystimes when temperatures are below about 700°C. The fact that a transformation from face-centered cubic to close-packed hexagonal readily tered takes place at temperatures below this in the cobalt-rich solid solutions is not an indication that thermally activated processes occur at an appreciable rate, for the transformation is well established as martensitic in nature. Wide divergence between heating and cooling experiments and high sensitivity to prior heat treatment make it difficult to judge temperatures of equilibrium between the phases.&apos; One object of the present work was to see if the information object of on the relative stability of phases could be gained by substituting plastic deformation for thermal agitation. Procedures were worked out that led to the determination of a diffusionless type of phase diagram, which represents the temperature of of phase equal stability for phases of the same composition, and the technique was applied to the Co-Ni system. Another object of the work was to see whether or not deformation would generate frequent stacking faults when these were thin lamellae of quentstackingfaultsa phase having higher free energy than the parent phase. The alloys were prepared in 80 to 100 g melts from cobalt (with metallic impurities estimated spectrochemically as follows: Ni, 0.05 pct; Fe, 0.001 pct.; Mg, Si, Cu, Cr, Al, < 0.001 pct) and Mond Car-bony1 nickel (with Fe, 0.05 pct; Si, 0.003 pct; C, 0.61 pct.; Cu, 0.001 pct; Co, Cr not detected, < 0.01 pct). The metals were melted in pure Al2O3 crucibles. An atmosphere of argon, that had been purified by passing over hot magnesium chips, was used for the alloys that, by analysis of the portions of the ingots actually used, were found to contain 15.3, 25.7, and 35.0 pct Ni, and vacuum melting (after degassing) was used for those containing 29.4 and 31.5 pct Ni. After induction melting the alloys were allowed to solidify in the crucible, and slices % in. thick x ½ in. in diam were annealed 12 hr at 1350°C for homogenization. These same specimens were used throughout the series of experiments, with annealing treatments of 4 hr at 900°C in purified hydrogen followed by furnace cooling, alternating with the deformation and X-ray tests discussed below. Results Spontaneous transformation was observed on cooling to room temperature in all alloys containing 29.4 pct Ni or less and by cooling the 31.5 pct alloy to — 195°C but was not observed in the 35 pct alloys after cooling to —195°C. These results are in satisfactory agreement with the cooling experiments of Masimoto.4 From these data it is clear that the temperature of beginning transformation M,,, drops to 20°C with the addition of about 30 pct Ni. The test for spontaneous transformation was metallographic. Specimens were thermally polished by annealing 10 hr in hydrogen at 1350°C, then furnace cooled; if trans- formation had occurred there were relief effects visible on the thermally polished surfaces. These markings were narrow straight lines, usually resolvable at high magnification as clusters of fine lines that resembled slip lines. It was concluded that they resulted from displacements on (111) planes, for the number of directions in individual grains often reached but never exceeded four, and lines could always be found parallel to the thermally etched (111) boundaries of annealing twins. The markings were thus consistent with the idea that the transformation occurs by (111) plane displacements (Shockley partial dislocations moving on (111) planes). This was further confirmed by X-ray tests for stacking disorders. Using an oscillating crystal technique previously employed to detect strain-induced faulting in Cu-Si alloys," streaks indicative of the stacking faults were looked for and found on X-ray films of the spontaneously transformed 25.7 pct Ni alloys, as expected by analogy with Edwards and Lipson&apos;s results on pure cobalt." The streaks were much intensified after rolling at room temperature. Transformation induced by plastic strain was investigated as a function of alloy composition and temperature of deformation. A series of tests was made to determine suitable straining and X-raying techniques. Filing was found inferior to abrasion in converting cubic samples to hexagonal, and abrasion was less effective than peening in producing smooth unspotty Debye rings in the X-ray patterns. Because the diffraction lines were broad, Geiger-counter spectrometer records of filings were less sensitive in revealing small amounts of transformed material than X-ray patterns recorded on films in a small diameter camera. After these exploratory tests the following methods were adopted. Specimens that had been annealed at least 4 hr at 900°C and furnace cooled were mounted in a block of aluminum, brought to temperature, and peened thoroughly with a mullite pestle preheated to the same temperature. The specimens were then quenched to room temperature. In peening, a circular area of % in. diam was given 500 blows. A few control tests showed that an additional 1000 blows did not detectably change the proportions of the phases present. The amount of transformation was judged by X-ray reflection patterns from the peened surface, using the innermost four lines of the cubic and the hexagonal patterns with filtered CoKa radiation,

Jan 1, 1953

By H. J. Tschirner, L. P. Davidson, R. K. Carpenter

HE electrolytic zinc plant of the American Zinc Co. of Illinois, at Monsanto, was expanded in 1943 to a capacity of 100 tons of slab zinc daily. This capacity was not attained because of inability of the leaching plant to deliver an adequate amount of solution for electrolysis. Changing the leaching method so that the acid was added to the roasted zinc material reversed the usual procedure and made it possible to attain the desired capacity. The conditions which prevented satisfactory work before this change and the difficulties which arose in reversing the usual leaching procedure are described. The "reverse" leach operation as now practiced is carried out as follows: All the calcine to be leached is fed continuously to a slurry mixing tank. About one third of the acid to be used is fed to the tank with the calcine. The slurry is discharged continuously to a Dorr duplex classifier in closed circuit with a Hardinge mill. The classifier overflow is pumped to any of six leaching tanks where the leach is completed. A finished leach is discharged through Allen-Sherman-Hoff pumps to Dorr thickeners, from which the overflow goes to the zinc dust purification and the underflow to vacuum filters. This change in leaching procedure from the usual one of adding calcine to a large amount of acid made it possible to provide an adequate amount of purified solution to the electrolyzing division and at the same time filter and dry all the residue produced. Operating savings in reagents and better metallurgical recoveries were also important benefits. The original flowsheet of the leaching plant provided leaching, sedimentation of the insoluble residue, and purification of the neutral zinc sulphate solution with zinc dust. The thickened residue was filtered and washed. The purification cake of excess zinc dust, precipitated copper and cadmium, and any insoluble residue was filtered off on plate-and-frame duplex classifier. Settlement in the thickeners was inadequate and the suspended solids in the thickener overflow gave rise to filtration difficulties after the zinc dust purification. Further, the filtration and washing of the leach residue was poor, and it became necessary to pump a large amount of unwashed or poorly washed residue to storage ponds outside the plant building. Two causes of the poor settling and filtration were determined: Soluble silica and ferrous iron in the calcine treated. The latter was a result of poor roasting and with more experience ceased to be a major problem. The silica was a normal constituent of the feed and the working out of the problem became a matter of controlling its solubility. The obvious method to render the silica insoluble was by intensive roasting. This, however, met with total failure as such roasting resulted in silicates, probably zinc, soluble in the 13 pct acid used for leaching. Attempts were made to coagulate the fine gelatinous slime with addition agents. Glue, lime, starch, beef-blood serum and others were tried without success. All the suggested tried-and-tested means of operating the thickeners gave no consistently good results. Variations in leaching time, in addition of calcine to the leaching tanks, "conditioning" of the pulp by prolonged agitation, immediate discharge of the leach upon completion to avoid breaking up flocs were all tried and given up as ineffective. Byron Marquis, of Singmaster and Breyer, worked with the plant staff on a beaker scale until a leaching procedure was developed which gave consistent results and a promise of overcoming the difficulties which had plagued the plant operation. It was suggested that the difference in solubility of silicates and zinc oxide in sulphuric acid could be made use of in a leaching method where the acidity was controlled carefully. Such control is possible when acid is added to a slurry of calcine. This process reverses the normal procedure of adding calcine to a vessel of acid, hence the term "reverse leach" was applied. In this way, the overall acid concentration can be kept very low. In the tests made, it did not exceed 0.05 g per liter free sulphuric acid. Numerous advantages were realized when no silicates were taken into solution and later precipitated as a bulky gel. The gel had made reasonable thickening and filtration of the leach pulp and practical drying of the residue impossible. When the gel was eliminated, thickening rates were increased as much as five times. The volume of residue after thickening represented about 10 pct of the total leach pulp and had been as high as 95 pct when the gel was present. The thickened pulp was filterable and the filtered cake was dried readily after washing. The zinc extraction from the calcine was slightly lower. This was more than compensated for by the increase in zinc recovered in solution from zinc which had been trapped in the gelatinous residue. The amount of copper recovered was lower. However, the amounts of other impurities, such as arsenic, antimony, and germanium, taken into solution were lower. This was particularly true of antimony. Since the inception of reverse leaching, no concentrates have failed to yield solutions free of antimony even when present in the calcine to the extent of 0.2 to 0.3 pct. Oxidation of ferrous iron is a problem of reverse leaching. Ferrous hydrate does not precipitate at pH 5.3 to 5.4 where a leach is finished. The usual oxida-

Jan 1, 1952

By W. W. Vaughn, R. H. Barnett, E. E. Wilson

Soon after the search for uranium ores on the Colorado Plateau began in earnest, thousands of feet of drill core ranging from 1 1/8 to 2 1/8 in. diam became available for study. Although significant advances had been made in the technique of quantitative gamma-ray borehole logging, instrumentation was in the development stage, and complete reliance could not be placed on gamma-ray logs alone to interpret quantitatively the meaning of radioactivity in a drillhole. A method that would be faster than chemical analysis and still give reproducible and reliable results for various drill core sizes was desirable to provide additional information on the enormous footage of drill core being accumulated. A solid phosphor scintillation drill core scanner was designed and constructed. Basically the instrument was developed to measure radiation from a drill core which would not be clearly recorded by a gamma-ray logger using a Geiger tube as the sensitive element. Such data would be beneficial in constructing isorad maps to delineate ore-bearing zones. A calibration in the range 0.01 to 0.1 pct eU.,O, was provided; above 0.1 pct eU3O8 gamma-ray logs were available and were being used to calculate grade and tonnage of ore reserves. The core scanner, however, has been used to estimate equivalent uranium content of ore-grade materials containing as much as 2.2 pct eU3O8 with an accuracy of ± 10 pct, the sample being in the form of a BX drill core. Actually, an apparent calibration of eU3O8 vs counts per unit time is a straight line with a slope that is a function of the sensitive element and the geometry of the counting assembly. A true calibration that will show the expected departure from a straight line is due principally to the random nature of the pulse from a radiation source and the nonlinearity of the electron circuitry. Design and Construction: Three methods of detecting radioactivity were considered and applied in developing the core scanner now in use: 1) the Geiger tube, 2) liquid scintillation phosphors, and 3) solid scintillation phosphors. The desired sensitivity and long-term drift characteristics needed for this operation could be attained only by using solid scintillation phosphors. All three methods are discussed. Before scintillation counters were common, nine beta-gamma sensitive Geiger tubes 7/8 in. diam by 12 in. long were used, arranged to surround the drill core with tube axes parallel to the axis of the core. This arrangement of Geiger tubes was en- closed in a lead shield 1 in. thick, and provision was made to slide a 6-ft length of drill core manually into the counting chamber, one foot at a time. A count for each segment was taken with a scaler while the core remained stationary. The equivalent uranium content of the different sections of drill core could then be estimated with the aid of a calibration curve of counts per unit time vs percent equivalent uranium (eU). In rare cases the effects of the radioactivity concentrated in small areas within the core introduced errors in the readings made with the Geiger tube arrangement owing to the geometry of the measurement. The variability of counting rate due to a localized concentration of radioactivity in a spot in the wall of a drill core is illustrated in Fig. 1. This effect and the inherent low efficiency of the Geiger tube were considered major disadvantages of this counting arrangement. When liquid scintillation phosphors became available the core scanner in Fig. 2 was constructed to make a more accurate measurement of the equivalent uranium content of a sample. This instrument contains about 4 liters of liquid phosphor in a stainless steel coaxial cylinder 1 ft long, with inner and outer walls 0.060 in. and 0.125 in. thick, respectively. Four end-window type photomulti-plier tube with cathodes of 2 in. diam, immersed in the solution at right angles to the axis of the core, were used to observe light flashes in the phosphor. The liquid phosphor offered equal sensitivity to radiation originating at any point in the enclosure and represented geometrically the optimum in design. However, providing a semi-permanent leak-proof seal between the glass envelope of the phototube and the metal walls of the container proved to be a serious problem in constructing the equipment. The most effective seals were especially machined O-rings from sections of large tygon tubing. The tygon took a permanent set owing to cold flow characteristics and in most cases sealed completely. The light absorption characteristics of the liquid phosphor changed gradually with time, and after one month the counting rate had decreased to half the original value. The most sensitive liquid phosphor tested proved to be a solution containing 4 g of 2.5-diphenyloxazole and 0.01 g of 2-(1-naphthy1)-5-phenyloxazole per liter of toluene. With fresh solution in the chamber and with all photomultiplier tubes operating in parallel, the counting rate contributed by any one of the four photomultiplier tubes was about 85 pct of the counting rate from a single tube operated individually. From these observations it was concluded that owing to coincident loss and light attenuation within the liquid phosphor, the apparent sensitivity could not have been materially increased by additional phototubes. However, this approach to core

Jan 1, 1960

By Wieland D. R., Hurst R. E., A. R. Hendrickson

Analysis of acidizing techniques, in correlation with reservoir data and a backlog of past treatments, has resulted in the development of a valuable engineering guide for planning acidizing treatments. Such treatments fall into three categories: (I) acid injection into the pores of the matrix; (2) acid injection into natural formation fractures at less than parting pressure; and (3) combination acidizing-fracturing treatments in which acid solutions (without propping agents) are injected at treating pressures sufficient to open and extend fractures through which the acid flows. Because the spending tirnze of acid during a specific well treatment does not change appreciably, maximunl penetration is attained when the first increment of injected acid is completely spent. Additional acid injection cannot be expected to further extend the benefits of the treatment. Depth of penetration will depend upon the reaction rate of the acid under treatment conditions, the injection rate of the acid into the matrix or fractures and the area-volume relationship existing in the flow channels. Based on Darcy&apos;s flow formula, extremely low injection rates must be used in order to keep bottom-hole injection pressures below formation fracturing pressure. As a result, only limited penetration of unspent acid will occur. Treatment records indicate that, in most acidizing treatments, formation parting pressures are exceeded, greatly extending acid penetration. Under these conditions, stimulation benefits are limited to the fracture area produced during the spending time of the first increment of acid injected into the formation. This area may be calculated from laboratory and well data to estimate depth of penetration. This, in turn, may be correlated with productivity data to assist The art of gas and oil well acidizing has been characterized by many changes in treating materials and techniques since its inception. These developments have been designed to provide greater production increases. prolong production declines and shorten payout time. Such improvements have been based primarily on data derived from laboratory research and field experience. As more of the variables influencing these treatments have been recognized and evaluated, acidizing has become less of an art and more of a science. Recent studies of fracturing treatments,&apos; in light of individual well conditions and the results of thousands of fracturing treatments, made possible the formulation of an engineering guide that is now being used to select optimum treating techniques and to forecast probable results of such treatments. A similar analysis of the factors controlling acidizing treatments has been made and is the basis for this paper, The findings herein can be used as a guide in the selection of acidizing solutions and techniques, tailored to fit specific well conditions and to provide optimum stimulation per dollar cost. Acidizing treatments may be classified into three basic categories—(1) treatments in which the acid is injected uniformly into the pores and flow channels of the matrix, (2) treatments in which the acid enters natural fissures and fractures in the formation at less than fracturing pressures and (3) injection of acid into the formation at a pressure sufficient to open and extend fractures into the rock through which the acid penetrates (without the inclusion of a propping agent). TYPE 1 — MATRIX ACIDIZING This category consists of treatments in which acid solutions are injected into a homogeneous carbonate

By G. W. Binkley, R. E. Collins, G. K. Dumbauld

A mathematical analysis has shown that the primary factors affecting the deposition of cement in unfractured perforations during squeeze-cementing operations are: the properties of the cement slurry, the geometry of the perforations, and the filtration time. The validity of the analysis has been substantiated by laboratory investigations. The information presented in this paper makes possible the prediction of the rate of deposition of cement in and about unfractured perforations under given squeeze-cementing conditions, the proper filtration time to control the amount of deposition to any desired value, and the deposition properties needed in cement slurries to restrict to any desired degree the formation of nodes of cement .Solids inside the casing. INTRODUCTION The deposition of solids against a permeable medium by the process of filtration is an important property of a cement slurry. General recognition of the role of filtration in the use of cement in wells is evident in view of the fact that several patents on low-water-loss cements have been issued during the past few years. In the conventional, high-pressure squeeze-cementing technique, a large volume of cement slurry is usually displaced into the area surrounding the perforated interval after the formation has been fractured hydraulically.&apos; Near the end of the job, the pumping rate is slowed or stopped intermittently in an effort to obtain a high pressure in the wellbore. The way in which a high pressure is obtained is not understood thoroughly. but it is be- lieved to be caused by the deposition of a rigid mass of compacted cement particles either in the fractures of the formations or inside the casing opposite the perforated interval. In a method of squeeze-cementing introduced several years ago, a small amount of cement slurry is squeezed into the perforations at a low pressure to avoid fracturing the formation. The filling of the unfractured perforations with cement particles by the process of filtration is important to the success of this technique. Early in the development of this low-pressure squeeze-cementing technique, laboratory and field-size experiments showed that conventional, neat cement slurries were unsatisfactory if the tubing was extended into or through the perforated section of the casing. The extremely high filtration rate of neat cement slurries caused the deposition of a compacted mass of cement inside the casing and made it impossible to remove excess cement by reverse circulation and difficult to withdraw the tubing. Because the need for cements with a reduced filtration rate was obvioils and urgent, modified cements containing 12 per cent bentonite were used until research was completed on modified cements containing 25 per cent bentonite.< These modified cements were useful in the solution of the immediate problem, but the following questions remained unanswered: (I) what is the optimum filtration rate of cement slurries for this application, (2) how long should the squeeze pressure be applied. and (3) how great are the effects of squeeze pressure and well temperature on the rate of deposition? Furthermore, the relationship of the filtration properties of cement slurries to the dimensions of the perforations and the wellbore was unknown. In order to obtain information relative to these basic considerations, a systematic evaluation of all the factors involved in the deposition of Cement during low-pressure squeeze-cementing operations was initiated. Although the work was directed toward an evaluation of the factors influencing the deposition of Cement in the low-pressure squeeze-

By Roland de Wit

Conclusions reached in a paper by weertmanl are amplified in a mathematical and graphical way. It is shown that in a stressed crystal a straight dis-location may be in a position of unstable equilibrium with respect to helix development, and how a small perturbation may start the dislocation off on its helical path. Helix development occurs by diffision; bulk diffusion is necessary for development from a screw, but core diffision is sufficient for development from an edge dislocation. For a mixed dislocation helix development can take place by core diffusion if the helix also climbs; a diffusion reversal takes place when the slope of the helix equals the slope of the Burgers vector. The work done on a crystal by the external forces is graphically shown to be consistent with the direction of motion of the dislocation in helix development. Finally a detailed mechanism for tangle formation from helices is presented. In the course of helix development a glide situation may be reached where a segment of each helix loop lies in a slip plane in which it can expand by glide. Thus is it visualized how a helix can deteriorate into a tangle. A paper by weertmanl proposes dislocation-tangle formation by a helical dislocation mechanism. The present paper amplifies Weertman&apos;s arguments in a mathematical and graphical way and presents some further ramifications of the proposed model. The importance of dislocation tangles is discussed in Weertman&apos;s paper and the references cited therein. The mechanism of their formation is not yet understood. Weertman proposes that in cold-worked crystals conditions exist suitable for the conversion of straight dislocations into helices and subsequently into tangles. Helix formation occurs by a diffusion process and Weertman proposes that at low temperatures only core diffusion is important. The present paper necessarily repeats some of Weertman&apos;s work. Since the mathematical development and notation used are slightly different from his, this was thought necessary for clarity. GEOMETRY OF THE HELIX weertman2 has shown that the equilibrium form of any dislocation line is a helix if it is assumed that the energy per unit length (line tension) of the dis- location is constant. For the special case that no external forces act on the dislocation, the helix reduces to a straight line. We shall assume in this paper that the dislocation has a helical form even when it is not in equilibrium. The parametric equation of a helix is, see Fig. l: where a is the radius of the cylinder tangent to the helix, and 270 the pitch of the helix. The pitch is related to v, the number of turns per unit length (along the axis) by the relation: When a = 0 Eq. [I] gives a straight line in the z direction. The growth of a straight dislocation into a helix is now described mathematically by letting a vary from zero to its final value. The tangent to the helix is given by where is the path length along the helix. This gives the direction of t and since its magnitude is unity we must have So that dcp/ds = (a2 +p2)-"&apos;. The curvature of the helix is given by where n = -(cos + sin) is a unit vector normal to the helix. Note that the vectors k and n always point toward the axis of the helix, Fig. 1. FORCE ON THE HELIX The external force which makes the straight dis-

Jan 1, 1963

By W. B. Hickman, J. J. Pickell, B. F. Swanson

Many physical properties of the porous media-immiscible liquid system are dependent upon the distribution of fluids within the pores; this in turn, is primarily a function of pore structure, liquid-liquiri interfacial tcnsion and liquid-solid wetting conditions. The cnpillary pressure hysteresis process provides a means of investigating the influence of pore structure upon fluid distribution for consistent sur/acc conditions. Invcstigntiot2s indicate that residual non-wetting-phase saturations /ollozuir,g the imbibition process (i.e.,wetting phase displacing nor2-wctting phase) are dependent upon both pore structure and initial non-raetting phase saturation and suggest that residual fluid is distributed as Discontinuous ,globules, one to a few pore sizes in dimension, thrnugh the entire range 01 pore sizes originally occupied. It clppears that air-mercury capillary pressure dala adequntely rellect the distribution of fluiris in a water-oil system when strong wetting condition preliczil. An oil-air counter-current imbibition technique has also been found to provide a rapid rneans of obtaining residual-initial saturation data. In a majority of cnses, rcsidual saturations detf-rniinecl from the oil-air or air-mercury process reasonably approximate residual oil saturation following water drive of a strongly water-wet medium. INTRODUCTION A reliable estimate of recoverable reserves depends not only on the amount of original oil-in-place but also on pore geometry and distribution of fluids within the pores. A critical parameter determining the recovery from a reservoir under waterflood, for example, is the amount and distribution of residual oil within the various rock types present. The purpose of this paper is to investigate the mechanism of capillary trapping and assess its importance in laboratory measureqents of residual oil saturation. The degree of wettability of a reservoir rock is recognized as an important factor in waterflood or imbibition experiments. In this paper, however, only the water-wet case has been considered. Considerable experimental evidence1 suggests that for water-wet rocks, capillary forces predominate in tile distribution of fluids and that viscous forces in the range normallv of interest in the reservoir have a minimum influence on residual oil saturation. It follows that if the ultimate recovery is controlled by pore geometry, a unique residual non-wetting phase saturation should exist for a given set of initial conditions. Two laboratory procedures.found to be extremely useful in the study of pore structure and degree of fluid interconnection at various saturations are decribed. Although air-nercury capillary injection curves have been used2 previously to characterize the drainage case, the withdrawal or imbibition case can provide valuable supplementary data. The air-mercury process, however, has several disadvantages; it is difficult to run in a sufficiently accurate manner, mercury does not always act as a strongly non-wetting liquid and in the air-mercury process the sample is rendered unsuitable for future analyses. An alternative process is described in which air is the non-wetting phase and naptha, hentane, octane or toluene is the wetting phase. INTERFACIAL TENSION AND CAPILLARY PRESSURE Interfacial tension between immiscible fluids is due to the difference in attraction of like molecules as compared with their attraction to molecules of the neighbouring fluid. This net attraction results in a tension at the interface. To extend the interface; thus, interfacial tension s can also be thought of as free surface energy. Interfacial tension is normally expressed as dynes/cm, and interfacial energy is measured in ergs/cm2 hence, both have dimensions ml A 2 and are numerically equal.

Jan 1, 1967

By A. O. P. Casbarian

An analytical method is developed to determine the variation of the ultimate lateral resistance of a plate in a cohesionless soil with depth. This analysis is based on a modification of Rankine&apos;s classical earth pressure theory and the theory of plasticity as applied to soils. The ultimate resistance is defined as the product of the effective stress at the midpoint of the plate, the area of the plate and a dimensionless variable termed the ultimate resistance factor. This variable has been plotted us the depth ratio: i.e., the ratio of of the depth of embedment us the height of the plate. The resistance of a plate may then be calculated using the values af the ultimate resistance factor from the chart provided or the equation may be programmed for use in an analysis of anchor systems in cohesionless soils. It is emphasized that the analysis is semitheoretical. The theory has been compared with experimental results reported in the literature and results indicate general agreement. Actual field tests are necessary to further verify this theory. INTRODUCTION With the exploration for oil offshore in waters all over the world, it is of importance to determine the behavior of the various soils in relation to their ultimate resistance to deformation. Examples of such problems are the holding capacity of anchors and the lateral resistance of piles. Very little information is available in the published literature on the design and performance of anchors, in either cohesive or cohesionless soils. The analysis developed in this report is the first step in obtaining a solution for the determination of anchor holding capacity in a cohesionless material. DISCUSSION The theory used in the analysis is based on the ultimate strength of the soil and is the maximum resistance developed by the plate against further movement. In such a state the elastic deformations are disregarded in comparison with the plastic deformations. Hence, the plate can be considered as completely rigid. The theory of plasticity determines the three unknown stresses at any point by means of two equilibrium conditions for a small earth element in combination with the failure condition. However, the exact solutions can only be carried out in a few simple cases such as, for example, when the rupture or failure lines are straight (Rankine theory) or with spiral and straight rupture lines (Prandtl theory).l Kiitter 2 derived a single equation expressing the variation of the stress in any given rupture line. To utilize this equation, it is necessary to know the stress in the rupture line at a certain point. Unfortunately, this is difficult to obtain unless the rupture line intersects the free surface at a certain angle or when the earth is cohesion-less and unloaded. A method to overcome this is to consider only the boundary conditions at both ends of a rupture line without investigating the equilibrium of the earth above the rupture line. This assumes that the rupture lines meet the surface at statically correct angles, so that boundary stresses may be determined. As Kiitter&apos;s equation furnished a relation between these stresses, the unit earth pressure may be calculated at the point where the rupture line meets the wall. Another way in which Kotter&apos;s equation may be applied is in investigating the equilibrium of a soil mass above a rupture line. This method assumes that the failure or rupture line is known and that the boundary stresses in the rupture line at the ground surface can be determined. In this case it is possible to determine the earth pressure from the equations of equilibrium.

Jan 1, 1967

By W. T. Cardwell

Physically absurd, triple-valued saturations appear in the straight-forward solution of the Buckley-Leverell equations for the displacement of oil by water or gas. From an engineering viewpoint, the triple value causen no difficulty. It is well known how it may be compensnted in order to obtain physically meaningful, numerical results. From a scientific viewpoint, the question still arises: What did the triple value mean? This paper explains how and why the triple value arose in non-capillary Buckley-Leverett theory. The discussion should serve as a background for the understanding and use of the modern method of characteristics in di.~pkzc(>ment theory. INTRODUCTION Displacement theory was introduced to petroleum technologists in 1 941 by Buckley and Leverett.&apos; Their first equation, which they wrote down without derivation, was equivalent to the following: ?s/?t= - qr/F ?f/?r (1) where S = saturation of displacing fluid (a fraction) r = time q,. = total volumetric velocity of both the displacing phase and the phase being displaced (usually, but not necessarily, assumed to be a constant) F = porosity (a fraction) f - fraction of the total volumetric velocity that is the volumetric velocity of the displacing phase (assumed to he a function of S only x = distance. Buckley and Leverett called Eq. I "a material balance equation". Actually it is derived from both a continuity equation, or material balance equation, and Darcy&apos;s law. Buckley and Leverett jumped from their Eq. 1 immediately to their Eq. 2, which was the equivalent of the following: (?x/?t)x = qr/F df/ds = qr/F f&apos;(s) (2) The jump from Eq. 1 to Eq. 2 involves apparently simple mathematics, but in that apparently simple mathematics lies a subtle point that is part of the key to the meaning of the triple value to be discussed here. Eq. 2 may be readily interpreted as saying that a point of constant saturation (on a saturation-vs-dis-tance curve) moves with a constant velocity that is proportional to the total volumetric rate, inversely proportional to the porosity, and is otherwise a function of the saturation itself. So that if one knows the derivativc with respect to saturation of the fractional flow function, f(S), for each saturation, one knows the velocity of each point of the moving saturation-vs-distance curve. The function f(S) can he determined experimentally and its derivative f&apos;(S) can be calculated. It turns out that the experimentally derived f&apos;(S) is not a monotonic function of S, but instead it has a definite maximum and declines away at both high and low saturations. This in turn means, in accordance with Eq. 2, that on a moving saturation-vs-distance curve, ccrtain intermediate saturations will travel faster than the saturations either higher or lower. The result is indicated in Fig. 1. In Fig. 1, the abscissas represent distances along a column of porous medium, which column is assumed to be uniform in cross-section perpendicular to the ab-scissal direction. The ordinates represent fractions of pore space occupied by the displacing phase, which may be either water or gas. It is assumed that the saturation is uniform over all planes perpendicular to the abscissal direction. The saturation is a function only of time and one space variable. Time variation of the saturation is represented by change in shape of a curve such as curve AGJ, which represents the initial saturation-vs-

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.&apos; Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By J. C. Rengel

Why and how the nuclear industry entered the electric power generation business is discussed in terms that nuclear energy was an undoubtedly additional energy resource and that it had promise of becoming a virtually inexhaustible generating power if breeder reactors could be devised. The growth of nuclear power, its total generation capacity, are related to the need of increasing energy requirements. The use of atomic energy for power generation will grow if it can compete economically with other fuels. The rate of growth, the time scale and direction of technical development is dependent on ore supplies. It is predicted that by 1980, 50% of all new power installations will be nuclear stations. INTRODUCTION Ten years ago, the nuclear industry was virtually unborn, the Atomic Energy Act of 1954 had just been signed, and peaceful applications of atomic power was little more than a phrase. Serious discussion of the practical application of nuclear energy to electric utility installations in the West was highly unlikely. The questions: Why and how did the nuclear industry enter the electric power generation business at all?; What is the predicted growth of nuclear power?; What technological changes do we predict?; How will the above changes affect the utilities? will in part be answered by this paper. WHY NUCLEAR POWER? The only justification for the West as for any other section of the country for atomic power is economics. Whatever energy source will provide the lowest generation cost will prevail; the only electric utilities which have shown an interest in nuclear power are those to whom it means lower generation costs. It is true that the Government sponsored the development of this technology long before there was any evidence of better economics; but a Government must take a very long-range view and it is the only type of organization that can afford to look more than twenty or thirty years into the future. The Government looked at projections such as shown in Fig. 1, which shows various rates of energy consumption, and matched these against estimates of fossil fuel resources. This showed that we will exhaust our low-cost fossil fuel supplies within 75 to 100 years and our total known fuel supplies within 150 to 200 years. The decision to invest in nuclear energy rested, therefore, on two arguments: a) It was undoubtedly an additional energy resource; and b) It has promise of becoming a virtually inex-haustable resource if breeder reactors could be devised if, while generating power, the reactors would produce more fissile materials than they consumed. This decision produced an unexpected bonus: nuclear power became competitive with fossil power much earlier than had been expected and, as shown in Fig. 2, forced the coal industry to take a hard look at its own position. I believe that the drop of coal prices shown here is the direct result of the entry of nuclear power into the energy supply business. At this point, it ought to be explained why and under what conditions nuclear power can be cheaper than fossil power. Fossil fuel cost to the utility is composed of two factors: a) Mining; and b) Transportation. As a result, the cost of fossil fuel to the utilities varies from 126, 106 Btu to 306, 106 Btu and higher. Nuclear energy is highly concentrated and the transportation factor becomes insignificant. Today the cost of nuclear fuel to the utility ranges between 156

Jan 1, 1967

By R. L. Rickett, S. H. Kalin, J. T. Mackenzie

Aluminum killed low carbon steel, § which is now used extensively for severe deep drawing or other difficult forming operations, is unusual in that its grain structure, after cold reduction and box annealing in accordance with conventional continuous sheet or strip mill practice, often is elongated, although at times it is equiaxed. Since this unusual structure has been found superior for many, but not all, severe forming operations, recrystallization of the steel, both at constant temperature and on continuous heating, was investigated and compared with that of rimmed steel in the hope that something might be learned about the mechanism of, and the factors controlling, the formation of such elongated grains. In this structure, the grains are elongated both in the lengthwise direction of the strip and transverse to this direction, even though nearly all of the extension in both hot and cold rolling is in the lengthwise direction. The grains are thus roughly pancake-shaped, being longer and wider than they are thick, as observed also by Burns and McCabe,1 and as illustrated by the typical structures shown in Fig 1. Fig la, representing a conventional longitudinal section, shows the length and thickness of the grains, whereas Fig Ib shows their length and width as seen by examining a section parallel to the sheet surface. Both illustrate the very irregular grain boundaries usually associated with the elongated grain shape. A finer equiaxed grain structure in this same grade is shown in Fig Ic. Either the elongated or the equiaxed structure may be present in the annealed product, and in rare instances the two types may coexist in a single specimen, as shown in Fig 1 d. Isothermal Recrystalliza-tion of Rimmed and Alamimum Killed Steel An aluminum killed steel known to have an elongated grain structure after conventional processing (Steel B, Table l), was selected for the initial recrystallization studies; for comparison, a rimmed steel, A in Table 1, was used. Samples of each in the form of hot rolled strip 0.075 and 0.095 in. thick, respectively, were cold rolled on a small laboratory mill in steps of about 0.010 in. per pass to obtain total reductions of 40 and 60 pct. Small pieces of the cold reduced strip were heated in lead at selected constant temperatures for one of several periods of time, then cooled in air. Rate of heating in the lead was, of course, very fast. Hardness of the cooled specimen was measured and a longitudinal section examined metallographically. Isothermal recrystallization curves for these two steels at 1050°F, based on hardness of the air cooled specimens, are shown in Fig 2 in which the amount of recrystallization corresponding to each plotted point is indicated. The marked difference in the behavior of these two types of steel is evident. After a corresponding amount of cold reduction, the rimmed steel recrys-tallizes in a much shorter time than the killed steel and the shape of its recrystallization curve, (plotted on a logarithmic time scale), is very different. The curve for rimmed steel indicates that recrystallization is analogous to isothermal transformation of aus-i.enite in that it proceeds at a progressively faster rate up to some 50 pct recrystallization, then at an increasingly slower rate. For the aluminum killed steel, however, the start of

Jan 1, 1950