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By J. D. Hunt, R. J. McDonald

It is proposed that extensive fluid motion occurs between the dendrites of a Partially solid casting and it is suggested the A segregates in steel castings are a direct result of this motion. The fluid flow arises because of density differences between liquid ahead of the dendrites and the interdendritic liquid. Experiments are described on a model system investigating this fluid motion. The importance of interdendritic fluid flow is discussed with reference to longitudinal segregation. SERIOUS macro segregation is often found in large killed steel ingots. Among the most common segregates are those known as A and V, Fig. 1. The A segregates are arranged over the surface of cones, the wide parts being at the base of the ingot. The A segregates are pencil like in shape and extend from the columnar into the equiaxed region. The V segregates are distributed over inverted cones but have a less well defined shape. They occur at the center of the ingot. Because of the commercial importance of macro inhomogenities these segregates have attracted wide-scale attention. The segregates contain alloying elements and impurities which depress the freezing temperature and are thus the last liquid to freeze. A number of explanations have been proposed to explain their presence. It has been suggested1'' that the segregates are the result of the equiaxed zone growing towards the columnar region together with the interaction of convection within the bulk liquid. It has also been proposed that the segregates are the result of nucleation and rapid growth ahead of the dendritic front.3 Neither of these explanations is completely satisfactory because A segregates are pencil shaped and are not found as continuous cones. In this paper an alternative mechanism is proposed, and experiments are described on a model system to determine whether the mechanism occurs in practice. It is thought that A and V segregates are not peculiar to steels but should occur in many other large castings. Fluid motion within the bulk liquid region of a casting has been extensively discussed. Little attention has been paid to fluid motion within the partially solid regions. The work415 that has been done has been mainly concerned with the fluid motion which results from the volume contraction on freezing. The volume contraction is used to explain various types of macro segregation. The present authors suggest that in many cases the fluid flow resulting from volume contraction will be small compared with that due to other causes. When the columnar region is growing, the liquid still remaining between the dendrites has a much lower temperature near the ingot walls than at the dendrite tips. The composition of the liquid in contact with solid will vary with temperature. The density of the liquid will thus vary both because of changes in temperature and composition. The layers of different density liquid will give rise to a slow but steady liquid flow through the interdendritic regions. If there is no density change with composition, the temperature gradient within the dendritic region should give rise to a downward flow between the dendrites, shown schematically in Fig. 2. When the liquid density changes appreciably with alloy concentration this motion could either be en-

Jan 1, 1970

By R. C. Buehl, M. B. Royer

A three ton per day blast furnace using blast temperatures up to 2200°F was operated to recover manganese from open-hearth slag and manganiferous iron ore. The spiegel product containing 12 to 24 pct Mn was blown in a basic converter to high manganese oxide slag as described in the paper which follows this one. HE steel industry, which uses over 900,000 short tons of contained manganese yearly, depends on the maintenance of supplies of manganese from foreign sources such as India, Gold Coast, and Union of South Africa. Domestic ores furnish less than 10 pct of the yearly requirements of metallurgical ores and, unfortunately, the United States has no large, or even moderate, grade deposits that could supply a major portion of the requirements for many years. It may be necessary to obtain manganese from low grade materials, even though the cost is appreciably higher than when imported ores are used. An American Iron and Steel Institute questionnaire prepared in 1949 revealed the startling fact that open-hearth slags contained about as much manganese as is imported annually. The quantity of slag produced each year by integrated steel plants (not including cold-melt shops) and the manganese contained in the slag follows: Flush slag, 4,500,000 net tons a year containing 408,000 net tons Mn; tap slag, 7,230,000 net tons a year containing 364,000 net tons Mn; for a total of 772,000 net tons Mn. Some of this slag is returned to blast furnaces but about 75 pct would be available for the recovery of manganese. In several decades, when many of the present sources of high manganese ores have been depleted, open-hearth slag and manganiferous iron ore may become the major source of the manganese required for steel production. In 1948, manganese-ore imports from the U.S.S.R. were 427,000 net tons or 34 pct of the foreign ore. Imports from this source were only 81,000 tons in 1949. It became evident that adequate stockpiles of manganese could not be accumulated for many years. The Bureau of Mines initiated an extensive research program on methods for increasing domestic production of manganese and entered into a cooperative agreement with the American Iron and Steel Institute for recovering manganese from open-hearth slags whereby the Institute provided additional research funds and trained operating personnel. Description of Process and Equipment Numerous pyrometallurgical and hydrometallur-gical processes and combinations of the two can be applied to the recovery of manganese from open-hearth slag and manganiferous iron ore. The process being developed at the Pittsburgh Station of the Bureau of Mines consists of: 1—Reduction of open-hearth slag in a blast furnace to recover the iron and manganese as spiegel-eisen with 12 to 24 pct Mn. 2—Selective oxidation of the manganese from the blast-furnace metal in a basic-lined converter to produce a high manganese slag with up to 60 pct Mn content, which is a synthetic ore for the production of ferromanganese. This process has the advantage over other processes in that the equipment which would be used, such as blast furnaces and converters, has been highly

Jan 1, 1953

By T. Leffers, A. Grum-Jensen

The development of texture in copper and brass (15 pct Zn by weight) rolled at room temperature and in copper rolled at -196°C has been followed by determination of pole figures for various degrees of reduction. The concurrent development in microstructure has been investigated by transmission electron microscopy. For low deformations, the texture in brass, and in copper rolled at -196°C, is the same as the texture in copper rolled at room temperature. The difference in texture does not show until 50 pct reduction. At the same reduction at which the difference in texture appears, mechanical twinning starts in brass and low-temperature rolled copper. Nevertheless, Wassermann's twinning theory is found to be incompatible with the present resulls. All fcc metals and alloys develop, by heavy rolling, one or the other of two types of texture, classified for convenience as copper type and brass type, or possibly a '(mixed" texture representing an intermediate stage between the two types. The pure fcc metals, except silver, develop copper-type texture by rolling at room temperature. Silver and many alloys, including brass with more than 10 pct Zn, develop brass-type texture.' By rolling at low temperatures a transition in texture from copper type to brass type has been observed for copper of commercial purity.2'3 It is generally accepted that there is a correlation between the type of texture developed and the stacking fault energy. Metals and alloys having fcc structure develop brass-type texture when rolled at room temperature if the stacking fault energy is low, whereas those with higher stacking fault energies have copper-type texture.2 Thus, the difference in stacking fault energy must cause a difference in deformation mechanism responsible for the difference in texture. Of the numerous theories advanced concerning the nature of this difference in deformation mechanism, four seem to be of current interest. Smallman and Greeen,2 Dillamore and Roberts,4 and Dillamore5 refer to the fact that cross slip more easily takes place in a material with a higher stacking fault energy and suggest that the copper-type texture is developed by deformation with extensive cross slip whereas the brass-type texture is developed by deformation without cross slip. Haessner6 has advanced the theory that the copper-tye texture is developed by a combination of normal {111} slip and slip on other planes, mainly 1100). Thus his theory, like the theory above, proposes an additional deformation mode for the formation of the copper-type texture. Contrary to this, wassermann7 and Ahlborn et al.8 believe that the copper-type texture is obtained by normal slip. In their opinion mechanical twins will change a copper texture into a brass texture. For this reason it is suggested that the brass-type texture is developed when, in addition to normal {111}(110) slip, mechanical twinning is present. None of these theories are, however, supported by direct experimental evidence. In a recent experiment Hu et al.9 have followed the development of rolling texture in copper and brass. The texture of copper and brass was found to be es-

Jan 1, 1969

By B. M. Larsen, T. E. Brower

In two previous paperslJ dealing with the carbon-oxygcn reaction, and the simultaneous content of each, in liquid steel in the furnace, we have made use of the quantity A[O], defined as the excess oxygen beyond what would be in equilibrium with carbon then present if the pressure of carbon monoxide were I atm.; that is, if [C] X [O] is taken as 0.00222, A[O] = [O] - 0.0022[C] where [O] is the percentage of oxygen by weight as measured by the method described earlier.3 This quantity ?[O] proves to be substantially independent of carbon content over the range 0.08 to I,z per cent, as well as of the basicity of the slag, and is nearly always within the limits o.o15 to o.oz5 per cent when the bath is boiling normally and is in what we have termed a steady state, Apparently it must be at least about 0.014 per cent before boiling occurs; but this threshold value seems to depend upon the ease of bubble formation at the metal-hearth interface, hence upon the condition of the surface of the hearth. In any case, ~(01, on the average, changes considerably following any disturbance of the bath, as by addition of ore. The present paper deals with the average changes in A[O] level following addition of spiegel or crop ends, or after procedures to promote stirring, or by tapping of the steel from the furnace. The observations were made on a large number of commercial heats, and consequently are subject to the influence of various disturbing factors; the results have the compensating merit of showing the consistency obtainable under the limitations imposed by practical operation. Variability of Excess Oxygen in Normal Open-hearth Operation The preceding genera' statements refer to the average value of A[0] particularly in heats that are boiling actively; on individual heats, which are less active, there may be a variable time lag between the disturbance and its effect, which complicates the interpretation of what is going on. For instance, if in the normal refining process boiling is sluggish, the slag usually is gaining Oxygen from the gas phase above it, Or from added Ore$ faster than it is losing oxygen to the metal; Yet when the bath starts to boil vigorously, the opposite condition may prevail for Some time. The consequence of this lag is a variation of A[o], the interpretation of which in a sing1e heat may not be immediately obvious. This condition is illustrated in Figs. I and 2. In Fig. 1, A[0] at the beginning of the test period was near the lower limit of its usual range (dashed lines) in the steady state as a consequence of the lime boil, which had ended about as indicated. The bath is now cold, carbon drop is slow, and the first small orc feed causes only a small rise in A[O]; as the temperature rises and as lime dissolves in the slag, and the bath becomes more active, the

Jan 1, 1948

By R. L. Robinson, P. DeFrank, R. F. Hatfield

Production equal to or greater than open-hole completions is possible through perforated completions if the flow paths throughout the perforations are free of obstructions.' Previous investigations have indicated that, in some cases, maximum productivity is not obtained due to plugging of the perforations with debris from the wellbore fluid and/or debris from the perforating process. Control of wellbore fluid and proper well completion techniques are very important in the elimination of perforation plugging.' Selection of properly designed perforating equipment also is quite important for maximum well productivity. Studies made with the use of the perforation flow laboratory, in which perforating tests are run under simulated well conditions, have shown that perforation plugging occasionally occurs. Plugs in perforations result from various causes. One of the contributors to plugging that can be controlled by the perforating device is the slug or carrot resulting from jet perforating. This condition has undergone extensive study, and previous developments have resulted in a decrease in carrot size—but not in complete elimination. It was felt that, if a method of completely eliminating the carrot could be found (with charge performance equal or better than previously obtained), a significant contribution would have been made. Such a charge has been developed and is reviewed in this paper. THEORETICAL CONSIDERATIONS OF CARROT ELIMINATION There are several popular theories of how a shaped charge jet is formed."," One of these is the hydrodynamic theory, wherein the liner is treated as a fluid under the impact of the explosive forces. Another is the spalling theory, where the interaction of shock waves in the liner causes small particles to be torn from the inner surface of the liner and projected at high velocity toward a common focal line to form the jet. It is not unreasonable to assume that both of these theories may be partially correct. For purposes of our discussion, it is simpler to use the second theory. Generally speaking, when a plate of metal is attacked by an explosive shock pulse, the pulse is transmitted through the metal at high velocity, as shown in Fig. 1(A). Pressures at the shock front may be 6 X 10' psi or higher. This shock wave (a compression wave) upon striking a free surface, Fig. 1(B), is partially reflected back as a tension wave. The interaction of the tension wave with the decaying compression wave causes a stress concentration in the metal; when this stress becomes great enough, a failure occurs and a small particle flies off and is projected away from the metal surface, as shown in Fig. 1(C). A new free surface is then presented to the shocks; the process repeats itself until there is no longer enough energy to cause failure, leaving a portion of the metal relativcly untouched. See Fig. 1(D). To apply this theory to a perforating shaped charge, consider the flat plate to be folded into a somewhat conical shape, with a column of explosive placed in intimate contact with the cone (Fig. 2). An explosive initiator detonates the charge, creating a shock wave

By Howard R. Keil

Reactor at Carlton mill successfully calcines pyrite-telluride flotation concentrate for cyanidation. CARLTON mill in the Cripple Creek district, 45 miles southwest of Colorado Springs, Colo., has been in operation for approximately three years, treating the custom sulpho-telluride ores formerly handled by the Golden Cycle mill in Colorado Springs. At the new mill the pyrite-telluride flotation concentrates have been roasted, prior to cyani-dation, in a Dorrco FluoSolids reactor, which has proved capable of yielding calcine readily amenable to cyanidation. Incoming ores are crushed at Carlton to % in. and sampled in 30 to 75-ton lots before the individual lots are mixed in the fine ore bin. The composite ore then goes to the grinding circuit. Classifier overflow from the grinding circuit is treated by flotation to produce a concentrate containing approximately 85 pct of the values in 5 pct of the weight. The flotation concentrate goes to the FluoSolids reactor prior to cyanidation. Cyanide solution values are recovered by zinc dust precipitation. Flotation tailings are thickened and cyanided, the values from this part of the circuit being recovered from solution by activated carbon. Gold values in the flotation concentrates consist of a small amount of finely divided metallic gold; the tellurides, sylvanite and calaverite; and gold very intimately associated with the pyrite. The metallic gold and a part of the telluride values can be extracted from the concentrates by cyaniding without roasting. However, extraction on the tellurides by this method is not satisfactory, and the pyrite values are so intimately associated with the pyrite that very fine grinding and cyanidation for a prolonged period under ideal laboratory conditions does not yield good recovery. Upon roasting, the tellurides are oxidized to very finely divided metallic gold which is readily soluble in cyanide. The pyrite is oxidized mainly to a porous iron oxide which allows cyanide solution to penetrate to gold particles and take them into solution. Feeding the Reactor Flotation concentrates move by gravity to a thickener. Thickener underflow is discharged at approximately 60 pct solids, by means of a diaphragm pump, into a storage and blending agitator. From here the concentrates are pumped to a disc filter. The filter cake, at 84 to 88 pct solids, drops directly into a repulper where it is repulped into a slurry of 78 to 80 pct solids. The repulped filter cake flows into a 6x6-ft slurry agitator from which it is fed directly into the reactor by the Moyno pump. The Moyno pump has eliminated a large number of difficulties that were first encountered in feeding a wet concentrate to the reactor. On the original installation in Canada a screw feeder was used to introduce the filter cake directly into the reactor. Since the reactor is under a slight positive pressure it was necessary to have a suitable seal to prevent gas escaping from the reactor at this point. When the concentrates produced in flotation were coarse or granular they could be readily fed to the reactor but when fine-textured, clayey concentrates were produced a great deal of trouble was encountered.

Jan 1, 1955

By J. F. Fidiam, T. F. Ford, A. G. Loomis

It is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analvsisl of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acidsl for example, sodium tannate or gallate—and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shutdowns. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells. It is safe to assume that the application of colloid chemical principles can also help in solving other outstanding problems of drilling fluids, such as the development of cheaper and more efficient viscosity reducers ; the development of chemicals that do not lose their effectiveness in a short time during drilling operations; the finding of chemicals to preserve the plastering properties of muds when concentrated brines are encountered or in drilling through salt beds; improvement in the plastering properties of poor muds by further defloc-culation, and, conversely, the prevention of excessive deflocculation of certain marine shales sometimes encountered; the preparation of muds suitable for the successful drilling of heaving shale formations; the finding 0f chemicals to treat the mud to prevent or to diminish lost circulation; the development 0f muds that will not impair 6

Jan 1, 1941

By R. C. Earlougher

Based on laboratory tests conducted with the use of fresh core samples as well as a considerable amount of field data obtained from numerous water floods in northeastern Oklahoma, it appears that for any given oil saturation there is a critical maximum velocity above which the oil-recovery efficiency falls off very rapidly. In effect, when a water flood is operated above this critical velocity, the injected water-oil ratio rises extremely fast, thus shortening the economic life of the flood and reducing the ultimate oil recovery. This critical velocity apparently varies considerably with the percentage of oil saturation of the sand, so that in effect the higher the oil saturation at the beginning of a flood the higher the velocity that can be used successfully. In reviewing several of the earlier floods in the Mid-Continent area, it is concluded that most of the failures were due to two things: (I) too low an oil saturation, such as 30 per cent, and (2) too high water-injection rates, Although considerably more field data are necessary to establish definite limits, it would seem that the proper field injection rate for a 330 by 330 or 440 by 440-ft. spacing varies from approximately I bbl. per foot of sand per day where the oil saturation is as low as 30 per cent up to 5 bbl per foot of sand per day when the oil saturation is as high as 45 to 50 per cent, Introduction With secondary recovery by water-flooding receiving more and more attention throughout the industry, a greater working knowledge of multiphase flow under field conditions becomes more and more necessary A great deal of research has been carried on in highly idealized laboratory conditions, from which certain trends have been indicated, but with few exceptions no direct application to field use has been reported. widely varying conclusions have been drawn from the mass of idealized laboratory experiments and often this divergence apparently was due to the neglect of connate or interstitial water. Since interstitial water is such an important factor in water-flooding operations, it then follows that any laboratory flooding experiment must necessarily take it into account; and since it is difficult to set up laboratory models to allow for interstitial water, the next best procedure is to use fresh core samples for such tests. Even this procedure has its difficulties, inasmuch as it is possible to run only one flooding test on each sample, as each sample differs somewhat in character from all other samples. However, this disadvantage can be overcome to a large degree by the use of an extremely large number of samples. The next question that arises is: "IS it possible to get uncontaminated core samples having a true oil and water saturation like that existing in the reservoir?" If the sand under consideration is still in the primary stage of production, with a normal or relatively high amount of gas still in solution in the oil, probably it is not possible to get a nonflushed core. On the other

Jan 1, 1943

By R. C. Earlougher

Based on laboratory tests conducted with the use of fresh core samples as well as a considerable amount of field data obtained from numerous water floods in northeastern Oklahoma, it appears that for any given oil saturation there is a critical maximum velocity above which the oil-recovery efficiency falls off very rapidly. In effect, when a water flood is operated above this critical velocity, the injected water-oil ratio rises extremely fast, thus shortening the economic life of the flood and reducing the ultimate oil recovery. This critical velocity apparently varies considerably with the percentage of oil saturation of the sand, so that in effect the higher the oil saturation at the beginning of a flood the higher the velocity that can be used successfully. In reviewing several of the earlier floods in the Mid-Continent area, it is concluded that most of the failures were due to two things: (I) too low an oil saturation, such as 30 per cent, and (2) too high water-injection rates, Although considerably more field data are necessary to establish definite limits, it would seem that the proper field injection rate for a 330 by 330 or 440 by 440-ft. spacing varies from approximately I bbl. per foot of sand per day where the oil saturation is as low as 30 per cent up to 5 bbl per foot of sand per day when the oil saturation is as high as 45 to 50 per cent, Introduction With secondary recovery by water-flooding receiving more and more attention throughout the industry, a greater working knowledge of multiphase flow under field conditions becomes more and more necessary A great deal of research has been carried on in highly idealized laboratory conditions, from which certain trends have been indicated, but with few exceptions no direct application to field use has been reported. widely varying conclusions have been drawn from the mass of idealized laboratory experiments and often this divergence apparently was due to the neglect of connate or interstitial water. Since interstitial water is such an important factor in water-flooding operations, it then follows that any laboratory flooding experiment must necessarily take it into account; and since it is difficult to set up laboratory models to allow for interstitial water, the next best procedure is to use fresh core samples for such tests. Even this procedure has its difficulties, inasmuch as it is possible to run only one flooding test on each sample, as each sample differs somewhat in character from all other samples. However, this disadvantage can be overcome to a large degree by the use of an extremely large number of samples. The next question that arises is: "IS it possible to get uncontaminated core samples having a true oil and water saturation like that existing in the reservoir?" If the sand under consideration is still in the primary stage of production, with a normal or relatively high amount of gas still in solution in the oil, probably it is not possible to get a nonflushed core. On the other

Jan 1, 1943

By R. Taggart, R. H. Ericksen, D. H. Polonis

Transmission electron microscopy techniques hare been used to study the spontaneous marfensite phase that forms during the thinning of Ti-Cr alloys. The structure of this phase has been found to differ. from the hcp martensite and has been identified as a clisforted fcc lattice. The spordaneous marlensile in this system is interpreted as a metastable isomorph of the equilibriunz TiCr, phase. WHEN thin-foil specimens for transmission electron microscopy were prepared from metastable alloys of the Ti-Cr system, a spontaneous transformation occurred' when the foils contained the untrans-formed 0 phase or two-phase mixtures of the 0 and w phases. The purpose of this paper is to examine the relationship that exists between the crystal structure of the spontaneous product and that of the matrix. The differences between the martensite transformation that occurs in the bulk material and the spontaneous reaction that occurs during the preparation of thin foils are compared with the observations that have been reported for similar phenomena in a commercial titanium alloy.' A spontaneous reaction that exhibits characteristics similar to a martensite transformation has been reported to occur in thin foils prepared from the retained metastable structures of several alloy systems.1'3"7 ~ull~ observed such a spontaneous reaction in 0 brass and attributed the apparent increase in the martensite transformation temperature to a decrease in the non-chemical free energy associated with bulk strain energy. He also showed that the spontaneous product did not have a specific habit plane, but that its orientation relationships to the parent matrix were dependen on the thickness of the transforming region. It has also been pointed out by Breedis6 that in thin films the absence of the constraints imposed by a bulk matrix can cause different requirements for the martensite plate interface and lattice distortion which is reflected bv a dependence of the transformation mechanism on the specimen geometry. In the case of the spontaneous reaction reported for Au-Zn alloys7 a definite habit plane was determined and shown to correspond with the habit plane calculated on the basis of the Bowles and Mackenzie crystallographic theory of the martensite transformation.'- lo EXPERIMENTAL PROCEDURE A series of titanium alloys containing 5.5, 5.9, 6.4: 7.6, 8.0, 11.3, and 18.7 at. pct Cr were prepared from high-purity (iochrome) chromium and iodide-grade titanium by levitation melting. The experimental procedure used for sectioning the alloys and for thin-foil preparation has been reported in an earlier paper.' X-ray diffraction patterns were obtained using a 114-mm Debye-Scherrer camera and Cu-Ka radiation. In order to minimize fluorescent radiation from the specimen, a strip of aluminum foil 0.002 in. thick was placed in contact with the X-ray film. After a specimen was removed from the camera: an additional X-ray experiment was performed, to insure that no spurious lines were obtained due to the presence of the aluminum foil. The interstitial impurity analysis for the alloys used in this study was as follows: oxygen, 100 ppm: hydrogen, 30 ppm: nitrogen, 28 ppm. EXPERIMENTAL RESULTS Electron diffraction patterns were obtained from several individual crystals of the spontaneous marten-

Jan 1, 1970

By T. F. Ford, J. F. Fidiam, A. G. Loomis

It is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analvsisl of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acidsl for example, sodium tannate or gallate—and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shutdowns. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells. It is safe to assume that the application of colloid chemical principles can also help in solving other outstanding problems of drilling fluids, such as the development of cheaper and more efficient viscosity reducers ; the development of chemicals that do not lose their effectiveness in a short time during drilling operations; the finding of chemicals to preserve the plastering properties of muds when concentrated brines are encountered or in drilling through salt beds; improvement in the plastering properties of poor muds by further defloc-culation, and, conversely, the prevention of excessive deflocculation of certain marine shales sometimes encountered; the preparation of muds suitable for the successful drilling of heaving shale formations; the finding 0f chemicals to treat the mud to prevent or to diminish lost circulation; the development 0f muds that will not impair 6

Jan 1, 1941

By J. R. Coleman, G. L. Corrigan

FOUR factors that largely determine the end product obtained when cement and water are mixed are the chemical composi-tion of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the moE finety-ground %cement, and the greater the surface exposed in propor-tion to its mass, the more rapid is the The work covered by this paper was done by the authors in pursuance of graduate studies in the ~epartment of petroleum Engineering at The University of Texas. The present paper is a condensation of a more detailed DaDer from which, for brevity, information such as the procedure for determining permeability and some of the discussion and procedure relevant to slurry volumes and fineness of cement have bsen deleted. It was felt that this information would not be of interest to most readers and should be outside the scope of this paper. Manuscript received at the office of the Institute Aug. 16, 1940. Issued as T.P. 1266 in Petroleum Technology. January 1941. hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.] Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are Poorer cementing materials than some of the more finely ground construction and on the other hand, often it is necessary to Pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concening the proper fineness range.

Jan 1, 1941

By M. A. Mayers, J. A. Thompson

In recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.l-14 Only in Russell's method" and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼-in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C, consisting of two annuli of 0.011-in. (o.a8-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944

By K. K. Clark, W. H. Somerton

The feasibility of reducing pressures needed to fracture formations by heating the borehole intensively has been investigated on a laboratory scale. Reductions in fracture pressures of heated Bandera, Berea and Boise sandstone cores were observed at various confining pressures, simulating reservoir stress conditions to a depth of 5,000 ft. Both permeable and impermeable borehole boundary conditions were tested. Three heating conditions were used in the tests. One group of samples was heated in a furnace to a temperature of 600C, cooled to room temperature., and then tested for fracture pressures. Two other groups of samples were heated with a borehole heater to maximum borehole wall temperatures of 625 and 792C, then cooled and tested. In all cases, heated samples showed substantial reductions in fracture pressures compared to unheated samples. The higher temperature borehole heated samples showed the greatest reduction, amounting to 70 per cent in the extreme case. In actual application to wells, it was concluded that fracture pressures may be reduced by 20 to 50 per cent by intensive borehole heating before fracturing. INTRODUCTION Hydraulic fracturing of oil and gas wells is an accepted and effective technique for increasing well productivity in many areas, but is notoriously unsuccessful in other areas. The technique becomes less interesting for production stimulation purposes when excessive fracture pressures are necessary. Formations which do fracture but require high pressures, probably form horizontal fractures. There is good evidence to indicate that some formations do not fracture at all, but yield plastically under high pressure. Thus, any technique which will make formations easier to fracture or will reduce fracture pressures is potentially interesting to petroleum producers. Horizontal fractures generally occur in planes of weakness, such as bedding planes, and at pressures equaling or exceeding the effective overburden stress. In the unusual case where planes of weakness do not exist, a slightly higher pressure must be applied to overcome the tensile strength of the rock. In general, high fluid-loss fracturing fluids are conducive to the formation of horizontal fractures.1 Vertical fractures, when they do occur, are initiated at pressures generally lower than overburden pressure and are favored by low fluid-loss fracturing fluids or impermeable boreholes. The pressure necessary to create a vertical fracture in an impermeable, elastic medium can be predicted from the so-called "thick-walled cylinder" equation: Pf = 2 or+ st.............(1) where pf = fracture pressure or = radial stress st = tensile strength of medium. This equation indicates that to fracture it is necessary to overcome a tangential compressive stress, induced by and equal to two times the radial confining stress, plus the tensile strength of the medium. If the above equation held strictly true for rocks, very little could be done to reduce fracture pressure. The tensile strength of the rock might be reduced somewhat, but any change in st would be small compared to the magnitude of the tangential stress at reasonable subsurface depths. Laboratory tests have shown that actual fracture pressures exceed values predicted from Eq. 1 by factors of 1.4 to 28.6.1,2 Eq. 1 thus does not properly describe the

Jan 1, 1966

By Kurt Kennedy

A method is described by which three elements can be condensed simirltaneously on a common substrate in such a way that the composition varies with position on the substrate. Almost all possible combinations of three solid elements can be formed in a single evaporation. The three elements are heated by magnetically deflected electron beams. The alloys and cornpounds formed by this method generally correspond to those trade by other methods; however, many exceptions exist. Simple symmetric crystallographic phases tend to form in preference to more complex phases. The Nb-Sn. Cr-Fe-Nt, and other systems of alloys made by this method will be discussed. Phases that form very slowly, such as the o phase in Cr-Fe alloys, may be formed rapidly by this method when certain substrate temperatures are used. STUDYING all the mixtures and compounds of two or more elements by the preparation of individual samples forces the investigator to make sampling sufficiently close together so that the properties of the intermediate compositions can be inferred. A completely unknown system will require a dis c our aging ly large number of preparations in order to fully know all its properties. For the purpose of expediting this type of investigation, methods have been devised to prepare samples that have a continuous variation in composition over some predefined area. The code-position of two elements onto suitable substrates has been used to produce alloys or compounds that have variable compositions depending on their positions on the substrates Composition gradients have been formed by depositing a wedge-shaped layer of one element and then depositing a second wedge-shaped layer on top of it such that the total film thickness is kept constant. Concentration equilibrium perpendicular to the surface is then established by annealing.4 This paper describes a method for the simultaneous condensation of three volatile components on a substrate such that there is a regular variation of composition with position on the substrate. The arrangement of the evaporation sources and the substrate is shown schematically in Fig. 1. Materials to be evaporated are placed in three water-cooled crucibles located at the corners of a 10-in. equilateral triangle. Electron beams from cathodes located below the crucibles are bent 180 deg by magnetic fields and focused on the material to be evaporated. The cathodes are connected in parallel to a constant-current 12-kv power supply. The distribution of emission current from each cathode is controlled by filament temperature. When materials that sublime are to be evaporated, the electron beam is deflected by an auxiliary ac magnetic field so that the beam moves over the surface of the evaporating material rather than digging a hole in one spot. The substrate is a 10-in. triangle of 2-mil stainless steel or molybdenum which is stretched against a slightly curved heat sink by a frame as shown in Fig. 2. This frame and heat sink are located so that each corner is directly above an evaporation source. The heat sink has three radiant heaters at each corner that can be separately controlled permitting the

Jan 1, 1967

By G. L. Corrigan, J. R. Coleman

FOUR factors that largely determine the end product obtained when cement and water are mixed are the chemical composi-tion of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the moE finety-ground %cement, and the greater the surface exposed in propor-tion to its mass, the more rapid is the The work covered by this paper was done by the authors in pursuance of graduate studies in the ~epartment of petroleum Engineering at The University of Texas. The present paper is a condensation of a more detailed DaDer from which, for brevity, information such as the procedure for determining permeability and some of the discussion and procedure relevant to slurry volumes and fineness of cement have bsen deleted. It was felt that this information would not be of interest to most readers and should be outside the scope of this paper. Manuscript received at the office of the Institute Aug. 16, 1940. Issued as T.P. 1266 in Petroleum Technology. January 1941. hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.] Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are Poorer cementing materials than some of the more finely ground construction and on the other hand, often it is necessary to Pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concening the proper fineness range.

Jan 1, 1941

By J. A. Thompson, M. A. Mayers

IN recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.1-14 Only in Russell's method11 and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce-the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼ in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C. consisting of two annuli of 0.011-in. (0.28-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944

By J. A. Thompson, M. A. Mayers

In recent years, the problem of damage to coke-oven walls by expanding coal charges undergoing carbonization has engaged great attention on the part of research workers in this field, and has led to the development of many devices for estimating these pressures.l-14 Only in Russell's method" and in the Koppers ovens7 are conditions quite similar to those in commercial ovens. Tests even in these ovens are empirical because no information has been published to permit an evaluation of "scale effects." Owing to the relatively large wall area in these test ovens, the average wall pressure determined may be lower than that existing in localized areas. This factor may be compensated for in part by the testing of coal charged into the test oven at a bulk density that is as high as the highest that is believed to exist in commercial ovens. Both of these lacks might be filled by the development of an adequate gauge for the direct measurement of wall pressure exerted by the charge in commercial coke ovens in normal operation. Previous attempts to elaborate such instruments7,15 have resulted in units which, because they had to be water-cooled, probably produced changes in the conditions of carbonization, and which had to be removed from the oven before carbonization was complete, to avoid their destruction. Late in 1941 the Coal Research Laboratory undertook to develop such a gauge, in which gas pressure was balanced against the charge pressure and which thus would not require water cooling, on a suggestion made in 1937 by one of the present authors and William B. Warren, a former member of the Laboratory staff. The gauge heads themselves were to be simple and cheap enough so that they might be discarded after each run if seriously damaged. This would permit them to be left in place throughout the carbonizing period, when they could be pushed out with the coke. The basis of the design, of which the latest exemplification is shown in Fig. I, was that as the internal gas pressure within a flexible metal envelope was increased, the flexible wall would move away from a stop when the gas pressure just overbalanced the charge pressure. If the stop were an insulated electrical contact, the point of balance could be indicated by the breaking of an electric circuit. It was anticipated that, while the instrument must operate at high temperature, the presence of a strongly reducing atmosphere throughout the carbonizing period would so reduce the danger of scaling that mild steel could be used for the gauge. This expectation has been justified. Danger of attack on silica oven walls by the steel gauge body can be eliminated by cementing asbestos paper or an alundum or silica plate to the back of the gauge body. The gauge head itself has a relatively heavy mild-steel body, A, into which standard ¼-in. pipe B is screwed to conduct gas and electrical leads. The body is closed by a single bellows C, consisting of two annuli of 0.011-in. (o.a8-mm.) cold-rolled shim-steel spot-welded together at their outside edges. The lower one is

Jan 1, 1944

By Jeffrey L. Thompson, Kenneth A. Gutschick, Robert C. Freas, Robert S. Boynton

Lime, the "versatile chemical," is, generally speaking, a calcined or burned form of limestone commonly known as quicklime, calcium oxide or calcia, or, when water is added, calcium hydroxide or slaked lime. Almost 40 different lime products are available, a fact which has contributed to the rather loose use of the term lime as well as to much confusion and misunderstanding. The term is frequently, albeit erroneously, used to denote almost any kind of calcareous material or finely ground form of limestone or dolomite. Lime is usually made from high-calcium or high-magnesium limestone, generally having a minimum of 97% combined carbonate content. Normally, high-calcium limes contain less than 5% MgO. When the lime is produced from a high-magnesium limestone, the product is referred to as dolomitic lime. Calcination, or the production of lime, has its origins in the earliest days of alchemy, with the general reaction class having been identified in an Arabic text printed in 1000 A.D. It was much later, however, in the mid-1700s to the mid-1800s before this basic reaction became understood from a scientific perspective. The production of lime has been so basic and simple that its underlying scientific principles have over the years received only intermittent investigation. Rather, much of the thought and inquiry has been directed toward the development of kilns. Thus, it has only been in the last 15 to 20 years that lime has received any concentrated scientific investigation relative to the thermodynamics and kinetics of the calcination and hydration reactions. Calcination refers to a broad class of reactions, of which the lime/limestone reaction is just one, wherein a substance is heated to less than its melting point, resulting in a weight gain or weight loss. In the calcination of limestone to produce lime, the basic chemical reaction is as follows: [CaCO3 (limestone) + heat (1000° to 1300°C)= 100 CaO (quicklime) + CO2 T 5644 or CaCO3 • MgCO3 (limestone) 10084 + heat (900°C to 1200°C) CaO • MgO (quicklime) + 2CO2 T 56 4088] While there is nearly universal agreement about the equilibrium conditions related to the limestone/lime reaction above, there have been numerous and varied calcination models developed for the reaction. Recent investigations have resulted in the development of the model shown in Fig. 1. From this model it can be seen that calcination is a function of both temperature and CO2 pressure. It does not, however, provide any indication of the rate at which the reaction takes place. Calcination is strongly time variant with different limestones. In a very broad sense this relates to the fact that the calcination reaction starts on the exterior surface of the limestone and then proceeds toward the center. As the calcination reaction takes place, the CO2 released at the reaction interface must make its way through the lime to the exterior surface. Therefore, because calcination is limited by gas diffusion to the surface of the partially calcined limestone, natural impurities in the stone, differences in crystallinity, grain boundary chemistry, density variations, and imperfections in the atomic lattice all play a significant role in

Jan 1, 1983

By W. R. Bull, J. R. Roos

A method is described whereby the true financial value of each constituent of each concentrate can be calculated. Each value is then compared with what this value would be in a perfect separation. The difference in each case represents the loss incurred by each aspect of an inefficient separation. The relative magnitudes of these losses indicate those avenues of plant investigation and research that offer the highest potential reward. The metallurgical efficiency of a concentration operation is difficult to express because there are two criteria of performance, namely, grade and recovery. Neither of these alone gives any indication of the effectiveness of an operation and, if they are combined in some formula, it must be empirical and unreliable because of many external factors. Since milling is an operation performed as one step in the most profitable overall method of producing a metal or other end product, the main objective of mill operation should be to make a maximum contribution to this maximum profit. When concentrates are sold to custom smelters, the income from the operation, and the costs, may be calculated. When concentrates are further processed by another division of the same company, and there is no formal financial relationship between, say, the milling and smelting divisions of the company, the mill superintendent's job is less well defined. But even so, if the mill superintendent works as though he were selling his concentrates, and uses reasonable, if fictitious, conditions of sale, then he can get a good indication of the effectiveness of his operation by calculating his "Economic Recovery". ECONOMIC RECOVERY This is a method used as a basis of operation by several mills and has been described in the literature. Very briefly, the "standard" of operation is taken as that of a mill separating the ore into perfectly pure concentrates with 100% recovery of each mineral in its respective concentrate. For example, a 4%Pb, 4% Zn ore (galena and sphalerite), would provide a lead concentrate weighing 4.62% of the feed and assaying 86.6% Pb and a zinc concentrate weighing 5.97% of the feed and assaying 67.1 % zinc. These perfect concentrates are (hypothetically) shipped to the appropriate smelters, freight and treatment charges and payments calculated, and the net return obtained. This is the optimum financial return for the operation of the mill and is used as the standard. Now the return for the actual, real-life, mill operation is calculated in the same way, and the ratio of the two is termed the Economic Recovery. Many additions and modifications may be made in any particular case. For example, if the zinc mineral is marmatite, the optimum grade of the zinc concentrate may be set lower than 67.1%. If silver is present, it will be recovered 100% in the lead concentrate in the perfect operation. Similarly, cadmium will be recovered 100% with the sphalerite. Mr. Weiss' paper' mentions a case where, because of extremely fine intergrowth between the valuable mineral, chalcocite, and pyrite, the optimum grade of copper concentrate was taken as 45% Cu instead of the theoretical 80%. Each operation will present its own possibilities in this way.

Jan 1, 1970