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By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three-phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.' Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use. In the general evaluation of suitability of coals for coke making, particular attention is given to: 1) reserve, 2) ash and sulfur content, 3) inherent properties of forming strong, well fused coke, 4) expanding characteristics, and 5) blending properties. Items 1 and 2 are covered in detail in the first two phases of the survey, and coking behavior is considered in items 3 through 5. Problems is Coal Evaluation: Although not all coal beds of immediate or potential use to the coking industry in the Pittsburgh area have been tested for their coking properties, enough tests have been made to permit certain generalized statements. Virtually all the coals that will be used in this district are from the Appalachian region, and except for high oxygen coals from outcrops or stripping operations, they are coking coals. Hence the evaluation problem is not so much that of distinguishing between coking and noncoking coals as attempting to measure quantitatively differences in the coking and expanding properties of the better coking coals. Quantitative differentiation between good coking coals, is complex, since differences in their coking abilities are frequently of about the same magnitude as the precision of the test. Small-scale tests are generally unsuitable for measuring these slight differences, and there has been gradual acceptance of pilot-scale tests. Test Methods Employed: All the data reported here were obtained in two units known as the Bureau of Mines-American Gas Association (BM-AGA) carbonization apparatus and the sole-heated expansion oven. The BM-AGA unit, which consists essentially of a cylindrical steel retort about 18 in. diam and 26 in. high, carbonizes enough coal (180 lb) to allow evaluation of the coke by standard methods of the American Society for Testing Materials. The BM-AGA carbonization procedure and methods of testing the gas, liquid, and solid products have been described.' Expanding characteristics of the coals were determined in the sole-heated expansion oven," wherein the coal charge, heated from the bottom only, is carbonized under a constant applied force and the linear expansion or contraction is measured. Although results in this oven have never been quantitatively correlated with the expansion behavior of coals in conventional slot ovens, they are useful in assessing expansion behavior. In this report discussion will be confined to results obtained from these pilot-scale units, although the following data are available for most coals: proximate and ultimate analyses, free swelling index, agglutinating value, and plasticity. Sources of Coals Tested: In selection of coals for coke manufacture, economic considerations are as important as quality, and each coke plant balances these two factors to meet requirements of the most satisfactory coke at lowest price. Although these economic factors may in some instances outbalance small differences in coke quality, they are usually specific to each coke plant and cannot be given in any general statement. Recognizing that coal and plant operating costs are beyond the scope of the survey, the USBM evaluates the coking quality of various coals without regard to their competitive economic status. For the purpose of this article, coals of interest to the Pittsburgh district are arbitrarily defined as

Jan 1, 1958

By R. J. Wasilewski

Electrical resistivity variation with temperature was measured on a series of alloys containting up to 33 at. pct of oxygen over the range 77° to1500°K. The resistivity behavior is highly anomalous and itzconsistent with simple metallic conduction. Both composition and temperature-depended resistivity singularities were observed. A few experiments carried out on Ti-N and Zr-O alloys indicate the presence of similar anomalies. These observations, together with the published data on effects of substi-tutional alloying on the resistiuity of titanium, suggest that the anomalies are inhevent in the electron structure of this group oj metals. The existence of two-band conduction, and a significant shift of bands relative to each other with temperature and/or the electron concentration are suggested. CONSIDERABLE advances have been made in recent years in the alloy theory of simple metals. Very little, however, is known about the bonding in transition metals and their alloys.&apos; Titanium, with its relatively few electrons, may be expected to show simpler alloying behavior than the more complex transition elements. Its alloys with the interstitial elements appear particularly attractive in an investigation of bonding characteristics because of a) the simple nature of the solute elements, b) the remarkable similarity between the equiatomic structures Tic, TiN, and TiO, and c) the extensive solid solubility ranges of oxygen and nitrogen in a titanium reported.2,3 The Ti-O system was chosen for the most extensive investigation because of the relative ease of preparation of suitable specimens. Since the main object of the work was to obtain data on the bonding and its changes on alloying, electron-sensitive properties were primarily investigated. The present work describes the investigation on the electrical resistivity-temperature-oxygen content relationships. A few experiments were also carried out at selected compositions in the Ti-N and Zr-O systems. EXPERIMENTAL Materials and Method. Polycrystalline specimens were prepared in the form of hairpin strips some 50 by 5 by 0.15 to 0.50 mm by direct metal-gas reaction. This was carried out by controlled oxidation followed by a homogenizing anneal at a higher temperature. All the test specimens were fully homogenized as judged from the uniform microstructure and microhardness. To avoid preferred orientation, each strip specimen was annealed in the ß range prior to the oxidation, this procedure assuring random orientation in the strip;4 hence any texture resulting from the oxidation reaction itself affected all the specimens to a similar extent. Titanium used was of high purity (66 DPN, 10 Kg load; major impurities 0,-43G ppm, N,-70 ppm, C-25 ppm, Fe-14G ppm). The solute content of the alloys was determined by weighing, after the reaction with a known amount of oxygen. The specimens in which the discrepancy between the volumetric and gravimetric measurements exceeded 2 pct (or 0.2 mg for the low oxygen alloys) were rejected. The mean between the two measurements was then taken as the oxygen content of the alloy. Check analyses showed no measurable nitrogen contamination. All oxygen contents are given in atomic percent. Zr-O alloys were prepared in identical manner from hafnium-free crystal bar metal, cold-rolled to strip 0.25 mm thick. Ti-N alloys required very long reaction times at the maximum temperature available (1250°C). In order, therefore, to detect possible oxygen contamination, duplicate specimens were reacted in every experimental run, and one of these was analyzed both for oxygen (vacuum fusion) and for nitrogen (Kjeldahl). Only the specimens in which the check analysis showed < 1000 ppm O were then used for resistivity investigation. Since only relatively high nitrogen alloys (7.1 at. pct; i.e., 2 wt pct N,) were investigated, this oxygen contamination was considered permissible. Dc resistance was measured by the four-probe method as previously described.= The temperature was determined with a calibrated thermocouple placed in the center of the specimen hairpin. The errors in the specimen resistance values thus obtained were estimated at 1 pct due almost exclusively to the finite thickness of the potential wires and the consequent uncertainty as regards the true resistance length of the specimen. For the calculation of the specific resistance, however, no dimensional measurements could be carried out on most of the

Jan 1, 1962

By P. Majani, F. P. Kokesh, M. Grosmangin

Determination of the quality of cementation of casing in oil wells in the past has involved inflow and circulation tests to insure that the producing zones were adequately sealed off from the adjacent zones. Existing logging methods, such as temperature and radioactivity surveys, may detect the presence of cement behind the casing. However, the qualities of the cement (i.e., its hardness and particularly its bond to the casing) are not indicated. The new logging method described in this paper operates on the principle that the attenuation of a sonic pulse transmitted by a casing is greatly increased when that casing is bonded to an outer annulus of hard material (such as set cement) which has an appreciably smaller sonic-wave velocity than that of the casing. The down-hole tool contains a source of recurrent sound pulses which are detected by a receiver spaced a few feet from the source The amplitude of the detected casing-borne pulse is measured, and the resulting signal is transmitted to the surface where it is recorded vs depth. Since amplitude is a function of attenuation, the log is readily interpreted. Laboratory studies have shown straightforward relationship between attenuation and such variables as source-detector spacing and per cent of circumference bonded. It is shown that cement not set or not bonded to the casing has compara- tively little attenuating effect. Field examples show not only the cement top, but also the variation in cementation quality below the top. Further, the increase of bonding with time and after squeeze cementation is depicted. The detection of poor cement jobs is confirmed by production tests and by formation-test results. It is anticipated that the method will have wide application in evaluating cementation quality prior to formation testing in completions and recompletions. The analysis it affords may aid in further improving cementation techniques. INTRODUCTION The main purpose of oilwell cementing is to isolate a production zone from other undesirable zones. To investigate whether this purpose has been accomplished, several logging methods have been used such as temperature logs, radioactive tracer logs, etc. While these logs all respond to the presence of cement behind the casing, they do not indicate the degree of bonding of the cement to the casing. Early in the application of sonic logging, it was noticed that considerable attenuation of sound signals takes place in cemented pipe and is often made evident on the standard Sonic log by cycle skipping.&apos; The development of a circuit capable of continuously recording the amplitude of the casing-borne sound signal has made possible an extensive series of laboratory and field tests, which gave the following results. The amplitude of a sound signal after it has traveled in a firmly cemented pipe is only a small fraction of that recorded by the same device in free pipe. This provides a wide spectrum of energy levels; for given local conditions, empirical values of the amplitude can be correlated with the quality of cementation. Interpretations made in this manner generally have been confirmed by production tests, circulation tests and squeeze cementation. The purposes of this paper are to give a general description of the new logging method and to present some laboratory and field results. CYCLE SKIPPING Early attempts to study the quality of the cement behind the casing were performed with a standard Sonic log, which measures the transit time At, and were based on the well known phenomenon of cycle skipping.&apos; Cycle skipping normally is interpreted as being a manifestation of weak signals at the receivers. The log of Fig. 1 was run with the recording instrumentation adjusted to enhance cycle skipping. A mirror-image presentation was used for better visual interpretation. The transit time of sound in steel is about 58 microseconds/ft (corresponding to a velocity of 17,000 ft/ sec), and the portions of the log where this value is recorded are interpreted as zones with no cement bond. Where cycle skipping produces a higher value of At, weak signals (or a high rate of attenuation) are indicated, and a good cement bond may be present. The occurrence of cycle skipping, however, depends too much on instrument adjustment to give a uni-

By A. Hultgren, B. Herrlander

The original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between A1 and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880&apos; was free from veining. Bannister and Jones&apos; considered veining in ferrite to be a manifestation of microscopical and sub-microscopica~ inclusions. NorthCOtt,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berg1und. TrittOn (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling. Slight distortion would not allow projecting parts of a growing crystal to join up with atomic symmetry. Hanemann and co-workers showed that veining in ferrite consisted of ridges

Jan 1, 1948

By Rachel S. Prudhomme, Michael L. Jeremic

"The consolidation of mine backfill by free zing is a concept which has been under study in the mining engineering laboratories at Laurentian University during the past three years. The proposed underground application of freezing involves the artificial freezing of in-situ backfill by means of a refrigerated brine solution which would be circulated through a circuit off freeze pipes. The most interesting findings to date are: (I) The uniaxial compressive strength off frozen fill is considerably higher than that of cemented fill in a ratio of 20:1 (aggregate to cement), and (2) load deformation characteristics of the frozen fill suggest that a higher ice content results in more brittle failure and that samples which have initially failed can still support up 10 one-half the ultimate load without additional failure.Although at this early stage a derailed economic analysis of the procedure has not been possible, a general evaluation of the costs involved suggests that the method could be competitive with the hydraulic placement of cemented backfill. Results obtained from laboratory investigations indicate that the freezing of backfill is a structurally feasible option .IntroductionGround consolidation by freezing is based on the principle of transformation o f water contained in an aggregate-slurry into ice, which act s as a binding agent between the bulk particles, and which results in the transformation of a granular soil into a ""rock -type"" material. The abrasive nature of the particles enhance s the strength o f the ice by providing internal friction. As a result of this internal friction, the chances of plastic flow of the frozen mass when in a loaded condition are reduced(1). T he strength of a frozen aggregate is al so dependent on the grain shape of the aggregate particles which may or may not promote particle interlocking(2) and on the temperature since, below the freezing point of the water/aggregate mixture, the strength of the frozen mass increase s with decreasing temperatures.In the shaft sinking industry, artificial freezing of loose , unconsolidated soils has been in practice for several decades. Shafts for Saskatchewan &apos;s potash industry have been sun k to depths of 3000 feet by employing artificial freezing to stabilize the Blairmore Formation(3). The common procedure for freezing ground for shaft sinking is summarized as follows(4,5): I) 150 mm diameter bore holes spaced on 1.5 m centres are drilled in a circular pattern with a radius of 1.5 m outside the periphery of the proposed shaft."

Jan 1, 1985

By L. F. Mondolfo, B. E. Sundquist

The undercooling associated with the nucleation of the secondary phase from the liquid by the solid primary phase was studied in sixty binary alloys by means of a hot-stage microscope. It was found that in a system of a and ß, a usually nucleates ß at low undercoolings, but ß does not nucleate a, except possibly at undercoolings approaching homogeneous nucleation. This behavior can be explained in terms of relative interfacial energies and shows that crystallographic disregistry is only a minor factor in heterogeneous nucleation from metallic liquids. PREVIOUS experimental work1-6 on nucleation of solids from liquids has shown that normally nucleation is heterogeneous, and that small solid particles present in the liquid are responsible for the nucleation. These experiments and the theory that has evolved from them have made apparent that there is a "characteristic undercooling" associated with the nucleation of the solid from a given liquid by a given impurity. Little is known, however, about the chemical and structural relationships between the nucleating agent and nucleated solid that control the effectiveness of the nucleating agent in catalyzing the nucleation, as measured by the required undercooling. A review of the literature has yielded seventeen undercoolingsL-6 for the nucleation of solid from liquid metals by "known" nucleating agents. All values come from experiments in which the metal studied was divided into a number of particles (10 to 300 pin diam.) much larger than the number of extraneous impurity particles so as to obtain a large number of particles free of foreign nucleating catalysts. Known nucleating agents are then introduced by coating the droplets with particles or a thin film of the catalyst. Six of the seventeen undercooling values referred to cases where, for various reasons, the identity of the nucleating species was not at all certain. Another six cases involved nucleating agents with a crystal structure that was not known. Four other cases involved undercoolings listed as greater than or equal to undercoolings which were very likely those for homogeneous nucleation. One investigation3 involved adding to droplets powdered oxides, carbides, and so forth that were doubtlessly covered with adsorbed oxide or nitride films. The highly variable nature of these films resulted in highly variable undercooling (as was also found in preliminary work in this investigation). It is apparent that the information on heterogeneous nucleation in liquid metals is too limited to give rise to any definite conclusions on the nature of the catalytic process. With these problems in mind a new method was

Jan 1, 1962

By Carl Pierce

The writer of this article has not attempted to write a technical paper; on the contrary, he has tried to express in "steel-plant English," for steel men, a viewpoint drawn from his practice and experience. It is not his thought that it shall be taken as the "last word" in the making of this class of steel, or that good rimming steel cannot be made by any other practice. The paper was written to serve as the basis of a discussion from which it is hoped much benefit may be derived. The paper deals only with rimming steel made by the open-hearth process, and with the lower carbon steels, such as sheet and tin bar, rivet stock, skelp, etc., although good rimming steel as high as 40 to 50 carbon can be made by having good open slags and giving proper attention to working and tapping temperatures. Definition of Rimmed Steel Rimmed steel is sometimes called open or effervescing steel to differentiate it from killed or partly killed steel. It is steel made by a process which permits the free escape of gases from the metal in the molds. In passing up through the metal, the gases keep it in a rolling action from the walls of the mold inward. The top of the ingot rims in as the metal chills and the walls of the ingot get thicker, the center part remaining fluid until it reaches a pasty condition when it is covered with a cast-iron cap. The Charge In making up a charge for rimming steel, clean stock of a known composition must be selected, special attention being given to the analysis of the materials. The silicon in good rimming steel must be eliminated to a trace, therefore it is advisable to have a uniform amount going into the charge. Too much silicon gives a raw melting heat from which rimming steel is unlikely to result. For this reason a charge containing not to exceed 40 per cent. pig iron and 60 per cent. scrap, with no iron ore, is preferred to the Monell type of charge in which as high as 65 to 70 per cent. pig iron is used with a proportional amount of iron ore for the removal of the excess silicon and carbon. The silicon content of pig iron varies so much from day to day in the average blast-furnace practice that there is danger of getting too much of this element in the latter mixture when

Jan 1, 1926

By B. Herrlander, A. Hultgren

The original aim of the present investigation was to study the mechanism of cracking on hot-deforming red-short steels. During the microscopical examination of hot-deformed soft steels attention was directed to various patterns of so-called veining in the ferrite, as related to variations in the deformation procedure and the heat-treatment of the steels. Later, a hot-short steel of higher carbon content was also studied. Historical Storey1 suggested in 1914 that veining developed during the gamma-alpha transformation from the growing together of several alpha nuclei within the same gamma grain. Rawdon and Berglund2 found that in soft steel, forged somewhat below A3, the ferrite showed profuse veining, while usually there was very little veining after forging at very high temperatures. They emphasized the similarity between the pattern of veining formed by deformation about 600°C and that of slip lines formed by deformation at room temperature. They also suggested a relation between the gamma-alpha transformation and veining. They became convinced from etching and from the slip-line pattern in cold-deformed material, that the orientation within any ferrite grain showing veining was uniform. In recrystallized alpha grains veining was absent. Veining did not appear materially to affect the properties of ferrite. Independent of veining, continuous networks, attributed to preexisting delta and gamma grain boundaries were sometimes found, the former only in cast steel. Those networks were usually connected with small inclusions. Ammermann and Kornfeld3 confirmed that recrystallized ferrite grains showed no veining. In soft steel annealed between A1 and A3 there was veining only in the ferrite grains formed during cooling. Electrolytic iron deformed at 880&apos; was free from veining. Bannister and Jones&apos; considered veining in ferrite to be a manifestation of microscopical and sub-microscopica~ inclusions. NorthCOtt,5,6 in studies on veining in steel and other metals and alloys, attributed veining to oxide inclusions. It could generally be removed by annealing in hydrogen, a suggestion earlier made by Rawdon and Berg1und. TrittOn (discussion in ref. 5) emphasized the importance of perfect polishing for bringing out veining by etching, and thought the veins or subboundaries were produced during the gamma-alpha transformation, when it was rapid, as a result of the volume change and contraction during cooling. Slight distortion would not allow projecting parts of a growing crystal to join up with atomic symmetry. Hanemann and co-workers showed that veining in ferrite consisted of ridges

Jan 1, 1948

By C. O. Lee, R. H. Feierabend, Z. W. Bartlett

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.&apos;.&apos; Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.&apos; Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By W. F. Kieschnick, C. C. Miller, E. R. Brownscombe

The possibility has been mentioned that large pressure gradients in a solution gas driven field caused by high production rates might lead to a reduction in the ultimate recovery obtainable compared to that which would be obtained by a very slow rate of production. In the present study the reservoir conditions accompanying a high rate of production and the corresponding ultimate recovery were compared with those obtained if the reservoir were produced at some marginal rate throughout its entire life. The method of calculation involved the application of fluid flow - material balance analysis to a series of successive steady state conditions in the reservoir. In the case studied very little difference in recovery was obtained at the abandonment pressure. An analysis of the basic factors involved indicates that the sane results would hold for considerable variation in properties of reservoir fluids, permeability of the formation or well spacing. Even if the reservoir has a water drive it appears that no harm will be done by- open flow production if the rate is cut back before any appreciable free gas is produced. However, any condition which leads to disproportionate withdrawal rates and which causes large pressure differences over large areas might result in substantial loss in ultimate recovery. INTRODUCTION When the pressure declines in a reservoir, gas is evolved from solution causing a shrinkage in the reservoir oil so that a stock tank barrel of oil with its residual dissolved gas occupies a smaller volume than originally. For a given reservoir oil saturation, therefore. stock tank oil content will be higher at the lower pressure. At the same time the evolved gas which remains in the reservoir reduces the reservoir oil saturation, and this would be expected perhaps to cause a reduction in stock tank oil content. However, around the well the shrinkage occurs so rapidly that stock tank oil may actually accumulate in this region in spite of the simultaneous reduction in reservoir oil saturation. If this accumulation should continue, spreading into a larger zone, the loss might be appreciable and because larger pressure gradients accompany higher rates the accumulation might possibly be large if wells are produced at too high a rate. It is the purpose of this paper to determine the effect of rate of flow on ultimate recovery by solution gas drive. The problem under consideration involves the unsteady state flow of oil in a closed radial system from which oil is produced by the evolution of gas as a finite drawdown is estalllished and the reservoir pressure declines. A somewhat similar unsteady state production problem dealing, however, with a linear system has been considered by Muskat and Meres, but these authors do not discuss the effects which rate may have on recovery. Other methods have been reported for estimaling recovery as a function of pressure decline when producing at an infinitesimal rate, and Muskat and Taylor&apos; have shown the effect of fluid and reservoir characteristics on recovery under these conditions. Assuming steady state to exist, Babson has given a procedure for computing the decline in well productivity as the field is depleted, and Moyer has combined these methods to estimate abandonment conditions and the resulting ultimate recovery. These latter approaches to the problem either do not consider the effect of rate or assume steady state can be established. In detail this paper presents the behavior of the reservoir producing under unsteady state conditions and considers the effect of production rate during this unsteady state flow on the recovery attained. The analysis also shows that there will exist at abandonment a type of steady state, and on this basis a method has been clevelopetl for rapid calculation of abandonment conditions.

Jan 1, 1949

By J. Orkiszewski

A method i.s presented which can accurately predict, with a precision of about 10 percent, two-phase pressure drops in flowing and gas-lift production wells over a wide range of well conditions. The method is an extension of the work done by Grifith and Wallis and was found to be superior to five other published methods. The precision of the method was verified when its predicted values were compared against 148 measured pressure drops. The unique features of this method over most others are that liquid holdup is derived from observed physical phenomena, the pressure gradient is related to the geometrical distribution of the liquid and gas phase (flow regimes), and the method provides a good analogy of what happens inside the pipe. It takes less than a second to obtain a prediction on the IBM 7044 computer. INTRODUCTION The problem of accurately predicting pressure drops in flowing or gas-lift wells has given rise to many specialized solutions for limited conditions, but not to any generally accepted one for broad conditions. The reason for these many solutions is that the two-phase flow is complex and difficult to analyze even for the limited conditions studied. Under some conditions, the gas moves at a much higher velocity than the liquid. As a result, the down-hole flowing density of the gas-liquid mixture is greater than the corresponding density, corrected for down-hole temperature and pressure, that would be calculated from the produced gas-liquid ratio. Also, the liquid&apos;s velocity along the pipe wall can vary appreciably over a short distance and result in a variable friction loss. Under other conditions, the liquid is almost completely entrained in the gas and has very little effect on the wall friction loss. The difference in velocity and the geometry of the two phases strongly influence pressure drop. These factors provide the basis for categorizing two-phase flow. The generally accepted categories (flow regimes) of two-phase flow are bubble, slug, (slug-annular) transition and annular-mist They are ideally depicted in Fig. 1 and briefly described as follows. RUBBLE FLOW (FIG. 1A) The pipe is almost completely filled with the liquid and the free-gas phase is small. The gas is present as small bubbles, randomly distributed, whose diameters also vary randomly. The bubbles move at different velocities depending upon their respective diameters. The liquid moves up the pipe at a fairly uniform velocity and, except for its density, the gas phase has little effect on the pressure gradient. SLUG FLOW (FIG. 1R) In this regime, the gas phase is more pronounced. Although the liquid phase is still continuous, the gas bubbler coalesce and form stable bubbles of approximately the rame size and shape which are nearly the diameter of the pipe. They are separated by slugs of liquid. The bubble velocity is greater than that of the liquid and can be predicted in relation to the velocity of the liquid slug." There is a film of liquid around the gas bubble. The liquid velocity is not constant—whereas the liquid slug always moves upward (in the direction of bulk flow); the liquid in the film may move upward but possibly at a lower velocity, or it may move downward. These varying liquid velocities will result not only in varying wall friction losses, but also in a "liquid holdup" which will influence flowing density. At higher flow velocities, liquid can even be entrained in the gas bubbles. Both the gas and liquid phases have significant effects on the pressure gradient. TRANSITION FLOW (FIG. 1C) The change from a continuous liquid phase to a continuous gas phase occurs in this region. The liquid slug between the bubbles virtually disappears, and a significant amount of liquid becomes entrained in the gas phase. Although the effects of the liquid are significant, the gas phase is more predominant.

By G. S. Cole, G. F. Bolling

Recent experitnents on crystal growth have indicated that thermal convection in the liquid influences the conditions of solidification and subsequent crystal characteristics. However, the important columnar-equiaxed transition in castings has not been examined as a function of this free convection. An experiment is presented here to demonstrate a change in the transition as convection is suppressed. Lead- and tin-based alloys were cast in stainless-steel molds either without special procedures or with thin grids placed horizontally across the tnold diameter in portions of the castings. While the grids allowed some diffusion of heat and mass transport to occur during solidification, massive fluid flow was hindered in the vegiotz of the grids. A larger percentage of columnar grains appeared in the grid region than in other parts of the special castings or than in all regions of normal castings. This structural difference can be explained in terms of thermal convection. THERE is little information about the possible effects of natural convection which may occur during the solidification of a casting. Ruddlel-3 has stated that the movement of liquid metal produced by convection might assist in the transfer of heat, but in the absence of confirmatory evidence he suggested that this idea be treated with caution. chalmers4 considers, but does not assess, the importance of fluid motion in casting, while Tiller5 suggests that, in liquid metals which have extremely high thermal diffusivities, the effects of thermal convection may be negligible. In addition, throughout the literature, there are statements indicating the possible presence of thermal convection but without proofs or evaluations of its influence. Natural convection may be divided into two categories: thermal convection, where liquid flow is due to density differences caused by temperature gradients in the liquid (e.g., liquid near a cold wall falling with respect to hotter liquid further away from the wall); and solute convection, where flow is due to density differences as a result of concentration gradients, see Wagner.6 In most instances thermal convection predominates over solute convection. Nevertheless, even thermal convection has not been studied in any detail and is difficult to handle, since it can vary quantitatively from one experiment to another depending upon the exact positions of heat sources and sinks or the attitude of the container with respect to gravity. In spite of these difficulties it is possible to realize that a higher rate of heat transfer must result with convection than in any situation where conduction acts alone. Thus, the degree of increased heat transfer is the important undecided question in considerations of casting. It will be demonstrated here that a reduction in convective flow leads to a suppression of the columnar-equiaxed transition in a casting and that this suppression is related to a decrease in the degree of heat transfer. Fortunately it is possible to do this by comparative rather than quantitative measures. The insertion of horizontal plates or grids into a simple mold does not appreciably influence heat transfer per se, but in reducing the allowable height through which colder liquid may fall freely it reduces natural thermal convection. This leads to a reduced fluid velocity, a different flow pattern, and an altered heat transfer which can be measured. EXPERIMENTS The alloys were prepared from elements of 99.9 pct nominal purity and cast into an uncoated 2-in.-diameter stainless-steel mold insulated at the bottom with a suitable refractory so as to ensure predominantly radial heat flow during freezing. Casting was performed either in empty molds or in molds containing grids or plates in various configurations . The grids were constructed of aluminum screen (1/32 in. thick) which was cut to the desired shape, cleaned in aqua regia, and coated with a mixture of 2 parts aqua dag graphite -1 part Sauereisen cement mixture, thus supplying a hard, protective, and insulating layer approximately 0.006 in. thick. The

Jan 1, 1965

By J. Chipman, N. J. Grant, H. L. Bishop

In a recent review1 of the iron-oxide activity of simple open-hearth type slags containing lime, magnesia, silica, and iron oxide, it was established that activity values were lacking in the range of slag composition most interesting to open-hearth operators. That is, laboratory experimental results were not available for simple slag compositions having basicity ratios ranging from about 1.5 to 4.0 and iron-oxide concentrations ranging from about 10 to 30 pct. However, in order to estimate iron-oxide activities for the range of slag compositions of interest to open-hearth operators, activity values were calculated using ionic concepts of slags by following the treatment of Flood and Grjotheim.2 A study of these data indicated that the desired slag compositions were probably not obtained due to the limited solubility of the basic constituents lime and magnesia. Thus, it was decided to make additional heats equilibrating molten carbon-free iron with slags containing MnO, P2O5, and A12O3 in percentages commonly found in open-hearth refining slags, and to examine the liquid slag field over a greater composition range than that of the simple slags studied previously. The ranges of the constituents used in the present study are summarized as follows: Metal Pct 0 0.070-0.201 PctMn 0.005-0.142 Slag Pet CaO 24.45-41.90 Pct MgO 3.23- 9.21 Pct MnO 1.13- 9.62 Pct FeO 20.08-48.7 Pet Fe2o3 2.23-10.14 Pct SiO, 3.51-28.50 Pct P2O5 0.23- 3.65 Pct A12O3 0.43- 3.38 The experimental procedure consisted of equilibrating the slag and metal in an induction furnace provided with a carbon-arc slag heater as described previously by Winkler and chipman.3 The data obtained were used to establish both the iron-oxide activity values and the activity coefficients for FeO and MnO in the open-hearth type slags. RESULTS AND DISCUSSION I) Iron-Oxide Activity of Open-Hearth Type Slags—The iron-oxide activities of various iron-oxide contents of the open-hearth type slags, as calculated from the oxygen content of the metal by the method of Taylor and Chipman, 4 are plotted against the molar ratio of bases to acids in Fig. 1. The data represent slag-metal studies carried out in the temperature range 1530" to 1700°C. For the purpose of this study, the constituents CaO, MgO, and MnO are assumed equal on a molar basis in their effect on the iron-oxide activity; and, PO2,5 is calculated as an equivalent to SiO2 and A12O3 on a molar basis. The total iron content of the slag is calculated to FeO and is represented by the symbol (FeO) The points presented in Fig. 1 represent the results of this investigation for iron-oxide slags containing between 1 and 8 mol pct MnO and less than about 2 mol pct each of A12o3 and PO2,5 The curved lines shown in Fig. 1 represent the results of the summary1 of the iron-oxide activities of simple slags of the system (CaO + MgO) - SiOz - (FeO),. The solid portions of the curved lines represent experimental data, and the broken portions represent iron-oxide activities calculated from ionic concepts of slags. The iron-oxide values of the open-hearth type slags of this study are in good agreement with the values of the simple iron-oxide slag system. Only a slight modification is indicated. The results of this study suggest that the line for 20 mol pct (FeO), should be lowered slightly in the basicity range 1.5 to about 3.

Jan 1, 1959

By Richard H. Siller, Rex B. McLellan

A model for interstitial solid solutions has been considered in which a repulsive Potential exists between interstitial atoms in the solvent lattice. It has been shown that this model is consistent with the thermodynamic Properties of certain interstitial solid solutions. The model is then applied to the calculation of the variation of the diffusivity of carbon in au-tenite with composition. Although the energy levels at the saddle point, and thus the absolute values of dif-fusivity, cannot be calculated, it is shown that by taking the repulsive interactions between the diffusing atoms into account the functional form of the dependence of diffusivity on solute concentration can be derived. ThE composition dependence of the diffusivity, D, of carbon in austenite at a given temperature is well-known.&apos;-3 smith3 tried to reconcile the observed composition dependence of D at 1000°C with the previously observed4 composition dependence of carbon activity using equations for D derived by arken5 and Fisher, Hollomon, and Turnbull,6 but was unsuccessful. In this paper we shall modify the approach of Fisher et al. by considering the "blocking" model7 for interstitial solid solutions, based on concept due to Speiser and Spretnak,&apos; in which a repulsive potential exists between interstitial solute atoms in the solvent lattice, causing a certain number of interstitial sites to be "blocked" from occupancy by further solute atoms. We shall thus be able to describe the intimate relationship between the composition dependence of carbon diffusivity, a kinetic phenomenon, and the composition dependence of carbon activity in austenite. THEORY Consider for convenience one-dimensional interstitial diffusion in an fcc lattice in the [loo] direction. Fig. 1. Assume that solute atoms occupy octahedral sites only.7,9&apos;10 These octahedral sites are located on {lOO} planes a/2Å apart. A solute atom, A, occupying an octahedral site on a {100 } plane denoted by 2, has twelve nearest-neighbor octahedral sites: four on plane 1, four on plane 2, and four on plane 3. Diffusion occurs when there is a net flux of solute atoms, through an imaginary plane shown with dashed lines, from plane 2 to plane 3. Fisher et al6. use the concept of activated complexes, as given in the theory of absolute reaction rates." They show that the number of solute atoms per cubic centimeter per second which pc — Fig. 1-Diagram showing the arrangement of octahedral sites (x) in the fcc lattice. pass in the direction of diffusion from activated to new interstitial position is: ?where C is the concentration of the solute in atoms per cubic centimeter, l/m + is the fraction of new interstitial positions corresponding to motion in the forward diffusion direction (transmission coefficient), ?F* is the free-energy difference between the activated complex and the reactants when each is in its standard state at the temperature of the reaction (independent of temperature and composition in the case of carbon in austenite), y is the activity coefficient of the solute species, and, finally, ym is the activity coefficient of the activated complex (assumed constant). The flux of atoms moving in the forward direction through an area of 1 sq cm perpendicular to the direction of diffusion is therefore: m+ Ym l &apos; atoms per second where is the distance between planes. The blocking model states that a nearest-neighbor octahedral site of a given solute atom has a probability, f, of being inaccessible to other solute atoms. The number of available sites for diffusion on a given plane will, therefore, depend on f, which is constant, and Nu, the number of solute atoms on that plane. The effect is to have more available sites in the diffusion direction, thereby increasing the net flux of solute atoms. This is reflected in the transmission coefficient, l/m. To calculate the transmission coefficient for solute

Jan 1, 1970

By M. E. Nicholson

The effect of boron on the austenitic transformation rate of iron is smaller than on low carbon steels. The influence of austenitizing temperature on B-Fe is the reverse of its influence on steels. THERE have been many studies made of the influence of boron on the hardenability of steel, but apparently none has been made of its influence on the y-a transformation of pure iron. There are several facts suggesting that boron should have a pronounced effect on the transformation rate of iron. First, Simcoe et a1.l indicated that boron reduces the nucleation rate of ferrite and bainite. Second, they showed, along with others,&apos;, " that the lower the carbon content of steel the greater the influence of boron on hardenability. If this trend extends to pure iron, the influence on rate of ferrite formation should be considerably greater for iron than for medium carbon steels. According to Rahrer and Armstrong," the multiplying factor for boron in pure iron should be about 2.40, compared with 1.50 in a 0.35 pet C steel. According to an extrapolation made by Grange and Mitchell,&apos; the effect should be even greater, and the multiplying factor should be about 3.5 in iron. Many investigations of the boron influence&apos;.7, 2, 5 indicated that boron is effective only when in solid solution. On the other hand, Chandler and Bredig" suggested that boron increases hardenability by combining with nitrogen, thereby preventing formation of AlN, which catalyzes the decomposition of austenite. If their hypothesis is valid, boron should have no effect on an alloy free from nitrogen. Digges et al." showed that so far as low nitrogen high purity Fe-C alloys are concerned this is not the case. No experiments, however, have been made on low nitrogen iron. To determine whether or not boron has an effect on low nitrogen iron and, if an effect exists, to determine whether it is as large as predicted from the investigations of boron treated steels, the following work was performed. Because of the rapidity with which iron transforms from austenite to ferrite at even a moderate degree of supercooling, it was decided to study the influence of boron on the transformation rate of iron by determining the effect of quenching rate on the temperature of the beginning of transformation. The technique, essentially that used by Greninger&apos; and Duwez,H consisted of heating small specimens, 0.1 in. sq and 0.010 in. thick, in an atmosphere of purified helium with a resistance heater coil, and then quenching the sample in a jet of helium gas. At the time the jet was applied, the heating coil was removed from around the sample. The sample was suspended in the furnace on 30 gage chrome1 and alumel wires, one welded to each side of the specimen, which also served as a thermocouple for measuring the specimen temperature. Specimens were prepared from vacuum-melted iron obtained from the National Research Corp. which was rolled to a thickness of 0.060 in. and then decarburized in wet hydrogen for 51/2 hr at 700°C. This treatment also removed any boron present in the iron. The resulting iron contained 0.001 pet C. 0.0002 pet N, and 0.005 pet 0. One half of the piece was then boronized by surrounding it with 325 mesh boron powder and heating it for about 2 hr at 900°C in H,. The boronized iron was then homogenized at 1100°C for 24 hr. The iron boride case formed by boronizing was removed by grinding 0.010 in. from each side of the plate, and the piece was finally rolled to a thickness of 0.010 in. The resulting alloy contained

Jan 1, 1957

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.&apos;.&apos; Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.&apos; Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By C. C. Miller, W. F. Kieschnick, E. R. Brownscombe

The possibility has been mentioned that large pressure gradients in a solution gas driven field caused by high production rates might lead to a reduction in the ultimate recovery obtainable compared to that which would be obtained by a very slow rate of production. In the present study the reservoir conditions accompanying a high rate of production and the corresponding ultimate recovery were compared with those obtained if the reservoir were produced at some marginal rate throughout its entire life. The method of calculation involved the application of fluid flow - material balance analysis to a series of successive steady state conditions in the reservoir. In the case studied very little difference in recovery was obtained at the abandonment pressure. An analysis of the basic factors involved indicates that the sane results would hold for considerable variation in properties of reservoir fluids, permeability of the formation or well spacing. Even if the reservoir has a water drive it appears that no harm will be done by- open flow production if the rate is cut back before any appreciable free gas is produced. However, any condition which leads to disproportionate withdrawal rates and which causes large pressure differences over large areas might result in substantial loss in ultimate recovery. INTRODUCTION When the pressure declines in a reservoir, gas is evolved from solution causing a shrinkage in the reservoir oil so that a stock tank barrel of oil with its residual dissolved gas occupies a smaller volume than originally. For a given reservoir oil saturation, therefore. stock tank oil content will be higher at the lower pressure. At the same time the evolved gas which remains in the reservoir reduces the reservoir oil saturation, and this would be expected perhaps to cause a reduction in stock tank oil content. However, around the well the shrinkage occurs so rapidly that stock tank oil may actually accumulate in this region in spite of the simultaneous reduction in reservoir oil saturation. If this accumulation should continue, spreading into a larger zone, the loss might be appreciable and because larger pressure gradients accompany higher rates the accumulation might possibly be large if wells are produced at too high a rate. It is the purpose of this paper to determine the effect of rate of flow on ultimate recovery by solution gas drive. The problem under consideration involves the unsteady state flow of oil in a closed radial system from which oil is produced by the evolution of gas as a finite drawdown is estalllished and the reservoir pressure declines. A somewhat similar unsteady state production problem dealing, however, with a linear system has been considered by Muskat and Meres, but these authors do not discuss the effects which rate may have on recovery. Other methods have been reported for estimaling recovery as a function of pressure decline when producing at an infinitesimal rate, and Muskat and Taylor&apos; have shown the effect of fluid and reservoir characteristics on recovery under these conditions. Assuming steady state to exist, Babson has given a procedure for computing the decline in well productivity as the field is depleted, and Moyer has combined these methods to estimate abandonment conditions and the resulting ultimate recovery. These latter approaches to the problem either do not consider the effect of rate or assume steady state can be established. In detail this paper presents the behavior of the reservoir producing under unsteady state conditions and considers the effect of production rate during this unsteady state flow on the recovery attained. The analysis also shows that there will exist at abandonment a type of steady state, and on this basis a method has been clevelopetl for rapid calculation of abandonment conditions.

Jan 1, 1949

By G. L. F. Powell, L. M. Hogan

Large degrees of undercooling have been produced in bulk samples, 400 g, of copper and Cu-O alloys by melting in a slag of commercial soda-lime glass. The maximum degrees of undercooling obtained for copper, hypoeutectic and hypereutectic Cu-O alloy samples were 208°, 218°, and 97°C, respectively. No grain refinement as a function of undercooling was observed for the pure copper samples although in Cu-O alloys there was a marked decrease in grain size at degrees of undercooling greater than 150°C. The grain size change is the result of recrystallization during or immediately following the freezing process. THE first report of a large degree of undercooling in a bulk sample of metal was that by Bardenheuer and Bleckmann1 who produced 258°C undercooling in a 150-g sample of iron by melting in a glass slag. Garbeck2 extended this technique to nickel, cobalt, and copper and reported maximum undercoolings of 220°, 230°, and 60°C, respectively, while Fehling and schei13 undercooled a large number of metals as 2 to 20-g samples slagged in glass. Subsequently, one of the authors4 applied the glass slag technique to bulk samples, -500 g, of silver and obtained a maximum undercooling of 250°C. It was concluded that impurities which normally catalyze nucleation at small degrees of undercooling could be removed by oxidation and solution in a glass slag. Large undercooling of bulk samples of iron, nickel, cobalt, and their alloys has also been reported by other authors.8&apos;10&apos;11 Of the five metals mentioned above, copper was the only one which had not been undercooled by at least 200°C in the form of a large bulk sample. Since copper exhibits high liquid solubility for oxygen, as do iron, nickel, cobalt, and silver, it was considered that a much larger degree of undercooling than that observed by Garbeck for copper should be possible. This was obtained by modification of the technique applied previously to silver and the results of undercooling experiments with 400-g samples of copper form part of this paper. The undercooling behavior of Cu-O alloys was also studied, and the influence of a small oxygen content on the grain structure of undercooled copper was observed metallographically. 1) EXPERIMENTAL The copper was obtained as oxygen-free high-conductivity copper, the major impurities of which were Fe 0.01 pct, Zn 0.015 pct, and Si 0.02 pct. Melting was carried out in an open-ended vertical cylindrical fur- nace wound with Kanthal wire. A schematic diagram of the experimental setup is shown in Fig. 1. The undercooling technique previously used for silver4 involved preoxidation of the samples by melting the silver in contact with the atmosphere. The oxygen content was subsequently reduced by freezing the samples under a glass slag, whereby the oxygen was evolved as gas and the continuous glass cover over the surface prevented re-solution of oxygen when the sample was remelted. Since oxygen is not released as gas when a Cu-O alloy is frozen. the technique had to be modified for use with copper. Also, copper is oxidized during fire refining so that an in situ preoxidation treatment of the samples was not considered to be a prerequisite to large undercooling. Experimentation proved that this supposition was correct. Instead, it was found that care was necessary during melting of the copper under glass to minimize oxygen pickup. Samples of copper weighing 400 g were prepared by adding 50-g pieces of copper to a vitreous silica crucible partly filled with soda lime glass at a temperature of approximately 1000°C. Each piece was quickly immersed in the glass slag and held at this temperature until the oxide coating on the surface decomposed. This change was easily observed and coincided with the formation of gas bubbles in the glass

Jan 1, 1969

By R. B. Adair, J. S. Browning

The laboratory batch and continuous flotation pilot plant tests demonstrated the technical feasibility of recovering high grade mica concentrates from weathered mica pegmatite ores of Alabama and Georgia. The research indicated that combinations of anionic and cationic collectors may be used effectively for flotation of fine size mica from weathered pegmatite ores. In continuous tests, concentrates containing 98.5% mica were obtained from the Georgia pegmatite ore; the Alabama pegmatite ore concentrates contained 98.4% mica. The recoveries were 91 and 89% respectively. INTRODUCTION The principal uses of fine ground mica are as a filler in wallboard joint cement, as a filler and surface coating for roofing, as an ingredient in paints, and in oil well drilling mud. The mineral has other uses in the manufacture of rubber, wallpaper, plastics, welding rods, electric insulation, house insulation, and textiles, and as an annealing agent in metal treatment. In recent years, more than 99% of the domestic mica produced has been scrap and flake mica (mica which does not meet specifications for sheet mica and is used for producing fine ground mica). There has been a continued increase in mica production for several years, the 1963 production of scrap and flake mica totaling 117,251 tons.1 Ground mica is obtained primarily by crushing and milling pegmatites and schists. To a lesser extent, mica is produced as a byproduct of kaolin washing and feldspar and spodumene flotation operations. The processes used in recovering mica by crushing and milling pegmatites are generally simple, consisting of various combinations of alternate roll crushers and trommel screens that separate the mica and gangue at screen sizes coarser than 6-mesh. As these processes are designed to recover only coarse mica, high losses in the plant rejects are common. Large tonnages of tailings from the crushing and screening plants have been accumulated in a number of areas. Methods for treating such products were developed by the Bureau of Mines in 1941,2 but have not been generally applied. More recently, mica flotation research has been completed and published by the Bureau of Mines.3 These methods required complete removal of 150- to 200-mesh materials from the flotation feed with consequent fine mica losses. Later, the Bureau of. Mines investigated methods for-recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials, but not so drastically as to remove the fine sands. This report summarizes the results of these studies. The process developed was effective on pegmatite ores from two locations and should be applicable to the commercial treatment of other mica-bearing pegmatite ores and fine rejects that have been accumulated at various mica-milling operations. DESCRIPTION OF ORES The ores used in the investigation were obtained from the Dixie Mines, Inc., Heflin, Alabama, and the Ruberoid Corporation, Hartwell, Georgia. The sample from Alabama contained muscovite and quartz, with a high percentage of clay, and minor amounts of biotite, kaolin, limonite and tourmaline. The mica in the ore was essentially all minus 4-mesh in size and was free of attached mineral grains. The Georgia sample contained muscovite and quartz, with minor amounts of biotite, kaolin, and limonite. The mica in the ore, which was essentially all minus 4-mesh, was liberated. Petrographic analyses of the two samples are given in Table I. THE ANIONIC-CATIONIC MICA FLOTATION METHOD Previous investigators2,3 have reported that complete desliming of mica ores at 150- to 200-mesh was required prior to flotation with cationic collectors to obtain satisfactory selective separation of the mica from the other mineral components. Numerous tests were made at the Tuscaloosa Metallurgy Research Center to determine if some reagent combination could be used to selectively float finer size mica without complete desliming. The investigation led to development of a process using a simple reagent com-

Jan 1, 1967