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By Roscoe C. Clark, Henry F. Coffer, J. J. Reynolds

A cement slurry lightweight additive has been adapted in the Conoco laboratories for use in oil well cements. This additive makes possible the use of air to lighten oil well cement slurries. Specifically, the additive consists of small clay bubbles of air having sufficient strength to resist crushing by bottom hole pressures. Clay bubble cement slurry weights can be safely reduced to 10 Ibs/gal. In addition, the clay bubbles tend to act as lost circulation materials and to provide a cement texture which should produce good perforating characteristics. Clay bubble cement is relatively impermeable. INTRODUCTION In many areas in Oklahoma, Texas, Wyoming, and California, difficulties are experienced during casing cementing operations with lost returns caused by the high density of the cement slurries. Wells in these areas are ordinarily drilled with 9 to 11 lbs/gal. drilling mud while neat cement slurries may range in densities from 14.5 to 17 lbs/gal. In these areas, cement slurry weights are at present being successfully reduced to around 12 lbs/gal. (under bottom-hole conditions) by the use of additives in the cement. Since the use of additives will decrease the strength which the cement will develop, the amount of additives which can be used must be based on the minimum cement strength which is acceptable; and thus the maximum slurry weight can be reduced. At present, the minimum tensile strength generally acceptable is 50 lbs/sq in. cured for 24 hours under bottom-hole temperature. This figure is based on laboratory tests1 and on a large number of cement jobs which have been conducted using cement which will not develop more than 50 psi tensile strength in 24 hours under bottom-hole conditions. Two additives are now in use for decreasing cement slurry weights. These are expanded perlite and/or bentonite. The density of both of these materials is greater than that of the cement slurry; however, large quantities of water may be added with these materials without producing a slurry which will settle out of suspension. It is these large quantities of water which contribute to the reduction in the slurry weight. The minimum slurry weight at present obtainable with expanded perlite and/or bentonite is approximately 12 lbs/gal. using a standard Portland cement slurry. In many areas, this weight reduction is insufficient; and returns are still lost during casing cementing operations. In many cases, the pay formation itself is fractured; and a considerable quantity of this cement is lost to the pay zone. It is therefore believed that if cement slurry weights can be reduced to as low as 10 lbs/gal., two advantages will accrue: 1. The lighter densities (10 to 12 lbs/gal.) should mitigate or eliminate lost returns during casing cementing operations. 2. Cement slurries above 12 Ibs/gal. (the present minimum limit ) should develop considerably more strength than is now being obtained. A tensile strength of 100 psi is desirable.' It is the object of this paper to describe a cement slurry having a weight of 10 lbs/gal. and capable of

Jan 1, 1955

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 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 A. W. Dana, F. J. Shortsleeve, A. R. Troiano

The phenomenon of flake formation which may occur during cooling or room temperature aging of large steel sections is caused by a combination of hydrogen and stress. As such, the transformation characteristics of austenite in a particular section play a major role in the occurrence of flakes. Isothermal and continuous cooling studies demonstrated that flake formation is particularly sensitive to nature, distribution, and relative proportions of the microconstituents in the cooled sections. In the absence of transformation stresses, abnormally high hydrogen contents could be tolerated without flaking. Flakes were not found in the absence of transformation stresses. No correlation existed between average hydrogen content and flake formation where cooling stresses were low. Hydrogen in the steel was a necessary but not sufficient condition for flake formation. DESPITE a long history of laboratory and commercial investigations, the mechanics of hairline crack or flake formation in large steel sections remains unresolved. Recent publications1-5 emphasize that flaking is still a serious problem.* immediate cause of flaking is the pressure exerted by entrapped hydrogen gas that collects in small internal cavities or voids during cooling. When the temperature of steel is low enough to preclude extensive plastic flow, the cavity pressures cause local brittle fractures (flakes). 2—The microsegregation and transformation stress theory. According to this theory, flaking results from stresses arising from the volume changes accompanying the formation of martensite and/or low temperature bainite after a large portion of the section has transformed at elevated temperatures. The proponents of the hydrogen theory suggest that stresses from other sources may be additive to the stresses produced by hydrogen and may, in some cases, provide the increment of stress necessary to produce flakes. However, the critical aspect of this theory is that no stress, except that produced by hydrogen pressure, is believed to be sufficient in itself to produce flakes. For practical considerations, this means that the only safe thermal cycle is one that reduces the hydrogen content to some low critical level below which flaking will not occur regardless of the state of transformation. On the other hand, the transformation stress theory does not rule out the embrittling effect of hydrogen. This theory simply proposes that flaking does not occur in the absence of transformation stresses. With the transformation stress theory as a basis, commercial antiflaking cycles would be designed to complete the transformation of austenite prior to cooling to ambient temperatures. Both of these theories appear compatible with industrial experience. Antiflaking cycles, such as cooling at extremely conservative rates or soaking for periods of time in the upper subcritical temperature ranges prior to cooling to ambient temperatures, may allow the following: 1—diffusion of hydrogen out of the section and, as a consequence, reduction of the hydrogen content to some safe minimum value (hydrogen pressure theory) and 2—complete decomposition of the austenite at rela-

Jan 1, 1956

By H. E. Elliott, R. S. Busk, A. T. Peters

ONE of the problems of the fabricator of metals and alloys is the propensity of some composition ranges toward abnormal grain growth during certain stages of fabrication. In this respect magnesium alloys are no exception among alloys. Fortunately, convenient foundry control methods have been developed by which the abnormal grain growth possible in certain magnesium-alloy castings can be suppressed. An unusual characteristic of magnesium alloys, however, is that castings of some composition ranges are subject to local grain growth during heat-treatment without the necessity of intentional mechanical stressing of the part prior to heat-treatment. This effect occurs only under certain critical casting conditions, and only in certain alloys of greater than about 8.5 per cent aluminum content, such as C alloy (Mg, o per cent Al, 2 per cent Zn, 0.2 per cent Mn) and G alloy (Mg, i0 per cent Al, 0.2 per cent Mn). The first observation of this phenomenon in cast magnesium alloys occasioned much surprise, since it is not observed in other metals. Jeffries and Archer' have stated that "the grain size of cast metals, provided they have not been plastically deformed, cannot be changed by heating below the melting point." The study of the conditions leading to abnormal grain growth in cast magnesium alloys, and of the mechanism of this phenomenon, has led to some very interesting observations. Perhaps the most significant of these was the observation that stresses originating from cooling contraction in magnesium-alloy castings are the only stresses necessary, under certain conditions, to cause local recrystallization and subsequent grain growth in the casting during heat-treatment. of abnormal local grain growth was a definite problem in the production foundry on C alloy sand castings. Illustrated (Fig. r) is a picture of a casting scrapped because of this defect. A mottled effect is produced in coarse-grained areas by suitable etching solutions. The properties of metal in the affected area are much impaired by such grain coarsening. Ultimate tensile strengths of half the normal value have been measured in metal of this nature. In this paper are described the techniques that have been developed by The Dow Chemical Co. for studying, and in large measure solving, this production problem. Also discussed are studies of the mechanism by which excessive grain coarsening occurs, and the fundamental conditions that produce this effect. The abnormal grain growth discussed in this paper will be referred to as "germination," since this term has been defined' as any process leading to an abnormally coarse grain size. This paper deals only with abnormal local grain growth that may occur during the solution heat-treatment of certain magnesium-alloy castings, as dis-

Jan 1, 1945

By H. F. Silliman, Daniel R. Hull, John R. Freeman

In the normal operation of a brass-rolling mill, sheet and strip has, for the most part, been finished in comparatively thin gauges, involving a substantial amount of cold-work and a considerable number of anneals. This condition has been disturbed by the preponderance of cartridge brass, which is not rolled to thin gauges, and particularly by brass for artillery cartridge cases, on which the mill may finish its work at a thickness between 0.400 and 0.900 in. Obviously, the amount of rolling and the number of anneals to which such a product can be subjected are small compared with strip that is carried to a thickness of a few hundredths of an inch. As a result, critical examination into the internal condition of metal has been made on an extensive scale at a stage of manufacture that would not, in normal times, have been chosen for complete inspection. Under these conditions, a type of defect has been recognized that is not seen at thinner gauges. It might be more accurate to call it the appearance of a defect, since it refers to an apparently laminated, discontinuous structure, which, in fact, does not exist as such, and disappears after suitable treatment. For this reason it has been called a phantom lamination, which the authors consider an appropriate term. It is the purpose of this paper to describe the phenomenon and the conditions of its occurrence and, at least tentatively, to discuss its nature and cause. Great numbers of phantoms may be found in 2:r brass, either hot-rolled or cold-rolled. They are also found in 70-30 brass, sometimes when hot-rolled and generally when cold-rolled. It is not believed that phantoms are confined to these alloys but this paper is limited to them for the purpose of description. Hot-rolled 2:1 Brass For illustration, therefore, a typical cake of hot-rolled 2:I brass has been chosen. This was rolled to a slab 36 in. thick, from a casting 5 in. thick by 24 in. wide by 18 in. high, which was believed to have been sound. After hot-rolling and cooling, the slab was sheared and a portion of such a shear cut is shown in Fig. I. It would be difficult to convince anyone viewing this specimen that the metal was not unsound. The impression would be confirmed by the appearance of a tensile break, as shown in Fig. 2. This is an ordinary tensile-test piece from metal just described. Although there was nothing in its tensile strength or elongation that suggested unsoundness, it appeared run through with pipes and laminations. To question the reality of such a condition would imply questioning the obvious. But, considering the history of the metal, it would be difficult to believe that it could be so bad as it appeared. It seemed reasonable, though, that if the defects were what they appeared to be, they could be traced back from the sheared or broken face.

Jan 1, 1945

By C. E. Nelson

The purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. Types oF Melting Practice All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.2 The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be ' parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drying out or thickening after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to be poured out directly into castings without fear of flux contamination. This flux is not

Jan 1, 1944

By P. R. Schmidt, N. J. Themelis

A study zvas made of the deoxidation of copper at 1170°C by injecting a jet of carbon monoxide vertically upwards into the melt. The effects of submersion depth (2 to 20 cm), orifice diameter (& to 5 in.), and gas velocity (100 to 3650 ft per sec) were examined. In the oxygen range 0.1 to 1.0 pct 0, the overall rate was conlrolled by gaseoLcs mass Lransfer. The results were interpreted in terms of a rate coefficient per unit depth which was found to be constant with distance along the jet axis and nearly proportional to the orifice Reynolds number in the range 1000 < NReo < 9100. AS the gas flow rate through an orifice submerged in a liquid is progressively increased, at least three regions of bubble formation may be distinguished. At very low rates, the formation of bubbles is practically a static phenomenon, depending on the orifice diameter, the liquid surface tension, and the densities of the two phases. In this region, the bubble size is constant while the frequency of bubble formation increases with gas flow rate.&apos;-3 At higher flows (500 < NR~, < 2100), the frequency of bubble formation reaches a steady value and the bubble size increases with gas flow rate; when the bubbles issuing from the orifice become so large that they start coalescing to form larger bubbles, the turbulence induced in the liquid by the passage of previous bubbles shatters them into small bubbles of varying size. Finally, for gas velocities in the intermediate and turbulent regions of flow (NR,, > 2100) a tangential separation surface is created around the jet and momentum transfer takes place between it and the surrounding liquid medium. The entrainment of liquid and the resulting deceleration of the gas-liquid dispersion causes the jet to expand forming a characteristic jet cone. The large velocity and density differences between the jet and the liquid result in a high degree of instability and the jet envelope fluctuates rapidly.The characteristic jet cone can be observed by means of time exposure photographs such as those shown in Fig. 1 for an air jet introduced vertically upwards in a water bath. High-speed photography has showns that the gas-liquid dispersion within the cone consists of small bubbles the size of which depends mainly on the jet orifice diameter and Reynolds number. In the laminar region of flow, the following correlation was obtained by Leibson: The results of Liebson et a1.&apos; are plotted in Fig. 2. It can be seen that the region 2000 < NReo c 10,000 is not well-defined experimentally. In the entrance to the fully turbulent region of flow (NR,, = 10,000), the mean bubble diameter decreased to about 0.4 cm and varied only slightly from there on according to the correlation:

Jan 1, 1968

By J. C. McCarthy, J. B. Stone

AT Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. LOCATION The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in the world. Another famous old silver district, Sombrerete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo station on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo ís surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proaño hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proano hill are the Fresnillo mines, and it is marked now by a great gash cut by glory-hole mining. HISTORY According to an account written in 1834 by Francisco García, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between Zacatecas and Sombrerete. Little is known of the earliest mining at Fresnillo, which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notably active ín 1751 under an administrator named Murguía, who left detailed notes describing them. In 1757, however, the mines became inactive because of difficulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresníllo became the property of the State of Zacatecas because the interest of Governor García had been aroused by the long disregarded notes of Murguía. Under García&apos;s energetic leadership the mines were reopened, and silver production began in 1832 ín spite of serious difficulties, including abnormal rains and an epidemic of cholera. In 1835 English capital was sought to allow installation of steam-driven Cornish pumps at the two principal shafts and to build the great hacienda de beneficio (the present Proaño hacienda). The company formed in 11835 (Cia. Zacatecano Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1942

By J. Hunter

DuXing 1942, Louisiana attained the rank of fourth among the great oil-producing states of this country. Its present prominent position is the result of an orderly and systematic program of exploitation with emphasis on conservation. Even before the functioning of M-68, the Federal spacing order, development and production in Louisiana were regulated by various acts of legislation, the most recent of which and by far the most effective is Act 157 of 1940. Under the authority of this act, it has been possible for the Department of Conservation to hold many public hearings and thereby to secure data and evidence regarding the feasibility of issuing rules and regulations for development of various oil and gas fields in the state. As a result of information compiled at such public hearings, many orders have been issued by the Commissioner of Conservation that have in most cases provided reasonable solutions to the problems that arise in the exploitation and development of fields in this state. Probably one of the most effective powers granted the Commissioner of Conservation in the state of Louisiana has been the authority to provide for fieldwide unitiza-tion and pooling of condensate fields. This has led to the erection of huge cycling plants in Louisiana, which permit the most efficient recovery of the liquid content of the reservoirs, and further conserve most of the gas reserve that undoubtedly will be of considerable future value. Many months have passed since various orders of the Department of Conservation were put into effect, and all are accomplishing their purpose; namely, the elimination of waste. Although the effectiveness of these orders provides considerable satisfaction to the members of the Department of Conservation, it is also a tribute to the members of the oil and gas industry in Louisiana, who, in addition to providing carefully prepared technical data, have also given unstinting cooperation and have thereby enabled the Department to cope intelligently with the many problems. Production On Dec. 31, 1942, oil and/or gas was being produced in 50 parishes, or 78 per cent of all the parishes in the state. Thirty-three of the parishes produced oil and gas, 12 produced oil, and 5 produced solely gas. This is indeed an enviable record for any state. However, it is reasonable to assume that eventually all parishes in the state of Louisiana will be productive. From a geological viewpoint, there is no apparent reason to assume otherwise—a point that a11 operators seeking oil and gas production in this state may well bear in mind. Twenty new fields were found during 1942—a rate of discovery that does not compare favorably with the 30 new fields found during 1941. The record of discoveries in Louisiana during 1942 is further disappointing when it is realized that 8 of the 20 new fields discovered were gas fields. During this period of war emergency, there are, of course, many

Jan 1, 1943

By J. Hunter

DuXing 1942, Louisiana attained the rank of fourth among the great oil-producing states of this country. Its present prominent position is the result of an orderly and systematic program of exploitation with emphasis on conservation. Even before the functioning of M-68, the Federal spacing order, development and production in Louisiana were regulated by various acts of legislation, the most recent of which and by far the most effective is Act 157 of 1940. Under the authority of this act, it has been possible for the Department of Conservation to hold many public hearings and thereby to secure data and evidence regarding the feasibility of issuing rules and regulations for development of various oil and gas fields in the state. As a result of information compiled at such public hearings, many orders have been issued by the Commissioner of Conservation that have in most cases provided reasonable solutions to the problems that arise in the exploitation and development of fields in this state. Probably one of the most effective powers granted the Commissioner of Conservation in the state of Louisiana has been the authority to provide for fieldwide unitiza-tion and pooling of condensate fields. This has led to the erection of huge cycling plants in Louisiana, which permit the most efficient recovery of the liquid content of the reservoirs, and further conserve most of the gas reserve that undoubtedly will be of considerable future value. Many months have passed since various orders of the Department of Conservation were put into effect, and all are accomplishing their purpose; namely, the elimination of waste. Although the effectiveness of these orders provides considerable satisfaction to the members of the Department of Conservation, it is also a tribute to the members of the oil and gas industry in Louisiana, who, in addition to providing carefully prepared technical data, have also given unstinting cooperation and have thereby enabled the Department to cope intelligently with the many problems. Production On Dec. 31, 1942, oil and/or gas was being produced in 50 parishes, or 78 per cent of all the parishes in the state. Thirty-three of the parishes produced oil and gas, 12 produced oil, and 5 produced solely gas. This is indeed an enviable record for any state. However, it is reasonable to assume that eventually all parishes in the state of Louisiana will be productive. From a geological viewpoint, there is no apparent reason to assume otherwise—a point that a11 operators seeking oil and gas production in this state may well bear in mind. Twenty new fields were found during 1942—a rate of discovery that does not compare favorably with the 30 new fields found during 1941. The record of discoveries in Louisiana during 1942 is further disappointing when it is realized that 8 of the 20 new fields discovered were gas fields. During this period of war emergency, there are, of course, many

Jan 1, 1943

By R. A. Wagstaff

Since the time of the early Egyptians, the use of copper: has been a boon to the life of most of the civilized world. Its use has been varied; in many connections, the art by which it attained its greatest usefulness has been lost. In this paper an endeavor will be made to take into consideration some of the many changes that have occurred during the last 40 years of copper-smelting operations. During that period the copper blast furnace has been almost forced out of existence by new methods of ore concen-tration—first, gravity concentration, and then flotation. These new methods of concentration introduced many new factors into the metallurgy of copper. The product was wet, it was fine and it was high grade. To overcome all these factors many changes have been necessary throughout the smelting agenda. New equipment has been necessary for transportation, unloading, sampling, bedding and moisturing in all smelting plants, especially the custom smelter&apos; During the early days of "flotation," little was known about filtering or the use of an alkaline circuit; often the concentrate going to the smelter contained 2&apos; to &apos;5 Per cent moisture. It is easy to imagine the difficulty arising with a product of this nature when it had to be shoveled by hand labor. To meet these conditions, mechanical unload- ing and sampling devices were soon developed. In many instances such good progress was made that actual costs for handling this unfavorable product were lower than those formerly incurred on the old product. Today most sampling of copper ores and concentrates is being done by mechanical sampling, pipe or augur sampling, or shovel sampling. Where concentrates are uniform in metal content, a great many of the plants now use pipe or augur sampling. For spotty ores, the old shovel sample with cone and quartering during the final stages is still in&apos; use. Where big tonnages are handled, mechanical sampling of concentrates is being done, with satisfactory results. To curtail slow and tedious cutting and mixing procedure, mechanical mixing boxes, splitters and cutters are used to cut down labor costs. Milling As crude ores become scarcer, the use of milling operations increases. The few crude ores that are still smelted are used as fluxing types. To use these ores finer grinding has been found advantageous. This has made for better bedding and fluxillg conditions, which in turn makes for faster smelting, lower fuel consumption and better metal recovery. The degree of fineness is more or less determined by the nature of the product. Most plants have set a standard of through 3/8-in. mesh screen for roaster -reverberatory smelting and through 3/4-in. mesh screen for converter fluxes. For some refractory Ores, even finer grinding has been found to be advantageous for good reverberatory smelting-

Jan 1, 1944

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675&apos; and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675&apos; and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By J. H. Henderson, J. Naar

The displacement of a wetting fluid from a porous medium by a non-wetting fluid (drainage) is now reasonably well understood. A complete explanation has yet to be found for the analogous case of a wetting fluid being spontaneously imbibed and the non-wetting phase displaced (imbibition). During the displacement of oil or gas by water in a water-wet sand, the porous medium ordinarily imbibes water. The amount of oil recovered, the cost of recovery and the production history seem then to be controlled mainly by pore geometry. The influence of pore geometry is reflected in drainage and imbibition capillary-pressure curves and relative permeability curves. Relative permeability curves for a particular consolidated sand show that at any given saturation the permeability to oil during imbibition is smaller than during drainage. &apos; Low imbibition permeabilities suggest that the non-wetting phase, oil or gas, is gradually trapped by the advancing water. This paper describes a mathematical image (model) of consolidated porous rock based on the concept of the trapping of the non-wetting phase during the imbibition process. The following items have been derived from the model. 1. A direct relation between the relative permeability characteristics during imbibition and those observed during drainage. 2. A theoretical limit for the fractional amount of oil or gas recoverable by imbibition. 3. An expression for the resistivity index which can be used in connection with the formula for wetting-phase relative permeability to check the consistency of the model. 4. The Iimits of flow performance for a given rock dictated by complete wetting by either oil or water. 5. The factors controlling oil recovery by imbibition in the presence of free gas. The complexity of a porous medium is such that drastic simplifications must be introduced to obtain a model amenable to mathematical treatment. Many parameters have been introduced by others in Iprogressing" from the parallel-capillary model to the randomly interconnected capillary models independently proposed by Wyllie and Gardner3 and Marshall4. To these a further complication must be added since an imbibition model must trap part of the non-wetting phase during imbibition of the wetting phase. Like so many of the previously introduced complications, this fluid-block was introduced to make the model performance fit the observed imbibition flow behavior. THE IMBIBITION MODEL ASSUMPTIONS The following assumptions are common to many two-phase models previously described. 1. The wetting characteristics of the medium are clearly defined. 2. When two fluids co-exist in the medium, the wetting phase will fill the smaller pores and the non-wetting fluid the bigger ones. 3. The pores have a circular cross section. 4. Apparent pore radii are related to the capillary pressure (drainage) by

By Thomas G. Murdock

ETHIOPIA, the first country to be liberated from Axis domination, has recovered remarkably from the ravages of occupation and war. Mineral production has contributed significantly towards this recovery, as it has provided a means of obtaining foreign exchange and has given employment to hundreds of workmen whose maintenance otherwise would have presented a problem. Although primarily an agricultural country, never with a large mineral production, Ethiopia has within its borders a variety of minerals, both precious metals and nonmetallics. Some of these are important to the country as a national asset and others contribute greatly to local economy and can be expected to do so even to a greater extent in the future1 (Fig I). PHYSIOGRAPHY AND GEOLOGY The Empire of Ethiopia is essentially a mountainous and volcanic country, in northeast Africa, situated principally between latitude 4° and I5°N and longitude 34° and 44°E. It is bounded on the north by Eritrea, on the northeast by French Somaliland, on the southeast by Italian Somaliland, on the south by Kenya Colony, and on the west by Anglo-Egyptian Sudan. These European possessions thus completely surround the country. Its access to the Red Sea is through Eritrea; to the Gulf of Aden, through French or British Somaliland; and, to the Indian Ocean, via Italian Somaliland. These routes range in length from 40 to 250 miles. Ethiopia has an area of approximately 350,000 square miles, with a width from north to south of 625 miles, and a maximum length from east to west, along latitude 8°N, of about 875 miles. Physiographically the country is characterized by two very extensive sub-tabular plateaus: the Ethiopian Plateau to the northwest and the Somaliland Plateau to the southeast, separated by a long tectonic graben-the Rift Valley of the Galla Lakes and Danakil. The Ethiopian Plateau, deeply cut and notched by the drainage, slopes in a general northwest direction toward the Sudanese Plains and the valley of the Nile; the Somaliland Plateau slopes to the southeast, toward the Indian Ocean. The valley of the Galla Lakes and its extension to the northeast-the Awash River Valley, separates the plateaus, from Lake Rudolph to Danakil. This depression which constitutes a continuation or ramification of the Great Rift Valley of Central Africa joins in turn the trough of the Gulf of Aden and the Danakil-Eritrean Rift, continuations of the Red Sea and the Jordan Valley. The general basement of Ethiopia is made up of very old rocks, usually considered as Archaen.2 These rocks are represented by the metamorphic crystallines, such as gneisses, different kinds of schists, included lenses of crystalline limestone, and massive intrusives such as granites, diorites, and syenites, all cut by

Jan 1, 1947

By K. E. Merklin, F. D. DeVaney

In the past most of the research in pelletizing has as its aim the production of a physically strong pellet. Now that this problem is solved, more attention is being paid to uniformity in grade and chemical composition. Consideration has been given in recent years to a study of additives which will make pellets partially or fully fluxed. Blast furnace tests show fluxed pellets to have advantages over both fluxed sinter and acid pellets. Lower slag volumes are used more frequently in the blast furnace and the uniformity of the charge, both physically and chemically, is becoming increasingly important. A considerable improvement can be secured by having all of the flux uniformly distributed through the pellets in a calcined state. A fluxed pellet, therefore, should be a superior product. The use of an ore burden that contains an appropriate quantity of fluxing materials is not new to the blast furnace industry. For years the Minette ores of France and Germany, the Clinton ores of the Birmingham, Ala., areas, as well as others, which are low in iron but contain calcium carbonate in sufficient quantities to give them self-fluxing properties, have proven economical. The adaption of the sintering process to the preparation of ore burdens provided a means for artifically associating the fluxstone with the iron ore prior to charging to the blast furnace. In 1944 Torpl discussed the effects of using lime in sinter made in Sweden on the sinter&apos;s metallurgical performance in a blast furnace. Hessle2 reported in 1945 on the advantages of using lime in sinter to increase the sintering plants&apos; capacity and reduce fuel requirements. Robinson3 discussed the use of lime in Swedish sintering practice at the 1950 Blast Furnace, Coke Oven, and Raw Materials meeting. One of the suggested advantages was the combining of lime with silica to prevent the formation of a fayalite slag, which is difficult to reduce in the blast furnace. Nilson4 at the same meeting commented briefly on experimental work that had just started in the U. S. on the use of lime in sinter. The literature tends to indicate that most of this early work was directed towards improvement in sinter physical quality, and the fact that the feed to the blast furnace was partially fluxed was incidental. It was not long, however, before blast furnace advantages were being claimed. The matter was forcibly called to the attention of North American operators by reports of remarkable production records established by the Russians using fluxed sinter. The leading step was taken on this continent by the Steel Company of Canada in 1957; McMahon5 reported on the marked improvement in performance of an 18-ft blast furnace using fluxed sinter at its Hamilton works. Other North American operators quickly followed theStelco lead.

Jan 1, 1963

By M. I. Sherman, J. D. H. Strickland

PRELIMINARY experiments in these laboratories showed that whereas pyrite1 produced only sul-fate the action of aqueous chlorine solutions on most other sulfide ores resulted in the formation of a mixture of sulfate and elemental sulfur, the production of the latter being favored by a very dilute solution of oxidant. The reactions taking place were obviously complex and only a detailed kinetic study could be expected to clarify the position and enable a prediction to be made of conditions leading to the rapid formation of metal salt and the economically desirable elemental form of sulfur. Galena was chosen for the first investigation as it is of widespread occurrence and is representative of a simple cubic lattice sulfide containing the monosulfide unit, S2-. Experimental Procedure The apparatus and general technique used in this work have already been described.&apos; Analyses for chlorine and sulfate were carried out by the same methods as those used for pyrite. The lead in 1 ml aliquots of solution was determined polarographi-cally, after destroying chlorine with hydrazine hy-drochloride and making solutions 0.5 molar with hydrochloric acid. A large sample of Kansas galena, assaying at better than 98 pet PbS, was crushed and wet sieved to give fractions of —10 + 14, —20 + 28, —28 + 35, and —48 + 65 Tyler screen. The particles were almost perfect cubes and the apparent surface Per gram was calculated assuming each particle a cube Of side equal to the mean mesh opening. A volume shape factor, calculated as for pyrite, was exactly unity. The main apparatus was unsuitable for direct visual examination of the ore particles during the reaction. For this purpose a small cell from a Spekker Absorptiometer optical flats 1 cm apart) was l by a greased microscope slide after filling with oxidant solution. One or two ore particles were placed in the cell and the solution was stirred by a glass covered speck of iron wire activated by an external rotating magnet. The surface of an ore particle was examined under a binocular microscope at between 10 and 40 magnifications. Results Experiments were made under a wide variety of conditions, the form of presentation of the data being illustrated by Fig. 1, where the concentrations of chlorine, sulfate, and sulfur are plotted against time. The fictitious concentration of solid sulfur is used for convenience and is the molarity of sulfur which would be recorded if the elementary sulfur formed during the reaction were dissolved in the liquid iii the reaction vessel. As some lead sulfate is occluded with the sulfur on the ore particles the amounts of sulfur and sulfate formed during a reaction cannot be calculated

Jan 1, 1958

By F. J. Fayers, S. A. Hovanessian

The one-dimensional displacement equation for a homogeneous porous medium, including the effects of gravity and capillaty forces, has been solved by a numerical method. A finite-difference scheme is developed for obtaining saturation, pressure and fractional flow profiles in waterflood recovety problems. From the numerical examples given, it is concluded that the gravitational forces have a pronounced effect on the saturation profiles and the pressure distribution curves of the system. INTRODUCTION Within the past 20 years, a number of papers have appeared in the literature dealing with the quantitative treatment of waterflood recovery problems. In their celebrated paper, Buckley and Leverett1 described a method for calculating saturation profiles when the effects of capillary pressure and gravity are excluded. Terwilliger, et al,2 included the effect of gravity in their theoretical and experimental investigation of oil recovery problems and obtained close correlation between experiment and theory. welge3 described a simplified method for obtaining the average saturation and the oil recovery from an oil reservoir. The effect of gravity can be included in this calculation. More recently (1958) Douglas, et al,4 presented a method for calculating saturation profiles which includes the effect of capillary pressure. The authors start with the one-dimensional displacement equation (which is nonlinear in the derivative) and, by a change of variable, transform this equation to a semi-linear partial differential equation. This equation is then solved by a finite-difference method on a high-speed digital computer. Fayers and Sheldon5 obtained the solution of the one-dimensional displacement equation by directly replacing the differential equation by a finite-difference equation. The effects of capillary pressure and gravity were in- cluded in their solution. Here, since the movement of the foot of the saturation front is governed by a separate equation, the elapsed time in attaining a particular saturation profile cannot be obtained. The results of these two papers indicate that the inclusion of capillary forces eliminates the triple-valued Buckley-Leverett saturation profiles. In the present paper, the one-dimensional displacement equation for a homogeneous permeable medium, including the effects of capillary and gravity forces, is solved. The method of solution resembles that described in the paper by Douglas, et al, since it involves a similar transformation of variable. However, it extends their work in that the effect of gravity is included and, in addition, pressure profiles may be calculated. Also, the functions of saturation [kro(S), krw(S) and Pc (S) ] required are entered in tabular form rather than as low-order polynomials. This simplifies data preparation and permits the use of a greater range of function types. Unlike the method of Fayers and Sheldon, the corresponding elapsed time required for the development of each saturation profile is calculated and, also, saturation profiles may be calculated after breakthrough. THEORETICAL CONSIDERATIONS The dimensionless form of the one-dimensional displacement equation for a homogeneous porous medium as obtained from Darcy&apos;s law and material balance relations can be written as follows.

By Wallace Thorneycroft

This paper by Mr. Thorneycroft, Past President of the Institution of Mining Engineers (Great Britain), and chairman of its Subsidence Committee, is a valuable contribution to the assemblage of data on ground movement and subsidence from coal mining. It deals with the effects of advancing longwall, a method almost universal in Europe but as yet little used in the United States outside of Northern Illinois and in a few scattered places elsewhere in thin coal beds, as in the Lexington field, Missouri. Canon City field, Colorado, and the Birmingham field, Alabama. Although by advancing lougwall, a maximum recovery of coal is obtained and it has to be employed where there are weak shale roofs, especially in deep mines, it is a more expensive method of operation unless the mining conditions are suitable, which is unusual in the United States. On the other hand, there is a growing use in this country of what is essentially retreating longwall, with an approximately straight break-line as described by Rayburn.1 With this method, in which the pillars are substantial, it was shown that the ground movement effect is practically identical with that of advancing longwall, hence the value to mining engineers of the precise data given by Mr. Thorneycroft. His study is unusual in several respects; it deals with conditions connected with the mining of a coal bed 20 in. thick, about 490 ft. below the surface, over a mined-out area in a 5-ft. bed about 90 ft. below, which had been mined about 12 years earlier. Both mines passed under Plean House, a building of massive cut stone construction built over a century ago, in which Mr. Thorneycroft resided throughout the under-mining period. Slight cracks opened in the walls as the longwall face approached the house in mining the upper seam, and closed after the face passed and subsidence took place. In the northwest wall, the last wall the face passed under, some stone blocks were broken, which was attributed to a strike period when the advance of face came nearly to a standstill. Other than this there was no perceptible permanent damage, as indicated by the photographs taken by the undersigned in 1923 (Figs. 1 and 2). Mr. Thorneycroft used a novel means of studying the successive positions of the corners of the building: he hung plumb bobs from the eaves and traced the paths of the respective plumb bob points on level surfaces. The angles made by the house walls with the plumb bob lines gave measures of the slope of the subsidence wave at the respective points. A slight upward wave was indicated by the surveys ahead of the subsidence, which would appear to be due to a tilting over of the massive sandstone stratum in the roof measures near the surface, the edge of the coal face acting as the fulcrum.

Jan 1, 1931