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By Robert D. Pehlke, Arden L. Bement

A mass transfer coefficient for the removal of hydrogen from liquid aluminum by inert flush degassing has been determined experimentally at 700°C. A mathematical model has been derived, assuming transport control, which adequately describes the experimental data. The removal of hydrogen is shown to increase with decreasing bubble size, and with increasing flow of flushing gas. The presence of hydrogen in liquid metals in amounts which exceed the solid solubility at one atmosphere hydrogen pressure is highly undesirable, causing unsound ingots or castings, or resulting in difficulties during further fabrication. The removal of hydrogen from liquid metals can be accomplished by several methods, the principal two being vacuum treating and inert flush degassing. The design of a process involving either of these techniques is based on the mass transfer coefficient for hydrogen between the liquid metal and a hydrogen-dilute gas phase. In an effort to extend our knowledge in this area, an investigation of the rate of removal of hydrogen from liquid metals by inert gas flushing was undertaken. In view of the difficulties encountered with gas porosity in the casting of aluminum and aluminum alloys, and because of certain experimental advantages, liquid aluminum was selected for the study. PREVIOUS INVESTIGATIONS The removal of gases from liquid metals, particularly steel, has received considerable attention in recent years, The first definitive work of a theoretical nature was presented by Geller1 who considered the case where equilibrium exists between purging gases and metal bath during flushing, and also deviations from this ideal case. Hulme2 has surveyed a number of experimental studies and discussed some of the practical limitations of removing dissolved gases from molten metals. More recently a number of studies have been reported on degassing of steel melts by flushing with an inert gas.3'4 Considerable work has also been reported on aqueous and organic liquid-gas systems, and an excellent summary prepared by Hovis.5 The treatment of liquid aluminum by a flushing gas to remove dissolved hydrogen has been known for several decades.6 A number of gases have been used for this purpose, including nitrogen, argon, and chlorine, or mixtures of these gases. Tikkanen and Erkko7 have studied the relative density changes of aluminum castings poured from melts degassed with chlorine, nitrogen, and mixtures of the two gases. Their

Jan 1, 1962

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

Lime and dicalcium-silicate crucibles were equilibrated with molten iron and liquid slags containing iron oxide and small amounts of sulfur. The oxygen content of metal, iron oxide activities, and desulfurization values of the slags were determined in the temperature range 1530 to 1700°C. The influence of magnesia in the slag and the temperature dependence of the solubility of lime in liquid iron oxide and the ferric oxide content were established. The temperature contour of the liquidus surface of iron-silicate slags saturated with lime and dicalcium silicate was also established at 1600°C. THE importance of the role that slag composition plays in the refining of steel has been known for many years. Numerous studies have been made using actual plant data in order to establish the relationship between the composition of the slag and metal during the refining of a heat of liquid steel. These results rarely represent equilibrium conditions since completion of the various chemical reactions involved in steelmaking is seldom realized. In order to establish quantitatively the equilibrium conditions existing between the slag and metal, several laboratory studies have been conducted in the past 20 years to determine the reactions important in slag control. These investigations have included studies of simple liquid basic and acid slags as well as more complex slag systems which approach those commonly found during the refining of a heat of steel. Since most of the previous studies of simple basic iron-oxide slags equilibriated with molten iron were made in magnesia crucibles, it was not possible to establish the distribution of sulfur and oxygen between molten iron and slags consisting only of the three essential components, lime, silica, and iron oxide. This investigation was undertaken to establish the equilibrium conditions for simple lime-iron oxide and lime-silica-iron oxide slags. Accordingly, it was expedient to prepare crucibles both of lime and dicalcium silicate to establish the equilibrium conditions between molten iron and iron-oxide slags saturated with the refractory materials and free from other components. The only other studies of the equilibrium between molten iron and lime-saturated slags are those of Fischer and vom Ende, 1, 2 in which the solubility of oxygen was determined in an air atmosphere. The

Jan 1, 1959

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By Ian Wark

IN the paper on the development of the flotation process at Broken Hill (Australia) prepared by the Broken Hill Branch of the Australasian Institute of Mining and Metallurgy and published in its Proceedings for 1930 (N. S. 80), it is stated that the concentration of ores by flotation has been established on a commercial basis in Australia since 1904 and that differential flotation was practiced at Broken Hill in 1912. Since then, progress in flotation practice throughout the world has been rapid, and during recent years the knowledge of the reactions between comparatively modern so-called chemical promoters or collecting agents and the mineral surfaces has been broadened by the published accounts off many investigators, particularly those working in American universities. Because of the benefits the Australian mining industry has derived from the flotation process, it was felt that the industry should take some part in the efforts that are being made to extend the knowledge of the principles on which the flotation process is based. Accordingly, early in 1930, three Broken Hill mining companies-the Broken Hill South, the North Broken Hill, and the Zinc Corporation-together with the Electrolytic Zinc Co. of Australasia, Ltd., and the Mount Lyell Mining & Railway Co., established a laboratory in the chemistry department of the University of Melbourne for the purpose of investigating the principles underlying flotation. Subsequently, the Burma Corporation, Ltd., expressed a desire to cooperate. The two authors are directly employed and controlled by these six organizations, and the cost of the investigation is divided equally among them. The research has been carried out under the general direction and in close cooperation with Harry Hey, chief metallurgist for the Electrolytic Zinc Co. of Australasia, Ltd., and the authors desire to place on record their indebtedness to him for his ever willing help and constructive criticism.

Jan 1, 1932

By G. L. Oldright, Henry de Rycker, S. F. Ravitz

The upper limit of richness of concentrates that can be smelted by means of the blast furnace without added diluents is fixed by the operation of sintering. A sinter feed with normal gangue constituents, containing more than about 50 per cent of lead, tends to fuse; as a result, air does not come sufficiently into contact with the sulphides at roasting temperatures, and sulphur elimination is poor. Since most lead concentrates now contain 55 to 80 per cent lead, it is necessary to add diluents to lower the grade of such sinter feed to about 50 per cent or less. This not only entails the expense of providing barren diluents when adequate diluents containing precious metals are not available but also appreciably lowers the capacity of the blast furnace to produce lead and increases slag losses. Attempts to desulphurize rich lead concentrates by methods other than sintering have not proved successful. Flash roasting, for example, converts much of the lead sulphide to lead sulphate rather than to oxide. However, this suggested the possibility that deliberate flash roasting of the concentrates to sulphate, followed by sinter roasting of the resulting product, might prove promising, particularly inasmuch as the elimination of sulphur from lead sulphate requires heat alone and not contact with atmospheric oxygen. The sintering of lead sulphate products has additional interest because important amounts of such products are now treated by lead smelters. Considerable quantities of lead sulphate are present in rich lead flue dusts and other by-products; lead-chamber sulphuric acid plants and other

Jan 1, 1944

By Arthur F. L. Bell

Prior to 1908 the oil production in the State of California had been almost entirely a heavy fuel oil, with a high flash point, but changed within a short period to a large percentage of refining oil with a low flash, by reason of the heavy production of light oil coming in from the Santa Maria field, the Midway field, and the increased production of the Fullerton field. This is clearly shown in the following tabulation of California's pro- The bringing in of these high percentages of light oil with their dangerous low flash and the increasing demand for the refined products necessitated the devising of some cheap and efficient means of quickly separating the lighter elements either in the field or at the main distributing points; also it became necessary to remove the excessive percentage of water which many of the light oils carried in emulsion. Union Oil Co. Port Harford Plant Probably the first important attempt to top light oil in California by other means than the ordinary stills was tried about 1908 by the Union Oil Co., at its plant at Port Harford, San Luis Obispo County, with Santa Maria oils. The process was the invention of Hubert G. Burroughs who afterward obtained a patent for the process, No. 998,837, dated July 25, 1911. The apparatus used consisted of a series of 12-in. pipes mounted in units of three pipes, one above the other, the crude oil being admitted to the upper pipe and filling it about two-thirds of its

Jan 1, 1916

By G. W. Healy, W. Craft, D. C. Hilty

By means of a theoretical extension of the Cr-C temperature relation in molten chromium steels to low chromium contents and by a correlation of the ratios of chromium to iron in the slag and metal, a method has been developed for estimating the amount of metallic oxidation during the oxidizing period of a chromium steel heat. Application of this method has indicated that due to temperature limitations metallic oxidation may be excessive for very low carbon steels charged with more than a small amount of chromium. IN the melting and refining of chromium steels the oxidation of carbon to a low level is accompanied by the oxidation of chromium and iron in considerable amounts. For the subsequent recovery of chromium and associated iron from the slag, the amounts of metal oxidized must be known for efficient reduction and control of composition. Further, in order to arrive at an accurate understanding of the process, so that chromium-bearing scrap can be used effectively, information is required on the relation between composition of the charge and weight of metal oxidized to reach the desired carbon content. Crafts and Rassbach1 recently developed an empirical relation between chromium, iron, and manganese oxidized per ton of steel charged, and final carbon content and temperature. This relation did not show any dependence on amount of chromium charged. However, it was felt that such a dependence might be present, so a further analysis of the data was undertaken. Cr-C Relation at Low Chromium Levels Crafts and Rassbach's results were based on temperatures estimated from the Cr-C relation previously established experimentally by Hilty,2 and on a single temperature observation (immersion thermocouple) on a heat made at low temperature from a charge of carbon steel scrap containing only a small amount of residual chromium. The temperatures estimated from the Cr-C relation were for heats charged with chromium-bearing scrap and which contained substantial amounts of chromium (2 to 10 pct) at the end of the oxidizing period. No data, other than that from the low temperature heat just mentioned, were available for the low and intermediate chromium ranges. In order to extend the range in which temperature may be estimated, the Cr-C relation requires further consideration. The Cr-C relation, expressed as suggests that carbon is zero at zero chromium in the bath. This is obviously absurd, because as chromium approaches zero the carbon content must approach the limit established by the Fe-C-O equilibrium. It is evident, therefore, that the Cr-C relation as defined by Eq. 1 is not valid below some minimum chromium content that may vary with temperature. On the other hand, it is probable that any such limiting chromium content is less than 4 pct at 3200°F, since the experimental data from which the Cr-C relation was derived included several observations at that level with no deviation. In any event, it is apparent that further evaluation of the results presented by Crafts and Rassbach is dependent upon a means for estimating the Cr-C temperature relation in the low chromium region. From the observations of Chen and Chipman9 and thermodynamic data given in Basic Open Hearth Steelmaking,4 the following relation can be calculated for melts containing small amounts of chromium and carbon assuming a carbon monoxide pressure of 1 atm: % Cr -21,250 K' = (%C)2; logK1 == —t— +13.88 [2] Moreover, by plotting Eq. 2 for any given temperature on cartesian coordinates, it can be extrapolated graphically to the limiting carbon content at zero chromium for the specified temperature without serious complications. By means of Eq. 2 and its extrapolation, the Cr-C temperature relations originally established experi-

Jan 1, 1954

By W. H. Adams

Virginia, a store-house of metals, is more and more a surprise to the present generation. With her enormous available mineral wealth, worked upon steadily for over a century, exploited SUEciently to demonstrate beyond question costs and values, reported upon by our most eminent scientists, written up by thoroughly earnest correspondents, we yet find her little understood by capitalists or practical men, and until very lately overlooked by the advanceguard of pioneers in metallurgy, whose restless energy conquered the wilderness of Northern Michigan years ago, and has written a new and startling history for almost impenetrable Western territories. The world is learning through the mouths of giant furnaces lately put in blast at Lowmoor, Goshen, and Roanoke, more of this wondcrful State. It is becoming plain that nearer home, amid all the surroundings of civilization, under an equable climate and with the advantage of a minimum cost for fuel and labor, there are stores of mineral, varied in character and deposited over a wide area, which exceed all ordinary calcnlations. Principal among these minerals, iron ores have been, and will probably continue to be, the leading product and the source of greatest revenue. My attention has been called during the past year to one particular section of the iron-belt, where for forty years charcoal-furnaces were successfully operated, the ores being mined in open pits, as can so frequently be seen from the Connecticut line southward into Georgia. There is, however, a significant peculiarity in the character of these deposits of Louisa county warranting special mention, as it is thought that nowhere on the earth's surface, within so moderate a distance of tidewater, can their like be fouad. Probably half a million tons of lump and wash-material have been taken from pits

Jan 1, 1884

By Frank C. Greene

The principal event in the development of oil and gas in Missouri in 1942 was the drilling of the Cities Service Oil Company's No. I Jim Cook, in the northwest corner, NW. 1/4 sec. 32, T. 65 N., R. 39 W., Atchison County, in the northwest corner of Missouri. This well, not yet completed, bailed several barrels of free oil in about 27° Baume from a sand called the Bartlesville by those in charge, at a depth of 1450 ft. The well is on a block of leases obtained after the area, which is covered by several hundred feet of glacial drift, had been prospected by core drilling. Earlier in the year the same company drilled a well on the Glen Gray farm in the southwest corner, SW. 1/4 sec. 29, T. 65 N., R. 39 w., to a depth of 2427 ft. in the Hunton lime with a rotary drill. Oil stains in this hole led to the drilling of the second well. Table i .—-Wells Drilled for Oil and Gas in Missouri in 1942 Country Number of Number of County Oil Wells Gas Wells Dry Andrew.......... Atchison.......... I Bates............ 2 6 Caldwell.......... I 3 Cass............. I Clinton........... I Holt............. I Jackson.......... I I Knox............ I Nodaway......... I Platte............ 4 4 Ray.............. 5 Sullivan.......... I Totals.......... I 7 28 Otherwise drilling in Missouri was uneventful, with a total of only 36 Completions, of which one was a very small oil well, Seven were small gas wells and 28 were dry holes. The total footage drilled was 24,7541/2 ft., of which 14,0281/2 was by cable tools and 10,726 ft. by rotary. Twelve of the dry holes were drilled into Mississip-pian or older beds. Table I gives a summary of activities by counties.

Jan 1, 1943

By Frank C. Greene

The principal event in the development of oil and gas in Missouri in 1942 was the drilling of the Cities Service Oil Company's No. I Jim Cook, in the northwest corner, NW. 1/4 sec. 32, T. 65 N., R. 39 W., Atchison County, in the northwest corner of Missouri. This well, not yet completed, bailed several barrels of free oil in about 27° Baume from a sand called the Bartlesville by those in charge, at a depth of 1450 ft. The well is on a block of leases obtained after the area, which is covered by several hundred feet of glacial drift, had been prospected by core drilling. Earlier in the year the same company drilled a well on the Glen Gray farm in the southwest corner, SW. 1/4 sec. 29, T. 65 N., R. 39 w., to a depth of 2427 ft. in the Hunton lime with a rotary drill. Oil stains in this hole led to the drilling of the second well. Table i .—-Wells Drilled for Oil and Gas in Missouri in 1942 Country Number of Number of County Oil Wells Gas Wells Dry Andrew.......... Atchison.......... I Bates............ 2 6 Caldwell.......... I 3 Cass............. I Clinton........... I Holt............. I Jackson.......... I I Knox............ I Nodaway......... I Platte............ 4 4 Ray.............. 5 Sullivan.......... I Totals.......... I 7 28 Otherwise drilling in Missouri was uneventful, with a total of only 36 Completions, of which one was a very small oil well, Seven were small gas wells and 28 were dry holes. The total footage drilled was 24,7541/2 ft., of which 14,0281/2 was by cable tools and 10,726 ft. by rotary. Twelve of the dry holes were drilled into Mississip-pian or older beds. Table I gives a summary of activities by counties.

Jan 1, 1943

By Eugene R. Rice

(Canal Zone Meeting, November, 1910.) THERE are many methods for determining the meridian, but all of those in common use involve at least two separate observations, one for latitude and one for azimuth. Such observations made upon a south star at any hour are open to the objection of possible inaccuracy due to ignorance of the absolute refraction, and also to slow change in the altitude of the star when near the meridian. The method of observing a circumpolar star at elongation, besides requiring a separate observation for latitude, is open to the serious objection that clouds may obscure the star at the critical moment. Moreover, a tedious wait for the star to come to elongation is sometimes necessary. Many of us can recall long, cold, weary vigils, waiting for Polaris to reach elongation. For observing a circumpolar star at any hour, not only the latitude, but also the true time, must be known. This it is practically impossible to obtain, except in regions reached by the telegraph, and usually then one has to know the longitude also, in order to reduce "standard time" to "local time." The results obtained by this method, when the star is at culmination, are not very good, unless the true local time is absolutely known. The methods of obtaining the meridian from the sun, by means of a solar attachment, or by direct observation, while good, are not absolute, by reason of refraction, change in declination of the sun, and small change in vertical angle, when the sun is near the meridian. For these two methods, latitude, time, and approximate longitude have to be known. In the method here described, only one observation is needed, and from it azimuth, latitude, and sidereal time are computed. In other words, one can observe a circumpolar star-Polaris

Nov 1, 1910

By R. J. Jackson, D. E. Williams, W. L. Larsen

The phase diagram of the Ta-Zr system is presented with a discussion of the methods used in its determination. The solidus contains a minimum at 1820°C near 25 wt pet Ta. A complete solid solution exists at elevated temperatures between tantalum and ß zirconium. This solid solution decomposes monotectoidally at 800°C and 12 wt pet Ta. The maximum solubility of tantalum in a zirconium is slightly less than 2 wt pet, and decreases with decreasing temperature. The solubility of zirconium in tantalum is 5 wt pet at the monotectoid temperature and about 2 wt pet at room temperature. THIS investigation was part of a program of research on refractory metal alloy systems having potential application in nuclear reactor technology. Preliminary prop-ess has been reported in the Ames Laboratory annual research reports.l Most of the previously reported work on the Ta-Zr alloy system consisted of partial phase diagram investigations and the determination of the mechanical properties of the zirconium-rich alloys. Anderson eta1.2 studied alloys containing up to 30 wt pet Ta as part of an investigation of several zirconium alloy systems. These investigators also determined some of the mechanical properties of the alloys at room temperature and 650°C. In a discussion of Anderson's work, Pfei13 suggested that the bright phase in the microstructures of the intermediate alloys is a tantalum-rich solid solution or an intermediate phase in a matrix of ß zirconium solid solution. Litton,4 Keeler,5 and Chubb6 determined the mechanical properties of zirconium-rich alloys at ambient and elevated temperatures. Van Thyne and McPherson7 reported the tensile properties

Jan 1, 1962

By J. L. Gillson

THE big mass of anorthosite in the Lake Sanford district and the bodies of titaniferous magnetite that occur in a small area near the south margin of the mass have been described repeatedly, and the puzzling problems of the genesis of the rocks and ores have stimulated the deductive reasoning of geologists for a hundred years. Some of these men have taken a leading part1-15 in describing the anorthosite rock and forming hypotheses concerning its origin; some have contributed most to the study of the ore deposits;'"= and some have made classical Studies3,4,21-27 introducing a basic approach to the problems of the anorthosite rock and genesis of the titaniferous magnetites. Much of the writing on the problems of rock and ore genesis has been based on physical-chemical reasoning rather than on field and microscope observations of the rocks and ores. Most of these geologists conclude that the anorthosite was formed by true magmatic crystallization, involving previous settling or squeezing out of ferromagnesian minerals from the parent magma. The associated gabbro is a separate segregation or later intrusion, and the lighter colored and finer grained facies of the anorthosite is either a chilled border zone of the anorthosite or the result of granulation by crushing of the coarse, dark blue rock of the main mass. This blue rock, called the Marcy type, is named after the higest peak in the range. The finer grained and lighter colored rock is called the White-face, after another mountain appropriately named for a cliff colored by this facies of the anorthosite. In explaining the genesis of the ores the authors have reached no general agreement, but all consider them to be dominantly the result of magmatic processes rather than the result of replacement by pneu-matolytic or hydrothermal processes. However, in the conclusions of two authors, Osborne27 and Ste-phenson," the reader is told positively that the ore minerals were introduced after the wall rock was solid and also that the oxides are later than the silicates. This seems to mean that the ore came in as a later intrusion, like a dike, since Osborne speaks of filter pressing and later injection of a residual magma. Stephenson agrees in general with Osborne but disagrees with his conclusion that ore does not grade into country rock. Singewald22 calls in "mineralizers" to participate in magmatic deposition. Stephenson ends his paper with a statement that replacement was the dominant process for the introduction of ore with anorthosite. Hence both Singewald and Stephenson call on pneumato-lytic or hydrothermal processes to supplement magmatic crystallization from a silicate melt, but they cannot quite bring themselves to state that the orebodies formed in that way. In their conclusions the ores are still magmatic segregations and magmatic injections and—almost as an afterthought— "replacements." According to Bateman18 there was a gravitational accumulation process of the iron silicates and oxides, which were injected later. Rambere explains the ores entirely on physical-chemical theory, as does Evrard.17 Buddington and associates,10 in a paper presented to the Geological Society of America in 1953, believe the facts observed prove that the magnetite-ilmenite formed at magmatic temperatures. The present writer's conclusions, given here, were first presented in 1947 in Industrial Minerals and Rocks.= Since the papers of Ramberg, Bateman, and Buddington, published after 1947, gave no recognition to those conclusions that differ from their own, the writer has taken an opportunity to restudy the area in the field, and to examine a number of microscopic sections, and now presents the evidence more thoroughly than he had an opportunity to do in the

Jan 1, 1957

By G. Derge, W. Peifer, J. H. Richards

INTRODUCTION A WIDE variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware. They have been related to hydrogen largely by circumstantial evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British Committee on the Heterogeneity of Steel Ingots,1 and current approaches to the problem were reviewed in a recent symposium of the AIME.12 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principle object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem. The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow cooling. However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross section large enough to develop cracks, yet small enough for convenient handling and sampling. Rails were also selected because they are made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitates early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion. (2) Vacuum extraction (without melting). (3) Total combustion.

Jan 1, 1948

By J. A. Brierley, Roshan B. Bhappu, D. H. Reynolds, P. H. Johnson

Although the economic importance of recovering copper by leaching of mine work dumps from open-pit operations has been realized for some time, serious attempts to understand and to improve such operations through scientifi research has been made only in recent years. This progress report covers the results of chemical, physical, and biological studies pertaining to the dump-leaching process and discusses salient features and parameters that may be helpful in improving such operations. The dump leaching of low-grade copper ores, as an integral part of the open-pit mining operations in the Southwest, has been practiced for the last 50 years and is increasing in importance as one of the major sources of copper. The recent acceleration in dump leaching can be attributed to: (1) the greater tonnages of low-grade ores mined and dumped at newer mines as well as resulting from increased stripping ratios at the older mines, (2) the relatively small investment required for dump leaching facilities per pound of copper recovered contrasted with expansion of milling facilities to recover equal amounts of the metal by raising tonnage throughout, (3) low labor requirements needed for leaching, and (4) the simple and continuous nature of the process needing little close supervision of trained operators. In the past, the mining companies have not worried about efficiency in dump leaching but have been satisfied with whatever metal recoveries could be made without much effort. However, because of the huge amounts of metal accumulating in the low-grade waste dumps, compared to the relatively small amount recovered annually, an operator today cannot leave dump leaching to chance. What appears to be a simple, empirical process is actually a very complex one involving a large number of critical factors that encompass Several Scientific disciplines, such as physics, chemistry, geology, biology, and hydrology. It is imperative that

Jan 1, 1970

By W. A. Bruce

Studies of reservoir behavior of 12 Smackover limestone oil and condensate pools are presented. Buckner, Midway, McKamie, Magnolia, Mt. Holly, Schuler (Reynolds) and Village are treated in considerable detail and subjected to analysis with an electrical device for analyzing reservoir behavior. Results and comparisons of these analyses are presented. In addition to these reservoir-behavior studies, an attempt is made to assemble trans-missibility and storage data on the Smackover limestone formation from cores and logs taken in dry holes and producers. This together with the behavior of individual reservoirs leads to a better understanding of the formation as a porous aquifer. The ultimate purpose of this type of study is to improve predictions concerning the future behavior of these pools in such a system. Predictions are presented for several pools. Introduction In 1937 the Phillips Petroleum Co. drilled its J. D. Reynolds No. I to the Smackover limestone formation at Snow Hill, Arkansas. This well found oil in the porous, permeable, upper part of the Smackover, thereafter referred to as the Reynolds lime. Since then, six oil pools and six condensate pools have been discovered in the Reynolds lime, and more than 75 dry holes have explored parts of this formation. By the first of 1943, 44 million barrels of oil and 83 billion cubic feet of gas had been withdrawn from the various reservoirs. The original reserves estimated by the Arkansas Oil and Gas Commission were 342 million barrels of oil and rzoo billion cubic feet of gas. So far all of the production has been from anticlinal structures, most of which are asymmetric and have their axes roughly perpendicular to the dip of the formation top. This is indicated in Fig. I, which shows the pools, dry holes drilled, and contours on top of the Smackover.' These pools are of particular interest for reservoir-behavior studies because the production and drilling has been controlled, and in most cases the records of reservoir data are complete. In addition to the excellent production and pressure information available, more than one half of the wells drilled were cored and all of them were electrically logged. All of the pools show evidence of water drive. While this paper is in a sense a collection of reservoir-behavior studies for several different pools, there has been an attempt to go one step further and to show the importance of the iormation as a porous continuum or a single aquifer in which the withdrawals of fluids from any pool has an important effect on the behavior of all of the pools. An effort will be made to show that the water drives of these pools are dependent upon a much larger area of the Smackover limestone than that occupied by the petroleum accumulations.

Jan 1, 1944

By W. A. Bruce

Studies of reservoir behavior of 12 Smackover limestone oil and condensate pools are presented. Buckner, Midway, McKamie, Magnolia, Mt. Holly, Schuler (Reynolds) and Village are treated in considerable detail and subjected to analysis with an electrical device for analyzing reservoir behavior. Results and comparisons of these analyses are presented. In addition to these reservoir-behavior studies, an attempt is made to assemble trans-missibility and storage data on the Smackover limestone formation from cores and logs taken in dry holes and producers. This together with the behavior of individual reservoirs leads to a better understanding of the formation as a porous aquifer. The ultimate purpose of this type of study is to improve predictions concerning the future behavior of these pools in such a system. Predictions are presented for several pools. Introduction In 1937 the Phillips Petroleum Co. drilled its J. D. Reynolds No. I to the Smackover limestone formation at Snow Hill, Arkansas. This well found oil in the porous, permeable, upper part of the Smackover, thereafter referred to as the Reynolds lime. Since then, six oil pools and six condensate pools have been discovered in the Reynolds lime, and more than 75 dry holes have explored parts of this formation. By the first of 1943, 44 million barrels of oil and 83 billion cubic feet of gas had been withdrawn from the various reservoirs. The original reserves estimated by the Arkansas Oil and Gas Commission were 342 million barrels of oil and rzoo billion cubic feet of gas. So far all of the production has been from anticlinal structures, most of which are asymmetric and have their axes roughly perpendicular to the dip of the formation top. This is indicated in Fig. I, which shows the pools, dry holes drilled, and contours on top of the Smackover.' These pools are of particular interest for reservoir-behavior studies because the production and drilling has been controlled, and in most cases the records of reservoir data are complete. In addition to the excellent production and pressure information available, more than one half of the wells drilled were cored and all of them were electrically logged. All of the pools show evidence of water drive. While this paper is in a sense a collection of reservoir-behavior studies for several different pools, there has been an attempt to go one step further and to show the importance of the iormation as a porous continuum or a single aquifer in which the withdrawals of fluids from any pool has an important effect on the behavior of all of the pools. An effort will be made to show that the water drives of these pools are dependent upon a much larger area of the Smackover limestone than that occupied by the petroleum accumulations.

Jan 1, 1944

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By W. A. Tiller, D. H. Lane

A simple zone melting technique for investigating the effect of ultrasonic irradiation upon ingot solidification is described. The effect of i) ultrasonic power level, ii) freezing velocity, iii) constant or variable frequency, iv) direction of irradiation, and v) transducer-cozlpling bar joint upon the grain size of type 316 stainless steel have been investigated. The results of this study support the postulate that the ultrasonic vibrations increase the nucleation probability in the layer of liquid adjacent to the freezing interface. In the first paper of this series,l the possible mechanisms whereby ingot structure may be altered by irradiating a solidifying melt with ultrasonic vibrations have been discussed. A new technique for efficiently introducing the ultrasonic energy into the solid-liquid interface region was presented and applied to ingot preparation by the consumable-electrode arc-melting technique. The experimental results support the postulate that the ultrasonic vibrations may refine the ingot structure by increasing the nucleation probability in the zone of liquid adjacent to the solid-liquid interface. The present paper describes the application of the same technique to a relatively simple laboratory-scale zone-melting apparatus. This apparatus is found to be well suited to the detailed study of ultrasonic technology in this area and allows one to determine, in particular, the minimum ultrasonic power level needed to produce a certain grain size in a particular material. The results of this study support the nucleation mechanism for grain refinement, but do not provide any deeper insight into the specific nucleation mechanism responsible for the effect. EXPERIMENT The apparatus used in these experiments is shown in Fig. 1 and illustrated schematically in Fig. 2. The material to be studied, type 316 stainless steel, was in the form of a 3/4-in. sq bar 30 in. long. This bar was placed in a square open-topped mold with open ends made from high-purity graphite coated with a flame-sprayed Al2O3, skin. Surrounding the crucible was a molybdenum susceptor with 3/8-in. diam holes spaced at 1-in. intervals along its length to serve as sight ports. A tapered transducer horn was brazed to one end of the specimen. The entire assemblage was enclosed in a quartz tube, the transducer itself projecting out one end and resting in a cooling tank. A vacuum seal between the coupling bar and the end plate enclosed one end. A similar plate and seal enclosed the other end. The system is gas tight and can be operated under vacuum or an inert atmosphere. For these experiments, flowing argon at 15 in. of Hg pressure was used. The heat source for melting the stainless steel specimen was a 2-in. long 3-kc induction coil placed around the quartz tube; this source heated the susceptor, inductively melting about a 3-in. zone of the sample by radiation. To move the molten zone at a specified rate, the induction coil was moved down the tube at this rate with the aid of a simple pulling device. Thus, the sample could be irradiated at varying ultrasonic frequencies and power levels and could be solidified at varying rates. The power input to the transducer was measured using a "John Fluke Model 120 VAW-Meter." 1 The power delivered to the interface region is probably only about 50 pct of that measured on the VAW-meter. In a typical run, when the ultrasonic power was turned on, the interface of the molten zone closest

Jan 1, 1961