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By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By E. A. Anderson, M. L. Fuller

The copper-zinc phase equilibrium diagram has been the subject of many investigations. Until recently, however, the boundary of the terminal solid solution of copper in zinc (eta) has not been thoroughly investigated. This paper reports determinations of the solid solubility of copper in zinc at temperatures from 100' to 400' C., the course of the liquidus and solidus for the eta solid solution and determinations of the peritectic temperature and peritectic point for the reaction between epsilon and the melt to form eta. The liquidus of the eta phase was determined by thermal analysis and the solidus by the microscopical examination of specimens quenched from temperatures above and below the solidus. The temperature of the peritectic horizontal was obtained by thermal analysis and the composition at the peritectic point was determined by extrapolation of the solid solubility boundary of the eta phase to the peritectic horizontal. The solid solubility boundary of the eta solid solution was investigated very carefully. Particular care was used to achieve equilibrium in the alloys at each temperature selected. The X-ray, electrical conductivity and microscopical methods mere used in determining the solid solubility limits. The X-ray method measures the changes in the solvent lattice with increasing solute content and in this manner locates the composition of the alloy at which no further change in the solvent lattice takes place, the limit of solid solubility. The method of electrical conductivity measures the conductivity of the alloys of a graded series of compositions, whereby the solubility limit is indicated by a discontinuity in the conductivity-composition relationship. The microscopical method distinguishes, by direct inspection, between the homogeneous solid solution alloys and those having a secondary constituent in addition to the solid solution phase, and thus indicates from the examination of a series of alloys the solid solubility limit.

Jan 1, 1934

By C. S. Blair

THE development of a geological department as an integral part of the Tennessee Coal, Iron & Railroad Co. in the Birmingham district, Ala-bama, in 1908 was an innovation probably unique for any mining organ-ization south of the Ohio River, At that time a few of the oil companies were starting geological departments, but there were no geologists among the larger industrial organizations. The Tennessee Coal, Iron & Railroad Co. had been a substantial producer of pig iron for many years and was just getting a start in the manufacture of steel products from the pig iron. It had large acreages of coal land, ore land and timber land, but there was lacking the detailed knowledge of the possible mineral resources of much (of its territory, and this territory at that time covered an area in the neighborhood of 500,000 acres in the states of Alabama, Tennessee and Georgia. Those responsible for the operations of the mining properties, not being familiar with the kind of help that might be expected from geologic work, were decidedly skeptical of the utility of the work. Therefore it was necessary to develop cooperation with the mining organization, by not infringing upon its functions, and by developing the work in such a manner as to demonstrate to the mining department its practical utility. In the first instance the man responsible for a mining operation is apt to assume the attitude that the geologist is a blockader, because the geologist, unfortunately, is obliged to point out difficulties in the carrying out of mining operations in the way originally planned. He points out the dangers of mining out one coal or metal seam at the ultimate expense of an upper or lower seam, and he develops structural features, such as faults and folds, which call to the attention of the mining operator diffi-culties in his future operations, which the latter had not anticipated. Eventually, however, -the value of having these data became ap to the Tennessee Coal, Iron and Railroad Co., and the operators not only welcomed the geological work and cooperated fully in its acquisition of essential information, but reached the point of asking assistance and advice; and complete coordination of the two activities has existed for many years.

Jan 1, 1933

By J. H. Hollomon, L. D. Jaffe

The hardenability concept has become widely used during the last few years for the choice and substitution of steels. Before the work of Grossmann,1 the systems for predicting hardenability from chemical composition could be used only over a narrow range of composition. Grossmann introduced a comprehensive system, which has been effective in calculating the hardenability of most types of moderate or low-alloy steels. However, occasions often arise that require the calculation of the hardenability of high-alloy steels from their chemical compositions. Experimental determinations of the hardenabilities of such steels indicate that the Grossmann system predicts much greater hardenabilities than are realized. The fact that cases do arise in which the Grossmann method does not apply indicates that the fundamental hypothesis of the system may not be generally applicable. It seems advisable to re-examine not only Grossmann's system but also the concept of hardenability itself. Hardenability If steel parts are to possess a martensitic structure after quenching, they must first be austenitized and then cooled through the pearlite and bainite transformation ranges sufficiently rapidly to avoid the formation of pearlite, bainite, and pro-eutectoid products.* If, on cooling, these transformations are avoided, the resulting structure can consist only of martensite (and retained austenite). The hardenability of a steel is measured in terms of the severity of the cooling conditions necessary to avoid the pearlite and bainite transformations. The less rapid is the cooling necessary to prevent the formation of bainite and pearlite, the higher is the hardenability. The pearlite and bainite reactions appear to be differently affected by the alloying elements. Not only is this indicated by the published isothermal transformation data, but recent work by Zener2 affords a rational interpretation of the differing effects of the alloying elements. Manganese,3 for example, appears to decrease the rates of the pearlite and bainite transformations by equal percentages, while molybdenum45 is approximately 10,000 times more effective in retarding the pearlite than in retarding the bainite transformation, on the basis of isothermal measurements. In some steels, the formation of bainite restricts the formation of martensite while

Jan 1, 1947

By L. D. Jaffe, J. H. Hollomon

The hardenability concept has become widely used during the last few years for the choice and substitution of steels. Before the work of Grossmann,1 the systems for predicting hardenability from chemical composition could be used only over a narrow range of composition. Grossmann introduced a comprehensive system, which has been effective in calculating the hardenability of most types of moderate or low-alloy steels. However, occasions often arise that require the calculation of the hardenability of high-alloy steels from their chemical compositions. Experimental determinations of the hardenabilities of such steels indicate that the Grossmann system predicts much greater hardenabilities than are realized. The fact that cases do arise in which the Grossmann method does not apply indicates that the fundamental hypothesis of the system may not be generally applicable. It seems advisable to re-examine not only Grossmann's system but also the concept of hardenability itself. Hardenability If steel parts are to possess a martensitic structure after quenching, they must first be austenitized and then cooled through the pearlite and bainite transformation ranges sufficiently rapidly to avoid the formation of pearlite, bainite, and pro-eutectoid products.* If, on cooling, these transformations are avoided, the resulting structure can consist only of martensite (and retained austenite). The hardenability of a steel is measured in terms of the severity of the cooling conditions necessary to avoid the pearlite and bainite transformations. The less rapid is the cooling necessary to prevent the formation of bainite and pearlite, the higher is the hardenability. The pearlite and bainite reactions appear to be differently affected by the alloying elements. Not only is this indicated by the published isothermal transformation data, but recent work by Zener2 affords a rational interpretation of the differing effects of the alloying elements. Manganese,3 for example, appears to decrease the rates of the pearlite and bainite transformations by equal percentages, while molybdenum45 is approximately 10,000 times more effective in retarding the pearlite than in retarding the bainite transformation, on the basis of isothermal measurements. In some steels, the formation of bainite restricts the formation of martensite while

Jan 1, 1947

By A. R. Kaufman, P. Gordon

THE large-scale manufacture and use of uranium in conjunction with the atomic energy development during the war led to a need for knowing the equilibrium diagrams of uranium with various other metals. The alloys of uranium with aluminum and with iron were among the first that were studied for this purpose. Much of the work was done in the manner of a survey since it was necessary to determine the important features of the phase diagrams rather than to obtain completely detailed results. For this reason no attempt was made to locate exactly such features as liquidus lines, solid solubility limits and compound and eutectic compositions. It is believed, however, that there are no great inaccuracies in the diagrams reported here and that no important points were overlooked. Earlier work on alloys of uranium with aluminum and iron is almost nonexistent and in each case is considered to have been of little value by M. Hansen. It is interesting to note, however, that the compound UAl3 was first reported in 1902 by L. Guillet. Experimental Procedure Materials: The uranium used for making most of the aluminum alloys was obtained from material prepared by Metal Hydrides, Inc., and melted in vacuum at M.I.T. Because of the lack of an adequate supply of metal, it was necessary to use material from several different batches and hence it is impossible to state an exact analysis. However, a few results indicated about 0.01 to 0.03 pct iron and probably about 0.03 to 0.05 pct carbon. Toward the end of the work a small amount of metal was obtained from Brown University and from Iowa State College and this was used in determining the transformations in pure metal and in some dilute alloys. All of the aluminum used in this investigation came from a supply of high purity metal (greater than 99.9 pct aluminum) which was obtained through the courtesy of Dr. Mehl of the Carnegie Institute of Technology. The uranium used for making the alloys with iron was produced by the bomb reduction process which has been described by J. Chipman.² This metal, after vacuum melting, contained about 99.9 pct uranium by weight with carbon and iron as the chief impurities. Electrolytic iron containing about 0.012 pct carbon, 0.020 pct nickel and 0.009 pct copper was used in making the melts. Melting Equipment: The melting of the alloys went through a stage of development which culminated in the use of beryllia or beryllia-lined crucibles and in the use of high frequency heating in either vacuum or in an atmosphere of argon. It was found that uranium at a few hundred degrees above its melting point would pick up aluminum and to a lesser extent silicon from an alundum thimble while aluminum above 1000°C would extract silicon from the impure alundum. No reaction of either metal with beryllia was noted at temperatures as high as 1800°C. The distillation of aluminum from the aluminum-rich alloys was quite troublesome at temperatures above about 1300°C and was only partially avoided by the use of argon instead of vacuum. Melting in resistance furnaces,

Jan 1, 1951

By Curtis L. Graversen, J. H. Hamilton, John C. Nixon, John R. Lewis

RECENTLY there has been much speculation concerning the advantages of using oxygen enriched air or pure oxygen in pyrometallurgical processes. The advantage of using oxygen in the iron blast furnace and elsewhere in ferrous production metallurgy has been given careful consideration and, as a result, several experiments have been tried and a number of papers have recently appeared on this subject.1.2 The use of oxygen in nonferrous smelting likewise poses interesting problems, therefore any experimental data obtained in this area should likewise be of general interest.3 Ashcroft4 in 1933 claimed to have obtained improved results when copper concentrates were roasted in pure oxygen. However, his' paper gives neither data nor experimental details. A few years ago a research program was started in this laboratory which had for its objective the determination of the mechanism of oxidation of metallic sulfides under varying conditions. To date we have studied the oxidation of galena, 5 sphalerite, and chalcocite. It is a well known fact that copper sulfide minerals are oxidized slowly by weathering agents, so that the sulfides of copper which find their way into a tailing pond are gradually changed into watersoluble and acid-soluble compounds. Commercially, the oxidation of copper sulfide minerals is accomplished by roasting them at elevated temperatures in air using a suitable (usually multiple-hearth) roaster. Most copper smelters are equipped with such roasters. In this phase of the study we were especially interested in determining the effect of temperature on: (I) the air oxidation of chalcocite and (2) the oxidation of chalcocite using commercial oxygen. The amount of sulphur removed as sulphur dioxide, the percentages of water-soluble copper, and of acid-soluble copper were determined for the air oxidation tests. In the tests using commercial oxygen, the percentages of sulphur dioxide, water-soluble copper, acid-soluble copper, water-soluble sulphur and acid-soluble sulphur were determined. For these experiments the temperature was varied from 250 to 700°°C. EXPERIMENTAL Preparation of Chalcocite (Cu2S) Natural chalcocite is not pure. Minerals such as bornite, covellite, and chalcopyrite may be present. It was decided, therefore, to prepare some chalcocite in our own laboratory. An intimate mixture of sulphur and finely divided metallic copper in the ratio of 4 g of copper to I g of sulphur was prepared. To this was added a slight excess of

Jan 1, 1948

By George H. C. Norman

A NUMBER of methods have been developed for the determination of the dust concentration in air, some of which have been reported as very efficient and for research may be more satisfactory than the method about to be described. In practical mine use, however, the accurate research equipment is unwieldy and requires a high degree of technical skill to manipulate it. Also, it gives less general practical information to the operator in the same length of time than the method described here. Moreover, it is doubtful whether at the present stage of affairs the results obtained from the precise methods have any more practical significance than those obtained with simpler and more portable apparatus, which can rapidly give a sufficiently reliable indication of the relative dust hazard. HISTORY OF DUST DETERMINATION IN ONTARIO The first record of mine-dust determination in Ontario is given in an article by Dr. J. H. Elliott,' in which he records a few dust counts made with the Palmer spray apparatus. There were insufficient data from which to draw any definite conclusions or reasonably compare with present-day counts using the konimeter. The first konimeter dust sampling was started in the Porcupine district in 1926, using light-field counting without adhesive and with no sample treatment before counting. A method of semidark-field counting was used from about 1928 to 1931 and dark-field illumination was adopted permanently about December 1931. The konimeter has been continued as the principal means of dust sampling in the mines of Ontario, where South African practice has been adopted because in South Africa most careful study has been given the problem of silicosis, and very complete records of work done there are

Jan 1, 1937

By J. C. Febles

HISTORY. THE use of iron for the precipitation of copper was known at least as early as the fifteenth century. Both Paracelsus and Basil Valentine refer to it in their writings, as early as 1500 A. D. It was used in Peru, for this purpose prior to 1637, and at Rio Tinto, Spain, as early as the sixteenth century. The statement has been made repeatedly that in the early history of the mining industry at Butte, the practicability of this method of recovering copper from solution was overlooked, and that enormous quantities of copper-bearing water were allowed to go to waste, the copper in which might easily have been recovered at small cost; and that this oversight on the part of the mine operators was due to ignorance of this method of recovering copper. As a matter of fact, very little copper-bearing mineral was encountered in the mines of Butte until a depth of 400 or 500 ft. bad been reached, and in many cases much greater depths were necessary to reach the copper-bearing zone. The water encountered in the upper levels (although in most cases quite highly mineralized) contained little or no copper, and it was only after considerable areas of copper-bearing ore had been uncovered and developed that copper sulphate began to. appear in the mine water in any considerable quantity. In fact, the first water that was observed to contain copper carried it in such small amounts as to be of little or no importance. It was only after years of underground work had opened extensive areas of stopes, drifts, and other underground workings, these being subsequently filled with waste, nearly all of which contained small copper values, which became oxidized by exposure to the air and were acted upon by the slowly percolating mineral water, that the recovery of copper from mine water became commercially important.

Jan 7, 1913

By S. J. Prison, C. R. Smith

The effect of fluid injection to control water coning in oil and gas wells was investigated. Analytical and model techniques were employed. The factors investigated were the position and length of the completion interval, the point of fluid injection, the viscosity of the injected fluid and the relative thickness of the oil and water sections. The resulting influence of these factors on the net producing water-oil ratio was determined. Several important conclusions can be drawn from the study. In general, it was found that the net producing water-oil ratio can be reduced by fluid injection. The magnitude of this reduction depended on the factors listed above. An important practical consideration is that the injection fluid may be either oil or water. If the injected fluid is less dense than the connate water of the reservoir, the fluid will not be lost. This fact is reassuring when valuable oil is being injected. Efforts to suppress water production were more successful when the injection fluid was more viscous than the reservoir oil, or when a zone of reduced permeability existed in the vicinity of the point of fluid injection. Under test conditions, little benefit was derived through the use of impermeable barriers or cement "pancakes". INTRODUCTION The occurrence of water coning has been known for at least 60 years. In thin oil or gas pay sections, the presence of an oil-water or gas-water contact hinders production and often causes early abandonment of the afflicted well if a completion is even attempted. Even when relatively thick pay sections are found, the encroachment of water when a water drive is present will eventually pose serious water coning problems. This water is often corrosive, expensive to separate from the oil or gas and is costly to dispose of. The theory of water coning has been discussed by a number of authors. 1,2,3,4 Briefly, water coning to the producing interval in a well is due to pressure gradients resulting from the production of fluid from the reservoir. These pressure gradients will cause a water cone to rise toward the bottom of the producing interval if a water-oil or water-gas contact exists. The tendency of the water to cone is offset or partially offset by gravity forces since the water has a higher specific gravity than the oil. A balance then exists between two forces, gravitational forces arising from the difference in specific gravities of the oil and water, and the pressure gradients causing the flow of fluids to the wellbore. If the pressure gradient exceeds the gravitational force, water coning to the wellbore occurs and water production results. Through the years considerable thought has been given to the water coning problem. More than 50 U. S. Patents have been granted to inventors on the subject. A relatively complete literature review of the water coning problem has been made. 5 A number of these patents hold considerable promise for the solution or the partial solution of the water and/or the coning problem. Very little has been written describing field tests of techniques for the suppression of water coning. A notable exception is the paperby West. 6 He reports success in reducing gas coning by a combination of gravel packing and oil injection above the oil-producing interval. He also describes a comparable method to prevent water coning, but provides no field examples. This study experimentally and analytically verifies the benefits of oil injection as a means of partially or completely suppressing the water cone. While the gas coning problem was not treated, it is anticipated that results comparable to those obtained in water suppression could be obtained with reduced oil injection since the viscosity contrast between oil and gas exceeds that between oil and water. For the purpose of this study, the conventional potential flow theory was applied to the water-coning problem. The experimental verification centered on both a radial and a linear model. The model study permitted the investigation of complex flow configurations and the use of fluids of differing densities and viscosities. No analytic expressions are available to permit a solution of the problem as stated (see Fig. 1).

By Thomas Read

PERSONNEL work is a term recently introduced to cover the great variety of activities in industrial work that deal with the human factor. Much attention has been focussed upon individual phases of personnel work, such as accident prevention, sanitation, "welfare" work, reducing labor' turnover, and so on. In most cases these activities have been carried on as though they were distinct and separate fields; as a matter of fact, they are only different phases of the single problem of human engineering, and each has important and fundamental relations with the others. Thus, for example, high labor turnover is one of the most .important causes of a high accident rate, and unsatisfactory housing conditions are an important cause of labor turnover. In the early stages of the study of these problems, it was necessary to take them up separately; the time has now arrived at which it is desirable to consider them as a whole in order to bring them into the right relation to each other. When thus considered as phases of an interrelated whole, they may be grouped as personnel work. A discussion of the importance of personnel work as a means of in creasing dividends in industry may be objected to by some as a too materialistic way of looking upon work that is humanitarian. Nothing could he more mistaken than such an opinion. Humanitarianism, per se, has no place in industry, and nothing is gained and much is lost in pre tending that it has. The only reason why a corporation engages in business is to make profits, and any activity of the corporation that does not tend either directly or indirectly toward that end is poor business. It is equally poor business to overlook any activities that do tend indirectly to the making of profits. On this basis, personnel work can be justified as a corporate activity; there is no justification whatever for abstract humanitarianism from the business standpoint. One characteristic of the American workman is a general high level of intelligence, and it is an insult to intelligence to ask a man to believe that anything so impersonal as a corporation is really desirous of benefiting

Jan 10, 1917

By M. Kaitz

A continuing discussion in both the petroleum engineering and economic literature is directed to the difficulties encountered in the use of discounted cash flow rate of return (DCF) as a measure of investment worth. Although useful in most Instances, DCF has been criticized because it is time-consuming in its trial-and-error solution, theoretically invalid, not adaptable to cash flow streams yielding multiple return solutions and not entirely reliable in selecting between mutually exclusive investments. The theoretical invalidity of DCF stems from the reinvestment assumption implicit in the calculation that earnings are reinvested at the DCF rate. The emerging consensus of the economic literature is that the net present value or the present worth of the net cash flow stream (discounting at the average opportunity or cost of capital rate) is more correct and reliable. Other criteria proposed have been ratios of net present value divided by initial investment or by present value of all investments in a project. All of these criteria are simple to determine and explicitly assume a reinvestment rate for [he income generated by a project. This paper develops and discusses a theoretically valid profitability criterion which is simple to compute and retains the appeal of a percent return on investment. It is called "percentage gain on investment" or PGI. It measures the gain an investment is expected to realize over like capital invested in the average opportunity and explicitly considers reinvestment potential. Why add another Concept to the large array of investment criteria now available, any one of which, or perhaps a combination of several, appears to embrace the form's (or individuals) objectives? The answer is that not one of the existing criteria provides both a readily comprehensible and theoretically valid measure of risk coverage that has general application. The proposed PGI does fulfill these requirements. INTRODUCTION An ancient expression warns that "one must yield to the times" — there are better ways of doing things. A review of the petroleum engineering and economic literature on one topic alone, measurement of investment worth, certainly is witness to this truth. In use for a number of years, the DCF has recently received attention, directed mainly to its theoretical invalidity. Several alternatives to DCF have been proposed to provide a valid, simply determined criterion to describe investment worth and to overcome the criticisms previously mentioned. This paper introduces another method called percentage gain on investment (PGI) and is proposed as but one of several yardsticks that should be used in making investment decisions. MEASURES OF INVESTMENT WORTH This paper will consider only those criteria which give weight to the time pattern of future earnings. These criteria are usually compared with an average opportunity rate or cost of capital of the firm to judge the relative worth of the investment. For purposes of demonstration, a 9 percent average opportunity rate will be used throughout this paper. Implicit in the DCF calculation is the assumption that earnings are reinvested at the DCF rate. Some argue, though, that there is no reinvestment assumption,' that the DCF rate is simply that maximum rate of interest one can pay on the investment over the life of the project and break even. The determination of DCF is accomplished by discounting the net cash flow stream at that rate (DCF) which will yield zero. The question is: why should reinvestment potential be explicitly considered in calculating return on investment or other criteria measuring economic worth? Perhaps the answer lies in consistent or equal treatment of future cash flow. It appears entirely illogical to give different present worth value to $1 received, say, 10 years from now, which is the circumstance resulting in comparing projects with different DCF returns. In fact, $1 received in 10 years has the same value regardless of which project generated the income. DCF return thus favors investment projects which are expected to provide early income as compared to those providing long-term income. Not surprisingly, the controversy on reinvestment assumption is an old one. Hoskold' discussed this same problem in 1877. He considered the future income from mineral properties as an annuity or a series of fixed future payments. (As will be demonstrated, his equation can be modified for variable income.) Prior to Hoskold, the value or what one could pay for the mine, was determined with the use of standard, single-interest tables. Here is what Hoskold said with regard to these tables. "This table, and others of its kind, to be found in most works on annuities, is constructed correctly according to

By V. A. Josendal, J. W. Wilson, B. B. Sandiford

Two radioactive tracers have been tested as a means of determining core saturation in multiphase flow studies. Cesium chloride was tried as a water-phase tracer, but complications in its use in low permeability cores resulted from sorption of cesium by the core or water-wet pads. IodoI3'ben-zene proved very satisfactory as an oil-phase tracer. The synthesis of iodobenzene from the sodium iodide as received from Oak Ridge is simple and direct. The tracer is insoluble in water and there was no evidence of sorption by any of the core materials used. use of the method to determine saturation profiles during capillary and dynamic desaturations and relative permeability measurements on oil-water and oil-gas systems is described. Comparisons of the dynamic and capillary methods of relative permeability determination were made using the tracer to check core saturation and saturation distribution. Other experiments are also described in which mobility of the oil phase at various saturations was measured by displacing labeled oil by flowing inactive oil. Similar experiments were made using water labeled with cesium 134. INTRODUCTION To be fundamentally sound. any laboratory method of determining relative permeability must meet, among others, the following requirements: (1) the core saturation between the pressure taps must be uniform, and (2) there must be uniform pressure difference between the phases in the region between the pressure taps. In practice it may eventually be shown that appreciable departure from either or both of these conditions may be permitted without introducing sensible error. but the magnitude of such error remains to be established. There is need then for methods of saturation determina- tion which will determine the saturation profile in a core as well as the overall average saturation given by the gravimetric or material balance methods usually employed. Methods which have received consideration include resistivity, X-ray absorption, gamma ray absorption, neutron diffraction, and radioactive tracers. The resistivity method has use in the determination of profile, but needs checking by independent means.' The X-ray method has been used successfully, but requires elaborate equipment and calibration.23 4 At present gamma ray absorption is practical only for very large cores. The neutron methodo does not appear adaptable to measurement of saturation variations in short cores since it is a scattering method. Russell, Morgan and Muskat' employed radiovanadium in a study of the mobility of interstitial water. Coomber and Tiratsook used radioiodine as an oil-phase tracer and measured profiles in unconsolidated sand packs. ADVANTAGES OF RADIOACTIVITY METHOD A thorough discussion of the theory of radioactive tracers and the technique of using them to study the movement of fluids in sands is given by Coomber and Tiratsoos and need not be detailed here. The method requires less equipment than the X-ray method; the counting problem is similar, but the generation and regulation of the radiation, which is a major problem in the X-ray method, is not required in the radioactivity method. In the X-ray method it is customary to add up to 20 per cent of absorber, usually an iodine compound, to the phase to be labeled. while in the radioactivity method a mere trace is sufficient. A possible disadvantage of the radioactivity method is that a disproportionate amount of the activity comes from the portion of the core nearest the counter, whereas the X-ray gives a true average saturation in the region traversed by the beam. 011 the other hand, this characteristic of the radioactivity method renders it peculiarly adaptable to study of certain types of radial variations in saturation. As with the X-ray method, a tracer may be added to either the oil or water-phase. An oil-phase tracer is more generally useful. however. since it permits work on oil and gas in the

Jan 1, 1952

By E. A. Gulbransen, W. S. Wysong

The behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance. The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotec-tive nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance studyl, 2 of the following problems: (I) the oxidation kinetics in the temperature range of 250°to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films; and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 2 50°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide Moo3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics: time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation. The general interpretation of many of these factors has been previously discussed. Literature The oxidation of molybdenum has not been studied critically. Although many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Gulbransen." Their results showed that Moo2 is the oxide which is stable in contact with the metallic substrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Moos is no longer observed, MoO2 being the only oxide found. Hagg and Magneli6 have shown from an X ray study that the a-phase, orthor-hombic Moo3 is stable up to 1050°C. Two other phases, ß and ß with compositions close to MoO2.90 are also obtained. The formula for the 0 phase is not given but that of the ß phase is defined as Mo9O26 The 0' phase is found to be built upon a monoclinic unit cell. A ?-phase is isolated from a preparation MoO2.75 heated for 17 hrs at 670°C. This phase is

Jan 1, 1949

By E. A. Farrell

A comprehensive survey is made of the status of the asbestos industry as it relates to marketing the product. Included are descriptions of the various types of asbestos and the grading and classification systems used. The uses of asbestos, distribution practices, and types of ore bodies are all related to marketing. World production, the producers and their capacities and world consumption for 1966-67 are summarized and statistical data are included. Asbestos is a general term describing a family of fibrous minerals of the serpentine and amphibole mineral groups. Asbestos has a long history going back to the time of the Egyptians, when it was used as a lamp wick. The commercial mining of asbestos started in Canada, Russia, and Africa in the 1800's, and the first asbestos products were made in Italy and Russia. The five main types of asbestos are: chrysotile, accounting for 95% of the total mined, amosite, crocido-lite, anthophyllite, and tremolite. Canada, Russia, and Africa are the major producers of asbestos. The commercial utility of asbestos was at first based on the heat resistance of the fibrous mineral in the form of packing, at the start of the industrial revolution. Its current utility is based more on its ability to reinforce binders such as portland cement, rubber, and plastics. Its inertness to the chemical nature of most binders is unique. Most important is its ability to maintain its reinforcing utility when the product is exposed to weather and soil conditions as in asbestos cement boards and pipe, and heat, pressure, and chemical exposure as in brake linings and gaskets and packings. The mineral asbestos is also unique because its fibrous form permits it to be spun and woven to cloth or formed into paper. Many asbestos applications are critical to national defense and at the present time, there are no satisfactory substitutes. Grading and Classification Canadian chrysotile asbestos fiber is graded and priced by length since basically the longer the fiber the higher the utility. The Canadian asbestos industry does not, however, classify the fiber by direct length measurement, but by a dry screening test. The method is called the Quebec Standard Screen (QS) test. One pound of fiber is mechanically shaken in four vertically stacked sieve boxes. The relative proportions remaining on the sieves defines the grade. The longer the fiber, the larger is the amount that stays on the top coarse screens and the less on the lower, finer mesh screens. Other tests can be used to further define the length distribution of fiber such as the wet screen Bauer McNett and the Suter Webb Comb (3 group only). The Canadian grading system divides the milled fibers into 5 main groups: group 3, 4, 5, 6, and 7, with 3 group being the longest, and 7 the shortest. Each group is further divided to subgrades, identified in each group by the letters A to Z, with "A" the longest and "Z" the shortest. See Appendix 1 for the Canadian QS classification system. The Russians also use the QS test on chrysotile. The Africans classify their chrysotile into grades similar to Canadian. The African crocidolite and amosite, however, are classified into actual length groups such as l to 2 in. and 2 to 3 in. Amosite and crocidolite are generally longer than chrysotile but also more brittle. Milled asbestos is not composed of staple length fibers like fiber glass or cotton, but of a mixture or blend of fibers ranging from long to short. Milled asbestos has a fiber length distribution similar to the particle size distribution of a powder. For example, the longest group 3 chrysotile grades have a high percentage of the longest fibers (1/2 to 3/4 in.) and low percentage of short fibers (0.003 in.). The figures in Table 1 give the approximate length distribution of the longest, middle, and shortest groups. A second and further method of classifying fiber is the degree to which the fiber bundles are separated to form a larger number of smaller diameter bundles. This property is normally described as the degree of fiberization, openness or surface area. Air permeability tests are used to measure surface area. Asbestos pro-

Jan 1, 1971

By P. E. Senseny

INTRODUCTION Massive hydraulic fractures have been used since 1949 in the petroleum industry to enhance production rates and increase recoverable reserves. Currently, a research program, the Multi-Well Experiment, is underway to develop the understanding and technology to a1 low economic production of the large gas reserves of the low permeability, lenticular sandstone formations in the western U.S. (Atkinson, et al, 1981; Northrop and Sattler, 1983). Use of state- of-the-art hydraulic fracturing techniques is a part of this investigation. As a portion of an extensive core program in support of this experiment (Sattler, 1983), fracture toughness has been determined for 56 sandstone, shale, mudstone, or siltstone horizons from three wells in the Piceance Basin. The role of fracture toughness in hydraulic fracturing is not well understood because other factors, such as in situ stress, dominate fracture geometry and containment. Rubin (1983) concluded from analysis of his laboratory hydrofracture experiments that fracture toughness should be included in design and numerical simulation of hydraulic fractures. However, van Eekelen (1982) contends that the stress intensity at the crack front should be so much greater than the fracture toughness of the rock that toughness can have no importance. Generally, fracture toughness and other material properties, such as elastic moduli and permeability, are thought to be of secondary importance in determining fracture geometry and containment. In spite of this, there is a need to acquire a more quantitative understanding of their importance for accurate design and simulation calculations. Analysis of fracture geometry and containment data from hydraulic fracturing experiments carried out in formations where fracture toughness and other rock properties are

Jan 1, 1984

By Leon W. Dupuy

Many articles have been written describing peculiar and particular types of drilling. Little correlation has been made between the character of ground to be drilled and sampled and the type of drilling most desirable for procuring satisfactory samples. In development work, the engineer and metallurgist often desire the recovery of a sample in as physically natural a condition as possible, particularly when the sample must provide material for process tests as well as chemical and physical analyses. This paper describes the results of experimentation in drilling unconsoli-dated materials carrying titanium minerals in the Magnet Cove area, Ark. The drilling was most difficult in that the ground varied much in consistency, and it was vitally necessary to recover a physically natural sample. Ordinary churn drilling recovered a sample that could be analyzed chemically, but the sample was not in its natural state. The problem was successfully solved by utilizing and further developing methods used in the oil and clay industries. In the Magnet Cove area of Hot Spring County, Ark., the titanium minerals include rutile, brookite, ana- tase, leucoxene, and others. They occur in soil, clays, and altered rocks adjacent to novaculite in contact meta-morphic deposits. In preparing titanium minerals for use in the industry, it is necessary to know the physical characteristics of the ore. Also it is believed that the particular physical character of the titanium mineral used is just as important as the chemical character. Brookite and rutile, for example, are the same chemically but differ in crystalline structure. In preparing titanium minerals for market, beneficia-tion is necessary. For the millman to make a satisfactory laboratory test, the sample he uses must be as nearly of the same physical character as he would have from mine run ore. In the past at Magnet Cove, churn drilling had been done on the properties, and assays of total titania had been obtained. It was found, however, that the total titania was indicative merely of the presence of titania but did not tell the metallurgist the character of the material or even give him the slightest indication of what he might expect to recover. When the Bureau of Mines entered the field in the winter of 1947 and 1948, it was therefore necessary that a natural sample be recovered. LIMITATlONS IN ORDINARY PRACTICE The churn drilling that had previously been done had shown that the occurrence of titanium-bearing mineral was somewhat widespread. The samples were, however, completely beaten up and in a finely powdered state. The minerals had been slimed, and such ore dressing tests as were made from the churn-drill samples were found to be worthless. Test pitting and outcrop sampling had provided satisfactory samples of surface ore but did not represent the entire ore body. A quantity of rutile had been produced from the surface residual concentrations in the westerly part of the cove, but production ran into metallurgical trouble as depth was attained. Representative deep samples upon which ore dressing research might depend were needed.

Jan 1, 1950

T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—Mr. Killian is to be commended for his inquiry as to why a decrease of 15.3 pct in coke consumption was accompanied by a decrease of only 1.9 pct in the CO/CO, ratio of the top gas. Although I encouraged him in his efforts to find a more significant and meaningful carbon-gas ratio, the method, calculations, and conclusions originated entirely with the author. Whether we agree entirely with the assumptions underlying his corrected ratio, I think we can all agree that a better ratio is needed, and that he deserves credit for recognizing the need and for doing something about it. To be most useful, the CO/CO, ratio for the top gas should reflect the way in which the carbon is gasified in the furnace, particularly the degree of oxidation and the extent of heat release. The effect of CO, from the decomposition of the limestone and the effect of the reaction of CO and water vapor in the upper part of the furnace on the quality of top gas should be isolated from the effect of more basic reactions such as ore reduction and solution loss. The reduction of sufficient iron oxide to produce a ton of pig iron and the accompanying changes in the proportions of the carbon gases can be expressed on a mol basis as follows: 16.5FeA + 16.5CO - 33FeO + 16.5CO, [1] 33FeO + 33.0CO = 33Fe + 33CO. [2] The CO, from eq 1 normally escapes from the furnace because it does not react with coke at the temperature of its release. However, as much as 50 pct of the CO, from eq 2 may react with coke because it is released at temperatures above 1000°C: 16.5CO. + 16.5CO2 = 33CO [3] Thus we see that the gasification of 16.5 mols or about 200 lb of C in solution loss will regenerate as much CO as is required for the last stage of reduction. The pronounced effect of reaction 3 on the final proportions of CO and CO, in the gas stream is obvious. It also follows that reaction 3 materially alters the heat release but it cannot be entirely eliminated in Lake ore practice. A previous study indicates that 100 lb of solution loss may be necessary to maintain the reducing power of the gas. A reduction of 100 lb from the normal level of 200 lb would mean that over 1,-000,000 additional Btu are released in the process. The 100 lb of additional carbon which will be burned at the tuyeres will release 437,000 Btu and the absorption of 583,000 Btu by eq 3 would be prevented. One of the chief objectives of sized ore burdens and more uniform distribution of the gas stream is to minimize solution loss by completing reduction higher in the furnace and in turn to release the maximum amount of heat from the carbon charged. It was odd, indeed, to find that the use of sized ore and sinter in the careful tests reported by Dobscha had changed the CO/CO2 ratio very little. The author has stressed the close correlation between his corrected CO/CO, ratio and production. A correlation of fuel consumption and the CO/CO, might be more logical. Fuel consumption on the prepared ore burden decreased 15.3 pct whereas the corrected CO/CO2 ratio decreased 19.0 pct. Although this agreement between the reduction in fuel and the reduction in corrected CO/CO2 ratio is not as close as the correlation with tonnage, it indicates the corrected ratio is superior to the normal ratio which decreased less than 4 pct. Some adjustment should be made for the reaction: CO + H2O = CO2 + H2 —700Btu [41 because there is evidence to indicate that about one half of the hydrogen is formed in the upper 21 ft of

Jan 1, 1953

By John Griffen

THE modern anthracite breaker or washery uses almost completely a wet method of preparation, which requires, roughly, 1 gal. of water per minute per ton of production per day. The entire anthracite industry uses about 320,000 gal. per min. of water for this purpose or 800,000 tons of water per day. As this water leaves the breakers, it contains fine solids-coal, slate, pyrite, and clay-and is then called silt or slush; as slush is the term most commonly used, it will be employed throughout this paper. The solid content of the slush will be referred to as solids. In the earlier days of anthracite mining, little coal was washed, less crushing was employed, and virgin coal was mined exclusively. As a result, the slush problem was not acute because of the relatively small quantity and the coarseness of the solids. Such slush as was produced could usually be easily impounded and retained or could be discharged into streams without any appreciable pollution being apparent. The character of the fine waste from the breakers, changed materially as its quantity increased until now about 40,000 tons of slush solids are produced daily. Second mining and robbing operations materially increased the quantity of fine solids delivered to the breaker in the mine car. The demand for chestnut, stove and egg sizes, to the exclusion of grate, steamboat, and lump sizes, require finer crushing of the mine-run coal with a consequent increase of fine solids in slush. The use of rice and barley sizes removed a considerable tonnage of coarser solids from the slush but left great quantities of fine solids difficult to retain completely and store and long considered of no possible fuel value. Despite the efforts of the coal operators, the slush solids have found their way into the streams causing, in some cases, serious pollution. The Water Supply Commission of Pennsylvania published, in 1916, a report on Culm in the Streams of the Anthracite Region,1 from which the following is taken: About 40,000,000,000 gal. of water carrying 10,000,000 tons of fine culm are discharged into the water-courses direct, flushed into the mines, or disposed of by various means on the surface. The extent to which the very small sizes of anthracite

Jan 9, 1921

By Blamey Stevens

(Butte Meeting, August, 1913.) THE following paper aims to make a full explanation of the phenomena of rock jointing: It may be unnecessary to give any general description of what are termed joints in rocks, but Professor Geikie's clear and faithful generalizations are so illuminating that no excuse need be given. for introducing the following and other quotations into this paper "Almost all rocks are traversed by vertical or highly inclined divisional planes termed joints. These have been regarded as due in some way to contraction during consolidation (fissures of retreat) ; and this is no doubt their origin in innumerable cases. But, on the other hand, their frequent regularity and persistence across materials of very varying texture suggest rather the effects of internal pressure and movement within the crust." 1 General Explanation.-In this paper I show that the phenomenon of jointing may to a large extent be accounted for by the pressure of the water contained in the pores of the rock. To understand this, each constituent grain of the porous material may be considered to be separately compressed by the water which submerges it. As all the grains are held together by cohesion, the whole mass is contracted by this pressure. In an indefinitely extended mass, however, there must be a limit to the possible contraction without rupture, because the material is restrained from moving freely by other material around its boundaries. The mass of rock thus becomes broken up. This phenomenon is known as '" shrinkage " jointing. The term " shrinkage " is an apt one, if it be understood that the shrinkage of the rock is often brought about by change of stress. Stresses.-The compressive component of water stress on the individual grains is evidently the same as that of the water with which it is in contact. This is so, both before and after the jointing is formed. Before the jointing is formed there is, however, a tensile stress in one or more directions which keeps the material from contracting. .

Jan 7, 1913