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By J. W. Spretnak, R. Speiser

IT has been suggested that boron in steel may form a film entirely around the austenite grain and that this film is responsible for the boron hardenability effect. In this connection, it is of interest to examine some of the ramifications of the concentration range of boron usually employed in hardenable steels, namely 0.0005 to 0.003 pct in a grain size range of ASTM grain size No. 1 through No. 10. The ratio of the iron to boron atoms and the number of unit cells of y iron per boron atom are listed in Table I. Even at the highest concentration considered, there are 1600 unit cells of y iron per boron atom, assuming a uniform distribution of boron. To investigate the possibility of the boron film formation, the number of boron atoms required to cover the grain surface completely must be calculated. With some transition elements, boron crystallizes in sheets composed of equilateral hexagons very much like graphite.' The selected value for the length of a side is 1.80Å. A simple calculation shows that two boron atoms cover an area of 8.4x l0 -16 sq cm. Table II lists the number of atoms of boron required for the formation of the monatomic film and Table III lists the number of boron atoms per grain. The hypothetical cases of 100 pct and 10 pct adsorption are calculated (all boron atoms in a grain and 10 pct of all boron atoms in a grain are located at the grain surface respectively). In Table 111, all combinations of grain size and composition below and to the left of the solid line (100 pct adsorption) and the dashed line (10 pct adsorption) are excluded as to the possibility of covering the grain surface with a continuous boron film. Thus, even for 100 pct adsorption, the smaller grains can form the film only at the higher concentrations. For the best case, grain size No. 1 and 0.0030 pct B, the required degree of adsorption is 3.9 pct. The above calculations deal only with the number of boron atoms required to form a monatomic film and do not take into account the mechanism of concentration of boron at the grain surface and the possible limitations to the extent of this concentration at a constant temperature, as for example in the austenitizing process. The question next arises as to how this surface concentration can occur during an isothermal treatment. Such surface enrichment of boron must occur through the phenomenon of surface adsorption, i.e., the concentration of solute atoms in solid solution in the vicinity of the surface without precipitation. A solute atom will tend to concentrate at the grain boundary if it reduces the interfacial tension. The possibility of adsorption effects involving both boron and carbon in iron has been discussed.' In general, the tendency for a sol-

Jan 1, 1954

By Benjamin L. Miller, Charles H. Breerwood

From earliest recorded times, limestone has been employed in the industrial life of peoples of all sections of the world where it exists. It is widely distributed and therefore has been available in almost every country and has been employed for a variety of purposes. Its earliest use was for buildings, since it is more easily quarried and dressed than most other kinds of rocks and so could be utilized by early inhabitants, poorly equipped with tools. The next use was in the manufacture of lime, which was employed by the ancients in mortar. These two uses of limestone are still all important, but they have been overshadowed in scores of regions by literally hundreds of new applications for raw limestone or products made from it. Anyone familiar with modern manufacturing processes can quickly call to mind many industries in which limestones are essential, and new uses are continually coming to notice. Any enumeration would probably be incomplete and soon out of date. Origin of Limestone Disregarding details and unusual types concerning which often there is insufficient evidence and considerable difference of opinion, limestones have been formed by the precipitation of calcium carbonate from solution through the action of organisms, both plants and animals, or in a limited number of instances by chemical reactions without the intervention of living forms. Some of the organisms extracted the calcareous material in order to build up hard structures, either as bony skeletons or as coverings (clams, snails, etc.), whereas others in their life functions emitted substances that resulted in the precipitation of the soluble constituents outside the organisms themselves. In some instances the organisms utilized only calcium carbonate but in some cases other compounds as well were precipitated. Various materials have been found in the hard parts of animals, and for that reason it is almost impossible to find a pure natural limestone; that is, one composed entirely of CaCO3.

Jan 1, 1938

By Charles H. Breerwood, Benjamin L. Miller

From earliest recorded times, limestone has been employed in the industrial life of peoples of all sections of the world where it exists. It is widely distributed and therefore has been available in almost every country and has been employed for a variety of purposes. Its earliest use was for buildings, since it is more easily quarried and dressed than most other kinds of rocks and so could be utilized by early inhabitants, poorly equipped with tools. The next use was in the manufacture of lime, which was employed by the ancients in mortar. These two uses of limestone are still all important, but they have been overshadowed in scores of regions by literally hundreds of new applications for raw limestone or products made from it. Anyone familiar with modern manufacturing processes can quickly call to mind many industries in which limestones are essential, and new uses are continually coming to notice. Any enumeration would probably be incomplete and soon out of date. Origin of Limestone Disregarding details and unusual types concerning which often there is insufficient evidence and considerable difference of opinion, limestones have been formed by the precipitation of calcium carbonate from solution through the action of organisms, both plants and animals, or in a limited number of instances by chemical reactions without the intervention of living forms. Some of the organisms extracted the calcareous material in order to build up hard structures, either as bony skeletons or as coverings (clams, snails, etc.), whereas others in their life functions emitted substances that resulted in the precipitation of the soluble constituents outside the organisms themselves. In some instances the organisms utilized only calcium carbonate but in some cases other compounds as well were precipitated. Various materials have been found in the hard parts of animals, and for that reason it is almost impossible to find a pure natural limestone; that is, one composed entirely of CaCO3.

Jan 1, 1938

By J. A. Herbst, A. L. Mular

Digital simulation is defined and simulation techniques are re- viewed. Typical methodology involves the selection of models, the adjustment of raw data, the selection of a fitting strategy, the assessment of model accuracy in a statistical sense, and the development of an executive simulation structure. Simulations serve as aids for process engineers in evaluating the feasibility of a proposed flowsheet and the effect of a modification to an existing flowsheet. In addition, simulation plays an important role in off-line optimization and in the evaluation of alternative circuit control strategies. Several examples are presented to illustrate these uses for simulation including applications in crushing circuits, grinding circuits, and flotation circuits. It is the opinion of the authors that, within the next decade, mineral processing plants will be studied routinely via digital simulation during the preliminary design stage. Simulation will constitute an important component of the design decision making process.

Jan 1, 1978

By M. R. Geer, H. F. Yancey

With the exception of pneumatic processes and a few special beneficiation methods of comparatively limited application, all mechanical coal-cleaning and mineral-dressing processes involve the admixture of solid particles with a liquid, generally water. Upon completion of the beneficia-tion process the solids must be reclaimed from the water. With coarse particles separation of solids from water is accomplished readily by the simple expedient of screening, but recovery of fine solids presents a much more difficult problem. Thickening and dewatering are practiced so generally, both within the mineral industry and elsewhere, that they have been the subject of study through the years and a number of processes for making the solid-liquid separation have been developed. Dorr-type thickeners have been standard equipment lor many years, and more recently driers employing centrifugal force have gained in popularity.' A cyclone device employed to thicken the loess suspension is a novel feature of the loess heavy-medium coal-cleaning process developed by the Netherlands State Mines in the thirties. The cyclone thickener was first mentioned by Driessen2 in 1939 in a paper describing the loess process and has been the subject of two more recent reports by the same author.3 The cyclone does not differ greatly from cyclone dust collectors used in this country for years, except that it is operated wet rather than dry. Advantages of the cyclone over other thickening devices are its simplicity of construction, high capacity, and the fact that, having no moving parts, it is simple and inexpensive to operate. The Bureau of Mines became interested in the cyclone after one of the present authors observed it in operation in the Netherlands in 1945. The first experimental work with the cyclone conducted by the Bureau of Mines was an investigation of the unit functioning as a heavy-medium cleaner for fine coal—a use for the cyclone that was conceived long after it had been perfected as a thickener. The results of this investigation were published last year.4 The present investigation deals exclusively with operation of the cyclone as a thickener. Object and Scope of Investigation Although the cyclone thickener has been dealt with in three reports by Driessen, its use as a thickener was not the principal subject of any of these reports and therefore neither the cyclone itself nor its operation was described completely. The design of the cyclone was described only in a very general way, only limited operating results were given, and virtually nothing was disclosed about the influence of the various possible operating variables. Moreover, the Netherlanders apparently had employed the cyclone exclusively for thickening loess and had not employed it On coal 'lurries. One English colliery has used a cyclone to thicken coal slurry,5 and as it appeared that

Jan 1, 1949

By Charles A. Ashburner

The manufacturing and domestic consumers of anthracite are beginning to realize the fact more fully, that the coal purchased for any one year does not seem to burn so freely, does not fire with so little trouble, and does not last so long as that purchased during other years, or vice versa. Where coals of different sizes, or from different districts, are offered to the trade by the same or competing salesmen, the question suggests itself, which shall we buy ? Among housekeepers, who are the most numerous class of consumers, though on the smallest scale, distinction is seldom recognized among these anthracites. By other consumers the coals are grouped into those which, when burned, will produce either a white or a red ash, special qualities being arbitrarily attached to each. Others, again, know only of three varieties : (1) Those from the WYoming and LacKawanna fields, or the coals shipped from the northernmost basins over the railroads running through northeastern Pennsylvania direct to New York—notably, the Delaware. Lackawanna and Western, Delaware and Hudson, and Erie railways; (2) those shipped by the Lehigh Valley Railroad and the Lehigh and Susqaehanna division of the Philadelphia and Reading Railroad down the Lehigh Valley ; and (3) those shipped over the main line of the Philadelphia and Reading Railroad down the Schuylkill Valley. In special localities, where a favorite coal is largely used, the consumer will speak of one class, composed of his favorite coal, which possibly comes from two or three collieries, with a total aggregate annual production of less than a million tons; and of a second class, composed of the coals from all the other collieries in the anthracite

Jan 1, 1886

By H. S. Munroe

THE native copper of Lake Superior occurs in the form of fine grains and scales, disseminated in small percentage through the copper-bearing rock ; and in large and small masses, from a few pounds to several hundred tons in weight. Formerly the bulk of the copper came from the mines of Ontonagon and Keweenaw counties, producing mass copper. At present these mines furnish less than one-tenth of the total product, and fully one-half of this is from a single mine. The masses are usually found irregularly distributed in nearly vertical fissure veins, and require much dead work in sinking, drifting, and stoping for their development. The risk and expense attending the working of these mines have made them, with few exceptions, anything but profitable. * Read at the Montreal meeting, September, 1880.

Jan 1, 1880

By H. T. Hildage

Although Greater New York does not bear any resemblance to a great mining district, the mining operations that are being conducted in and about the city are both extensive and interesting in character. With regard to the extent, it may be mentioned that, at present, there is more dynamite used in New York than in any mining district in the United States; that there are under construction about 38 miles of tunnel, and that 66 miles more are projected, most of which must be constructed .in the near future; that since 1903 at least 2,000,000 tons of earth has been removed in underground work, in addition to about 3,500,000 tons that has been removed in open-cut in connection with tunnel-work, and many times this quantity that has been removed in excavating foundations for buildings not connected with tunnel-work; and that there are to-day probably more than 5,000 men engaged in mining-work in and about New lrork City. These undertakings include almost every operation connected with underground work, from exploration by means of trench and boring, to the sinking of large shafts and the driving of large tunnels through every kind of ground from hard rock to soft, semi-fluid silt and quicksand. It is proposed in this paper to give a general description of some of the methods and appliances used in the opening-up of a " mine " in a large city, and a brief description of some of the &'mines" now being developed in New York, connecting as far as possible the methods described with the particular work for which they were designed, in order to give a general idea of the

Jan 1, 1908

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 Kenneth S. Ritchie

The natural emulsion samples used in this study were shipped directly from twelve California oil fields, through the courtesy of the superintendents of the main producing companies in those fields. Representative parts of each sample were chosen for the slides. Preparation of the slides was generally made in less than two minutes, including time of exposure; in a few cases, about five minutes was required. The short time was intended to minirmize the changes in conditions. Whenever comparison was of value, standard conditions were established. Spreading by gravity was adopted instead of smearing. Cover glasses were not allowed to rest on the films. General Characteristics of Emulsions The main purpose of the general views (Figs. 1-16) is to illustrate the general characteristics of the dispersed droplets together with any other constituent or impurity that may be found in each emulsion. The magnification is given so that dimensions could be measured from the plates. The slides used for these views had spherical recesses; they gave the best light. Where crystals were intended to be shown in the picture a filter (green was the best') was usually used. Emulsions that showed a tendency to move by concentrated light were pictured without a condenser.

Jan 1, 1931

By Lawrence K. Jetter, Robert F. Mehl

SOME advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory.? Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selected for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatometric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system-a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation ;2,3,4 there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type-the ideal case which Becker5 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1942

By P. H. Brace, N. A. Ziegler

THE study of the relations between gases and metals is one of perennial interest to all who are connected with the production of high-grade metallurgical products. The data reported here are the outcome of work of which the object is to determine the effects of dissolved gases upon the properties of metals and to gain a more detailed knowledge of the reactions between gases and molten metals, particularly iron, under definitely controlled conditions. We have attempted to reduce our margin of error by dealing with relatively large quantities of metal, from 4 to 13 lb. (2 to 6 kg.), and keeping the ratio of refractories to metal as small as practicable. The ingots produced are large enough to provide adequate material for making determinations of magnetic and other physical properties. In choosing the bell-jar type of furnace we were influenced by the results of considerable experimentation along the same general line which indicated that, for the scale on which we were to work, it was important to have the furnace structure independent of the vacuum enclosure. The use of a bell-jar surrounding the entire furnace accomplishes this and also gives great freedom of observation during operation and ready accessibility for the replacements which are necessary after each run. Our choice of analytical method was made in the light of the results secured by H. M. Ryder, who used a method similar in principle for the analysis of very small quantities of gas extracted from strips of metal heated electrically in high vacuum. We have presented some selected preliminary experimental data as being illustrative of the quantity and nature of the gases which occur in iron of different origins, but do not urge any hypothesis at this time. THE FURNACE Our furnace may be described as "a high-frequency induction furnace of the bell-jar type." It is similar in a general way to that described by Cain and Peterson' though we have introduced certain refinements of

Jan 1, 1928

By A. A. Bauer, F. A. Rough, G. H. Beatty

AS a result of recent studies, the constitution of the zirconium-uranium system has been fairly well defined. A diagram for the system is shown in Fig. 1. However, both oxygen and nitrogen are known1-3 to have a pronounced effect on the limits of both ß- and e -phase regions. It has been shown that small amounts of oxygen severely constrict the compositional limits of these phase regions in the ternary zirconium-uranium-oxygen system. A previously published tentative diagram shown in Fig. 2 illustrates the ß-phase constriction resulting from oxygen additions. Generally, iodide zirconium has been used in constitutional studies of zirconium-uranium alloys. While this is the highest purity material available, cast iodide zirconium-uranium alloys will generally average from 200 to 300 ppm 0 and from 50 to 60 ppm N. Thus, while the constitution of the zirconium-uranium system is fairly well defined, it must be realized that this definition applies to alloys containing in the vicinity of 250 ppm 0 and 50 ppm N. The present investigation was undertaken to accurately determine the boundary between the ß-plus-P and ß phases at a single temperature in the binary zirconium-uranium system by quantitatively

Jan 1, 1959

By Persifor Frazer

The mines which I am about to describe are all situated in the northern part of the States of Nuevo Leon and Coahuila, Mexico, between the twenty-sixth and twenty-seventh degrees of latitude. They might be grouped, orographically, into four classes: 1. Those in the Sierra de la Ygnana chain; 2. Those in the Sierra de Gomez chain; 3. Those in the Cerro Mercado; 4. Those in the Sierra de San Marcos chain. (See large map.) The first two of these may be further arranged in one geographical district, to which the name, "the Villaldatna. district," may be applied, and the last may be ascribed to the geographical district of " Monclova." Geologically described, the country rock, in which four of the six mines occnr, is a limestone, concerning which a few words will be said further on, to wit.: The Arroyo (gulch), the Montanos and the Pinitos (pines), in the Villaldama district, and La Paloma (the dove), or Iron Mine, in the Monclova district. The San Rafael appears to lie in granite, or a heavy-bedded gneiss, presenting most of the characteristics of the latter, though the contact plane of the limestone is not far off. It is certainly worthy of attention that the ore occurs in that portion of the crystalline rock, which is nearest to the limestone, and it has been thought by some observers to be a true contact vein. It is well known that veins of this character are very often distinguished for constancy and richness. Although the undersigned cannot entirely free himself from the impression that this proximity of different formations has had an important influence in the origin of the part of the vein on which this mine is situated; still he was unable to establish it actually at the contact of the limestone and granite, but rather a short distance within the latter. Two openings of the Riojas vein were respectively in limestone and in rotten whitish granite, but this fact, if established (as by the correspondence of the strike line of the vein in direction with that of a line joining the

Jan 1, 1884

By Theodore B. Comstock

The existing topographical features of the United States present many points of interest to the student of dynamical geology, but there is, perhaps, no subject which offers a more promising field for investigation than the relations between the geological structure and the mineralogical characteristics of the principal mining districts. There are seven prominent culminating points in the relief of North America, each one of which can be used as a type of the physical features of all the others. Again, if we divide these seven elevated districts into two sets, we shall discover a still more striking parallelism between the individual members of each group. But the most remarkable revelation is the fact that each one of these points is more or less closely the centre of an area of economically important mineral resources. It is interesting to note in this connection that six of these mineral tracts lie mainly within the borders of the United States, three of them being almost wholly in our territory. For

Jan 1, 1883

By John G. Tate, George W. Nicolson, James L. Bruce

For more than 25 years modern mining has been carried on in the Island of Cyprus, Mediterranean Sea, by the Cyprus Mines Corp. of Los Angeles, Calif. The general features of these operations have been described.' From 1935 to June 30, 1940, top slicing in the Mavrovouni mine produced in excess of 2,000,000 long tons. The rate for the last part of this period was approximately 50,000 tons per month. Description of Ore Bodies The shape Of the Ore body now being top sliced in the Mavrovouni mine is an inclined irregular pyritic pipe or chimney of large dimensions) extending from unknown depths below the bottom level at elevation 250 ft below sea level) to the highest level at elevation 400 ft above sea level. The present surface above the ore body lies between 550 and 650 ft elevation. Undoubtedly the Ore body extended to surface and was Mined by the ancients by opencast and underground methods. The old pits were gradually filled up by erosion until now they show as slight depressions in the topography. The largest area of the Ore body is at elevation 170 ft below sea level, where the horizontal section is almost elliptical, with a width of 600 ft and a length of 1000 ft. Below this elevation the shape of the ore body continues to be elliptical but with reduced dimensions. Above this elevation it rises flatly towards the south with a substantial depression in the upper-side of the chimney and irregular ridges or wings rising on each side. It gradually grows smaller as it rises. The ore body is a pyritic replacement of andesitic extrusives which occur as flows and pillow lavas. With the exception of the upper portions of one or two small offshoots rising from the main ore body, all ore is completely surrounded by andesite. Most of the andesite lying above the ore body is covered by marl and Clay sedimentaries of Miocene and later age, The Miocene is presumed to be older than the ore mineralization. That portion of the andesites which lies between the sedimentaries and the ore body has been broken by slumpage, and weathered, and iron-Stained by the descending meteoric waters, It is a mass of crushed material that caves and follows downward readily as the top-slice stopes retreat. The main ore body is a heavy cupreous pyrites mass assaying on the average about 4.0 pet Cu; 48.0, S; and 42.0, Fe. In places the copper drops below 1.0 pet. on the borders of this heavy sulphide ore body lie disseminated cupreous pyrites ore deposits of large dimensions. some portions of these appear to be closely related to the heavy sulphide ore, as the ratio of copper to pyrite is about the same. The greater part of the disseminated ore, most of which lies immediately to the east of the main Ore body, contains less than 0.10 pct Cu and about 25.0 to 30.0 pct S. 'This probably can

Jan 1, 1949

By John V. Beall

There is an underlying surge to mining in the Philippines." So said A. R. "Ham" Reed, general manager Itogon-Suyoc Mines, Inc., to this reporter last November. Itogon-Suyoc is a small company with a struggling gold mine, a mixed sulfide mine and some prospects. In the Republic of Philippines (ROP), politics, which have an effect on mining, create some uncertainties. By July 1974, no mining company may have more than 40% foreign ownership. The ownership provision is a matter of concern to such important companies as Atlas and Benguet Consolidated and is generally considered a deterrent to new foreign investment. Under these circumstances, Reed's comments are of interest. On foreign prospectors: Don't come in cold; find a Philippine partner or buy into a company already here. Physical conditions of exploration are tough-terrain, communications -but the mineral potential is excellent.

Jan 4, 1969

By Myers, J. F.

The purpose of the mill tests reported herein, was to determine the relative power efficiency of fast and slow rod mill speeds on the ores of the Tennessee Copper Co. The tests were carried out at the lsabella Mill of the Tennessee Copper Co. under normal operating conditions. Every effort was made to keep the ore supply and other conditions constant, but it will be noted that some slight variation did occur. The open circuit 6 by 9 rod mill, and ore, used in these tests have been previously described.' Four motor drive pinions were available and the tests were performed in the following manner: each pinion was used to drive the mill for a period of one week. Constant sampling prevailed during the test run, and a composite sample for each speed test was made. Realizing that some slight liner wear took place during the four-week test-run, and that some slight variation of the ore may have taken place, a second and then a third series of four-week test- runs were made with the four different pinions. The screen analysis of each of the thee-week run samples at the various speeds were composited and the results are shown in Table 1. The authors feel that the 12 weeks of operation consumed during these test-runs would represent fairly the effect of each mill speed. The data of line 37 show that within the error of sampling and plant operation, the tons of minus 65-mesh material generated per horsepower hour was the same at all four speeds.

Jan 1, 1949

By John Chipman

THE equilibrium between titanium in liquid iron and titanium oxides has been studied by Hadley and Derge.' They have shown that a minimum occurs in the oxygen content of the metal between 0.1 and 1.0 pct Ti, but its exact level was not fixed. The oxide phase in this minimum range was principally TiO, containing some iron oxide. On the other hand, for concentrations above 5 pct Ti the oxide phase was TiO and the oxygen content of the metal increased rapidly with increasing titanium content. From their observations and the free energy of Ti0 and TiOz reported by Kelley and ah,' it is possible to derive approximate values for the activity coefficients of titanium and oxygen in liquid iron-titanium alloys and the conditions for equilibrium in steel deoxidation. Neglecting possible departures from the stoichio-metric composition, the condition of equilibrium with Ti0 may be expressed as follows: TiO= Ti_ + C) log K = log NTl + log [% O] + log yTi + log fQ Here as a matter of convenience the titanium concentration is expressed in mol fraction while that of oxygen is in weight percent. The activity coefficients are yTi and fo. The value of log fo approaches zero as the concentration of titanium approaches zero, while that of log yTi approaches a limiting value of In Fig. 1 the sum of log NTi + log [% 0] is plotted for mol fractions of titanium between 0.05 and 0.50. The smooth extrapolation gives a value of —4.15 which corresponds to log K — log y:i . We therefore have the equation: According to the data of Kelley and Mah,' the free energy of formation of Ti0 at 1900°K is -82,400 cal. The free energy of solution of half a mol of oxygen in iron, taking 1 pct 0 as the standard state, is -29,300 cal. From these we write: From these equations the activity coefficient of titanium at infinite dilution in iron is found to have a value of 0.011 or log y°. = -1.96. This is only an approximate value but is certainly better than the estimated 0.05 in Basic Open Hearth Steelmaking To obtain approximate values for the activity coefficient at intermediate concentrations, it is as- sumed that log yTi(l is constant and equal to -1.96. This corresponds to a value of E;: = 3 In yTi/aNTi = 9.0 which is not unreasonable We now have the value for the activity of titanium and the percentage of oxygen in equilibrium with TiO. It is therefore a simple matter to calculate the activity coefficient of oxygen which is shown in Fig. 2. The effect of titanium is rather large, being comparable to that of vanadium, but not so large as has been reported for aluminum. The slope of the line at low concentrations corresponds to E: = aln yo/ aNTi=-0.37. At concentrations below 1 pct Ti the deoxidation constant and oxygen content for equilibrium with TiO, can be calculated from the foregoing data and the free energy of formation of TiO,, which according to Kelley and Mah is -144,600 cal at 1900°K. The free energy of solution of oxygen has been given; that of Ti to form a dilute solution with 1 pct Ti as the standard state is RT ln (0.5585 y:i/47.9) = -34,800 cal. From these data we find (for concentrations in wt pct): TiO, = Ti + 2 -0; hFTgO0= + 51,200 cal log if =-5.89 The interaction coefficients, concentrations being expressed as wt pct, are e;: = alogfTi/a[% Ti] = +0.048 and e:' = a logfo,/a[ojTi] = -0.187. The calculation gives the following results which, in view of the impurity of the oxide phase, must be regarded as approximate:

Jan 1, 1961

By B. Habermann

Artificially consolidated sand models, representing one-quarter of a five-spot, have been developed and used to study factors aflecting misciblt. displacrmenr. Sweep efficiency at breakthrough, size of the mixing zone between two miscible liquids and per cent area contacted by drive after breakthrough were determined tor the high mobility ratios encountered in actual resvrvoirs. Quantitative relationships between the degree of viscous fingering and mobility ratio were obtained by measuring the length of the fluid interface. Scaled miscible-slug experiments, supported by field evidence reported in the literature, have shown that when the slug is followed by dry gas the process is less efficient than expected. In addition to low areal sweep efficiencies encountered for high mobility ratio displacements, the effectiveness of a miscible slug is greatly reduced. This is caused by an accelerated growth of the mixing zone between the driving and the displacing fluids. INTRODUCTION Considerable interest in miscible displacement as a secondary recovery process has been shown by the oil industry in recent years. In addition to extensive laboratory investigations, numerous field operations have been initiated so that 39 miscible displacement projects had been reported' in the United States by early 1959. By far the most popular approach in these projects is the use of an LPG slug followed by dry gas. Laboratory tests have indicated that with a small miscible slug, amounting to several per cent of the hydrocarbon pore volume, practically 100 per cent recovery of the oil in place can be achieved and that all of the slug material can be recovered by a subsequellt gas drive. However, these experiments were conducted on small-diameter long cores that can be considered as essentially uni-dimensional reservoirs that do not represent actual field conditions. It soon became apparent that the inherently adverse mobility ratios existing in the reservoir cannot be ignored in any miscible displacement field project. When a less viscous fiuid such as an LPG slug drives a more viscous reservoir oil, fingers develop that reduce the areal sweep efficiency. The slze of the miscible slug to be used is a subject of some controversy. It has been proposed that the size of siug needed be calculated by setting lengths of the mixing zone proportional to the square root of the distance traveled. This proposal is based on experimental evidence' and theoretical considerations"' in which fingering was not a factor. A prerequisite for successful application of the miscible displacement process to field operations is a better understanding of the following factors. L What is the effect of mobility ratio on the rate of deterioration of a miscible slug? 2. How large a slug should be used for given reservoir conditions? 3. What is the sweep efficiency? The purpose of this investigation was to provide some additional laboratory data that should help to answer these questions. More specifically, it was intended to study more quantitatively the effect of viscous fiinger-ing, mobility ratio and slug size on the efficiency of this relatively new secondary recovery process by means of experiments on thin, horizontal, porous medium models.