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By R. C. Buehl, J. P. Morris

ACTIVITY values for sulphur dissolved in liquid iron and slags as functions of composition and temperature are needed in applying thermodynamics to sulphur-control problems in iron- and ' steel-making. The purpose of this investigation was to determine the effect of carbon on the activity of sulphur in the metal phase. The method employed was the same as that used in an earlier investigation' concerning the effect of silicon on sulphur activity in liquid iron. A study was made of the conditions of equilibrium in the reaction between hydrogen gas and sulphur dissolved in iron-carbon alloys. The chemical equation for this reaction can be written as follows: S (in liquid Fe-C alloy) + H2 (gas) = H2S (gas). It was found that the activity coefficient of sulphur in liquid iron increases as the carbon content increases. At 2.3 pct carbon and 1600 °C, the activity coefficient of sulphur is twice its value in carbon-free iron, and at carbon saturation it is more than six times as great. The effect of temperature on sulphur activity was found to be small. Previous work on the reaction between hydrogen gas and sulphur dissolved in liquid iron has been reported by several investigators2,³,4 but only recently have studies been made of the effect of alloying elements. Silicon1 is known to have a pronounced influence on the activity of sulphur in iron, its effect being similar to that shown by carbon as described in the present report. Kitchener, Bockris, and Liber-man5 recently have published a preliminary report of their work on the effect of carbon on sulphur activity in iron. Their experiments were made at 1570°C and carbon saturation in the melt. Under these conditions they found that the activity coefficient of sulphur was approximately doubled by the presence of carbon. This is a much smaller effect than that found in the present work. Experimental Method: The apparatus and procedure were essentially the same as those used in the earlier investigation of the effect of silicon on sulphur activity.' Briefly, the method was as follows: A molten iron-carbon alloy was brought to equilibrium at constant temperature with a mixture of H2 and H2S of constant composition by bubbling the gas through the metal. Samples of the melt were

Jan 1, 1951

By Marc Boyer

Modern civilization, modern industry, and modern standards of living, bring into, sharp relief the present-day essentiality of metals .and minerals, and the wide and diversified use which is made of them. Any attempt, therefore, to appraise the international situation today must take into consideration the metal and mineral resources of the world. If, as some believe, the world is divided into two distinct ideologies of political belief, one unalterably opposed to the other, so that armed conflict is unavoidable, then the question of national strength in mineral resources becomes of paramount importance. If, however, it is possible to avoid war by raising the standard of living in the underdeveloped ?areas of the world, thus ensuring all peoples everywhere against the dread spectres of starvation and disease, then the development of the world's mineral resources assumes even greater importance. Today it is difficult to realize that, prior to the industrial revolution in Great Britain, only a few of the metals and minerals now in common use entered into the everyday life of the people. !iron and steel, copper, lead, tin, and zinc, usually in .their unalloyed forms, along with the more common industrial minerals, were those most widely used, and then only in limited amount. With the advance of technology in metallurgy and in fabricating skills, the list of commercial metals and minerals has expanded until today they number more than eighty.

Jan 1, 1951

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps: 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the moleculea will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1951

By L. E. Shiffman

W. J. Parton—Those operators faced with the problem of treating fine coal whether in bituminous or anthracite will find this paper most timely. I would like to take this opportunity of discussing Mr. Schiffman's paper and at the same time express certain views relating to our Tamaqua plant. I would like to ask the author what type of impeller and diffuser is used in the Denver cells? Screen analysis of products from individual cells indicate that coarser material resists flotation and only floats after greater retention time in the last few cells. Also, the need for a scavenger screen to reclaim non-floated coal particles further stresses this point. I have always felt that more efficient means of cleaning coal between 10-mesh and 28-mesh existed than flotation. Reagent and power costs are high for the flotation process. When floating +28-mesh particles, cell capacity is lowered and some of the particles are lost with the refuse. The Tamaqua plant of the Lehigh Navigation Coal Co. floats —28-mesh coal and capacity of recoverable coal is 40 tph for 1800 cu ft of Denver cells; or 0.05 tons per cu ft of cell. At Kimberly 7.75 tph for 600 cu ft of cell gives 0.013 ton per cu ft of cell. At Bessie 14 tph for 800 cu ft of cell gives 0.017 tons per cu ft of cell. It would be appreciated if the author would comment on what he feels is the upper size limit of particle to attain most efficient utilization of the flotation process. The dewatering screw is a very interesting development since it offers a simple way to prepare coal sludge for more complete clewatering by drainage or mechanical dewatering on screen or filters. In other words it could be used to accomplish the same thing as a thickener tank. I would appreciate having the author's comment on how he thinks such a screw dewaterer would work on a froth.* The process as used in floating coal at the Bessie and Kimberly plants may be referred to as more of a bulk oil float in contrast to a froth flotation process. Experiments on increasing capacity of cells is most interesting since we are going through such an experi- mental period at the present time. Recently a double overflow was installed on our No. 30 Denver cells. So far results are not conclusive. In reviewing this paper the following comments are made pertaining to investigation of methods for increasing capacity: Supercharging: Supercharged air in matte flotation or for that matter the use of the normal amount of air drawn in by the impeller would in all probability cause such an aeration in the cell as to destroy the buoyant effect given to the coal particles by the excessive amount of kerosine used. In other words, air creates an agitation zone throughout the cell, creating a boiling and thereby giving a lower recovery in the cell. It would be interesting to know whether the 7 pct increase in recovery was with no air being admitted to the stand pipe. Changing Impeller Speed: The speed of a receded disc impeller for a No. 30 cell as recommended by the Denver Equipment Co. is, I believe, approximately 250 rpm. At this speed and using supercharged air in excess of 8-oz pressure, we have observed a boiling action in the cells. In our flotation we endeavor to obtain some degree of froth flotation using pine oil as a frother. The boiling action as caused by increasing the amount of air added to the cells is detrimental to recovery in froth flotation. It is our belief that to obtain increased recovery from a cell in froth flotation, additional air must be introduced but at the same time this air must be dispersed throughout the pulp in the form of small bubbles and this can only be done by increasing the speed of the impeller. Therefore, if Mr. Schiffman decreased the speed of the No. 30 impellers and at the same time continued to use supercharged air, the boiling action may have been increased because larger bubbles developed. The lower recovery as reported could be due to this factor. Decreasing the impeller speed will definitely decrease the power consumed but may have other disadvantages. First, we believe it will permit "sanding" in the cell and this in our opinion will increase the wear on the impeller and diffuser, especially so, if there is pyrite and/or sand present in the feed. "Sanding" in the cell when air is used, as in froth flotation, will effect the dispersion of this air and cause boiling.

Jan 1, 1951

By C. E. Baltzer

This is the fourth in a series of coal technology reviews being prepared. in accordance with a recommendation voted by the Coal Division C.I.M. in session at the Jubilee Meeting, Vancouver, 1948, that the Department of Mines and Resources be requested to arrange for publication by the proper Government authority of a Quarterly Review of Coal Technology for distribution among those concerned in the production and use of coal in Canada. Copies of the first review, which appeared in the November, 1948, BULLETIN, pp. 612-614, of the second review in the June, 1949, BULLETIN, pp. 272-275, and of the third review in April, 1950, BUL-LETIN, pp. 1,9?3-196 (also, respectively, in Transactions, Vol. LI, 1948, pp. 262-264 Vol. LU, 1949, pp. 117-120, and Vol: LIU, 1950, pp. 133-136), were distributed by the Dominion Coal Board and are still available on request. In this review, the first in the series in the field of combustion, development and trends during the period approximately from World War II to the present time are described and therefore the presentation is general. Later reviews will particularize developments in relation to the range of coals available in Canada.-ED. INTRODUCTION THE utilization of coal in heat and power producing equipment has become of paramount importance to the coal industry in maintaining stable and profitable markets. In the past, the chief concern was with mining, transportation, and overall supply problems, but modern conditions demand interest in and knowledge of all phases of the product, from coal in situ to its ultimate disappearance in the form of products of combustion. Even the last mentoined factor has caused complications, as is shown by current widespread activity in the field of smoke abatement

Jan 1, 1951

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951

HE purpose of this chapter is to present a general outline of the basic open-hearth process for the benefit of students, practicing open-hearth operators, and metallurgists who wish to review the subject. The discussion is limited to a description of the sequence and purpose of the operations, illustrated by data and examples. Subsequent chapters deal with more detailed and fundamental studies of the subject. The function of the basic open-hearth furnace is to convert various types of ferrous material into finished steel of given composition and quality. In comparison with other steelmaking methods, the basic open-hearth process is one of the most versa- tile, both from the standpoint of the raw materials that can be used and the types of steel that can be produced. The process can be considered as a sequence involving melting, refining, and deoxidation. With some types of liquid-metal charges, the melting stage is not present, but refining and deoxidation in varying degrees are fundamental features of the process. GENERAL DISCUSSION OF BASIC OPEN-HEARTH PROCESS The first consideration in open-hearth practice is the type of charge on which the operation is based. This consists of three components-fluxing, oxidizing, and metallic materials. Fluxes. In the basic process the fluxing material is primarily lime, added in the form of either limestone (CaC03) or burnt lime (CaO). This is supplemented by magnesia (MgO) and lime from the furnace bottom and banks. The function of these fluxes is to form a slag with the silica (SiO2) , manganese oxide (MnO), iron oxides (FeO and Fe2O3), and phosphorus oxide (P2O5) that are produced by the oxidation of varying amounts of the silicon, manganese, iron, and phosphorus in the charge during melting and refining. The slag, composed of the basic fluxes and the neutral and acid oxides, floats on top of the steel bath when the charge is melted. The composition of this slag depends on the amount of each slag-forming element present in the charge and on the extent of oxidation of these elements during the course

Jan 1, 1951

By James J. Bean

F. M. Lewis—I believe that density recorders are a prerequisite to all well operated ore concentrators. Well designed density instruments are very accurate and give an excellent record of the steadiness of the operation. Controlling the density of a pulp with an instrument, as described by Mr. Bean, is new and the experiences in developing this controller at the American Cyanimid Co.'s Mineral Dressing Laboratory are very interesting and should be extremely helpful to others who are planning on designing or installing controlling density instruments. Instruments for recording the density of the classifier overflow or flotation feed are rather common in ore concentrators, but there are a number of profitable uses for these instruments that are not too well known. Density recorders with bubble tubes submerged to different depth in a classifier pool give an excellent record of the classifier operation. The loading and unloading of the machine, that is so easily masked in the density of the overflow, can be easily recorded if the instrument is installed at some depth in the classifier pool. On some occasions, two instruments with bubble tubes at different depths give a more candid picture of the irregularities in the classifier operation. When cleaner machines are operated in closed circuit with roughers, a record of the density of the cleaner tails will indicate the circulating load in the circuit and is very helpful in coordinating different operators, because quite often the circulating load will be increasing for some time before the analyses of the products will change. Density recorders are used to record the variations in the dilution of the underflow from thickening tanks and in at least one plant the instrument controls the underflow.

Jan 1, 1951

By N. S. Spence

INTRODUCTION WHILE TITANIUM, the element, has been known for over 150 years, titanium, the metal, is a relative newcomer to the metallurgical and industrial scene. The reasons for this chiefly lie in the refract1Hy nature of titanium compounds; the high melting point of the metal; the great activity of elemental titanium, particularly at temperatures close to .and above the melting point; and the pronounced deleterious influence of certain impurities on its mechanical proper-ties. Early efforts at production of the metal were, consequently, either unsuccessful or resulted in products having sub-metallic properties. With the considerable improvement in equipment, materials, and skills that have developed within the past twenty-five years, later investigators have had a better opportunity to overcome some of the inherent practical obstacles and to come to grips with the essential technical problems. NATURAL ABUNDANCE OF TITANIUM Titanium is one of the most abundant metallic elements. It has been estimated (1) that titanium comp-rises about 0.65 per cent of the earth's crust, and therefore ranks fourth among the structurally useful metals in the order: aluminum, iron, magnesium, titanium. It must be appreciated that the relative abundance of the element is only a crude indication of its potential availability, since a very substantial proportion is present as a minor constituent in practically all igneous rocks. By comparison, present-day ores of titanium are relatively few and are but a minor fraction of the estimated total titanium contained in the earth' s crust.

Jan 1, 1951

By V. Runolinna, R. T. Hukki

Preliminary separation of precious metals by flotation can offer a simplification of the conventional method of treatment of anode slimes. Laboratory flotation experiments show that rich gold and silver concentrate can be obtained with excellent recoveries. THE purpose of this paper is to present the results of an investigation into the possibilities of separating precious metals from anode slimes by selective flotation. The work was carried out at the State Research Institute in Helsinki, Finland. The sample of anode slimes tested was submitted by the Outo-kumpu Co. in Finland. In 1947 the average assay of filtered and dried anode slimes in the Outokumpu refinery in Pori was as follows: Au, 0.50 pct; Ag, 9.38 pct; Cu, 11.02 pct; Ni, 45.21 pct; Pb, 2.62 pct; Fe, 0.60 pct; Sn, 1.00 pct; Sb, 0.04 pct; As, 0.70 pct; Se, 4.33 pct; S, 2.32 pct; SO,, 2.17 pct; SiO2, 2.25 pct. The daily assay naturally varies considerably from the figures presented above. The present conventional method of treatment of anode slimes consists of the steps shown in the flowsheet in fig. 1. As seen from this simplified flowsheet, the present method of treatment involves many steps by which the components of the anode slimes are removed one after another until the main products, gold and silver, may be separated. Due to the small scale of operations, the above procedure is carried out in small batches requiring considerable amount of manual labor. If, however, the anode slimes could be treated in

Jan 1, 1951

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By Howard B. Bradley, Charles F. Weinaug

The phase behavior of a naturally occurring hydrocarbon system whose critical temperature is near the reservoir temperature has been described. The same volume per cent liquid was observed for the firkt time at three different pressures for isotherms immediately below the critical temperature. The shapes of the isothermal equilibrium constant curves necessary to predict this phenomena are discussed and illustrated. INTRODUCTION The phase behavior of a number of hydrocarbon systems has been reported; however, very little data are available on natural occurring hydrocarbon systems whose critical temperature is near the reservoir temperature. This appeared to be the case for the fluid studied here; therefore the pressure-volume-temperature data for this system were determined for preqentation. METHOD The PVT data were obtained with equipment similar to hat described by Weinaug and Katz,1 consisting principally of a two-section, double-windowed gauge mounted in a conktant temperature air bath. The procedure followed was essentially that used by Katz and Kurata5 except that a cathetom-eter, reading direct to 0.01 cm, was used to determine the height of each extreme phase limit. The system studied was formed by recombining -.vapor and liquid samples from the first stage separator of the well. Portions of these samples were displaced with mercury into the cell which had previously been filled with mercury. A predetermined amount of the liquid sample was introduced, while an excess of vapor was admitted. The resulting mixture was brought to equilibrium at the condition of the separator during sampling. By adding mercury to maintain the pressure, enough vapor was displaced to give a gas/oil ratio within the cell equal to that produced by the separator at the time of sampling. The remaining material was then considered to be equivalent to the reservoir fluid. An analysis of material in the cell, computed from analysis of vapor and liquid samples and the separator gas/oil ratio. is given in Table I. Table I — Composition of Hydrocarbon System Component Mole Per Cent Carbon Dioxide 0.13 Nitrogen 0.76 Methane 53.91 Ethane 14.20 Propane 9.64 Iso Butane 1.25 Normal Butane 4.29 Iso Pentane 1.12 Normal Pentane 1.87 Hexane 2.72 Heptanes + 10.11 hloleculal. Weight of Heptanes + 178.50

Jan 1, 1951

By T. C. King

AT the new Graham-Central Mill of Eagle-Picher, near Galena, Ill., material is simultaneously dewatered and introduced into the ball-mill scoop boxes by the use of variable-speed, 24-in. spiral classifiers. This arrangement has proved satisfactory in that the moisture content of the wet feed is reduced, thus allowing maintenance of density within the mills, and a constant feed at any desired rate to the mills is provided. In this mill the primary feed is wet crushed to minus 1/2 in. and preconcentrated by jigs to produce a bulk lead-zinc-iron concentrate and a waste tailing. The jig concentrate is then dewatered by a conventional dewatering classifier and stored in bins ahead of the ball mills. Even though this material is well dewatered, the discharge at the bin bottom is sloppy because of the gradual drainage of the water from the surface of the particles. Conventional belt feeders with vertical cutoff gates are unsatisfactory because of the flushing characteristic of the wet sand. The new installation employs 24 in. x 10 ft, 9-in. Simplex double-pitch spiral classifiers for feeders from the bin bottoms to the ball mill scoop boxes (fig. 1). These units are arranged with straight tanks and are driven by 5 hp motors through a U. S. Vari-Drive to provide a 4 to 1 speed ratio. Each bin discharges through a chute into the rising side of the spiral. The flushing characteristic of the material from the bottom of the bin is utilized to maintain a steady feed. A small amount of water tapped into the bottom of the bin insures uniform feed to the classifier. Excess clear water drains over the weirs. Feed rate to the mills is controlled by the variable-speed drives. The feed delivered by the spiral at a given speed setting is relatively dry, uniform, and steady, and as such is easily controlled by the operator. The classifiers are set on a pitch of 5 in. per ft and have a sand-raking capacity of from 8 to 32 tons per hr. It is believed that the solution of this problem offers possibilities for the storage of deslimed rod-mill sands and other similar products of the industry.

Jan 1, 1951

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By W. A. Lang

Introduction In this review, which is the fifth of the series on the Progress in Coal Technology, an attempt has been made to outline some of the more important developments that have taken place in coal carbonization during the last decade. Research into both high-and low-temperature carbonization has been active for three principal reasons: (1) the growing shortages in most countries of high-quality coking coals; (2) the demand for smokeless fuels for domestic purposes; (3) the need for metallurgical coke for the increased output of steel in the post-war years. The growing importance of coal tars as a source of chemicals for the preparation of synthetic products and of coal gases for the recovery of sulphur is evident. Many of the researches initiated because of wartime necessity have been continued .and even expanded in the post-war years. High-temperature carbonization with a suitable coal yields a strong coke which is used primarily for metallurgical purposes, a tar with good marketable value, and a large yield of gas of medium calorific value. Low-temperature carbonization gives a more free-burning solid product suitable for a domestic fuel, a high yield of a tar which is generally regarded as superior to high-temperature tar for chemical purposes, and a smaller yield of a higher-heat-value gas.

Jan 1, 1951

By Jack White

W. I. Garms-—The authors state that when they added 11 tons of balls to the 45 pct volume ball load, the power needle did not budge. The question arises as to whether any increase in capacity accompanied the 11-ton addition. It is hardly conceivable that all of the balls making up the l l-ton addition were sterile. However, as the work done in the ball mill is not by kilo-watthours per se or balls per se but by kilowatthour-balls, it is possible that the kilowatthourballs in the mill before the ll-ton addition had a different amperage, voltage or robustage than those in the mill after the addition and that the overall outcome was that equal work was done before and after the addition. The authors can keep the efficiency that they got with the 45 pct volume 1-in. ball charge and get additional capacity by putting more kilowatthourballs to work in the form of the addition of 11 tons of 2-in. balls to the present ball charge, and subsequent makeup additions by weight of 20 pct 2-in. balls and 80 pct 1-in. balls. J. F. Myers (authors' reply)-—Mr. Garms points his finger at the 11 tons of "sterile" balls added to the Tri-cone mill. A fact so interesting to us that we felt it should be reported. Clearly, ball slippage at the existing mill speed prevented any further transfer of power from the shell to the ball mass. We agree that the kilowatthourballs would increase, were we charging rough 2-in. balls as suggested by Mr. Garms. The assumption is, of course, that we would get a corresponding increase in work done. Our reported data (CIME meeting, Vancouver, 1946) shows a gain of work accomplished of 7.6 pct as we decreased the ball size from 2 in. to 1% in. and a further gain of work accomplished of 2.1 pct when we went from 1 % in. to 1 in. The small ball results reported by H. R. Banks at Chapman Camp are also very convincing. In the case of 2-in. balls they would take the conventional ball path and start cascading. They would thus destroy the classifying pool over the "foot" of the

Jan 1, 1951

By R. W. Gurry

In a series of charts this paper presents the composition of all gas mixtures, composed of the elements carbon, hydrogen, oxygen and nitrogen, which at temperatures from 1000° to 1800°F are in equilibrium with (1) austenite of various carbon contents, (2) iron and iron carbide, (3) graphite, (4) iron and its oxide. THIS paper presents the results of calculations made to determine the proportions of CO, CO2, CH4, H2, H2O and N2 in gas mixtures which, at temperatures from 1000" to 1800°F, satisfy, individually, the following conditions: (1) equilibrium with carbon steel of specified carbon content throughout the stable 7 iron region; (2) equilibrium with iron and iron carbide, both above and below the eutectoid temperature; (3) equilibrium with graphite; (4) equilibrium with iron and its oxide. From these data a new type of chart has been prepared which permits one to determine, from a room-temperature analysis of the furnace gas in question, the effect of the gas upon the steel at furnace temperature. Thus a guide is provided as to the carbon content which will result and as to the possibility of oxidation or sooting. All of the atmospheres commonly used in the commercial heat treatment of steel are composed of some or all of the simple constituents CO, CO2, CH4, H2, H2O and N2, and also in some cases oxygen or higher hydrocarbons. As the gas mixture is heated certain alterations in the proportions of the constituents take place, and at the temperature of the furnace the composition is, in general, not at all that of the entering gas. If equilibrium in the gas phase is presumed a calculation involving the use of certain fundamental data predicts for a certain temperature the carburizing, decarburizing, or sooting characteristics of a given atmosphere, and, upon the additional assumption of equilibrium between gas and metal, also the oxidizing ability of the gas and the ultimate carbon content of the steel. The extent to which these predictions are fulfilled will depend upon how closely the assumptions of equilibrium are realized in any particular case. Although at lower temperatures equilibrium is often not reached, there is considerable evidence indicating that above about 1000°F the approach to equilibrium in the gas phase is generally substantially complete, particularly in the vicinity of the steel which acts as a powerful catalyst in promoting reactions in the gas phase. The extent of the gas-metal reactions is commonly affected essentially by the sojourn at temperature; equilibrium with respect to carbon, for example, is accomplished simply by continuing the treatment long enough. However close the approximation of equilibrium may be in any instance, the above mentioned calculation indicates the condition of the steel at equilibrium, and at the present time this is the only basis of control of a furnace atmosphere. The effect at elevated temperature of a gas of a certain composition at room temperature upon a given steel has customarily been judged by first calculating from gas equilibrium constants the proportions of the gas constituents at the temperature of the steel, then comparing certain of these with the proportions known to be in carbon or oxygen equilibrium. This process is tedious and time-consuming, in particular because the calculation generally involves a series of successive approximations; and since some knowledge and familiarity with this type of computation are required, not everyone needing the information has been, in the past, in a position to obtain it. By making a series of equilibrium calculations, combining with fundamental data for gas-metal reactions, and plotting the results in a special way, a chart has been prepared which enables anyone

Jan 1, 1951

By Phillip E. La Moreaux

Fluoride, generally less than 0.5 ppm, is present in ground water from rocks of Paleozoic age and older, in northern and eastern Alabama. Some of the water-bearing formations in the Coastal Plain area of the State yield water with as much as 6.8 ppm fluoride. IN June 1940, the U. S. Geological Survey, in cooperation with the Geological Survey of Alabama, began a study of the ground-water resources of the part of Alabama where water is obtained from Cretaceous rocks. The purpose of the study was to determine the quality, quantity, occurrence, and availability of ground water in that area. These studies have been expanded to include ground-water investigations in the area of Tertiary rocks, or southern quarter of the State, and certain areas in northern Alabama. The first report issued on these studies was by C. W. Carlston,1 of the Alabama Geological Survey. In the present paper all references to ground-water data for the Cretaceous area are taken from this earlier publication. In 1945, the Dentistry Division of the Alabama Department of Public Health became interested in the correlation of tooth decay and mottled enamel with the chemical quality of ground water used for public supplies in the State. Through a cooperative arrangement between the State Department of Public Health and the Ground Water Division (now Branch) of the U. S. Geological Survey, a report by the author2 was published in 1948. These two reports give accurate information on the occurrence of fluoride in the Coastal Plain of Alabama. At present, only scattered information is available on fluoride in ground water of the crystalline-rock or Piedmont area and for the Paleozoic area of Alabama, but it is hoped that in the future more complete information on the presence of fluoride in ground water in these areas can be collected. Outline of Geology and Ground Water: As described by Adams,3 the State of Alabama includes parts of two major geologic divisions, the Appalachian region and the Coastal Plain. The boundary between these divisions is irregular and is known as the Fall Line of the Atlantic and Gulf Coast States. The Fall Line enters Alabama near Phoenix City, extends westward to Wetumpka, Clanton, and Tuscaloosa, and then swings northwestward to the northwest corner of the State. The Appalachian region in Alabama includes three major provinces, the Piedmont province, the Appalachian Ridge and Valley province, and the Appalachian Plateau province (fig. 1). The rock formations in the Piedmont province in east-central Alabama are mainly of pre-Cambrian age, chiefly crystalline schists and gneisses injected by younger igneous rocks (fig. 1, I). They are faulted and folded and have a complicated structure. These rocks are the oldest and among the most complex rocks in the State. Generally, only small yields of ground water are obtained from rocks in this area. Even though ground water is of great importance for the development of domestic and farm supplies in rural areas and a few small industrial and municipal wells, yields in the area from individual wells generally range from 5 to 25 gpm and rarely exceed 50 gpm. The geologic formations of the Appalachian Ridge and Valley province and the Appalachian Plateau province (see fig. 1, II, and III) are separated on the basis of their structure. These rocks are of Paleozoic age, ranging from Cambrian to Carboniferous, and comprise a succession of formations consisting chiefly of shale, sandstone, limestone, and dolomite, aggregating many thousands of feet in

Jan 1, 1951

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen' to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By R. J. Franklin, G. W. Beckman, D. Warren, E. Both, J. F. Libsch

BINARY and ternary alloys of iron, nickel and cobalt respond to annealing in a magnetic field by a characteristic change in the shape of their hysteresis 100p.l,2 An increase in retentivity and a decrease in coercive force produced by the magnetic treatment cause the hysteresis loop to approach the appearance of a rectangle. Materials with a rectangular hysteresis loop have made possible the contact-rectifier³ and have greatly improved the performance of pulse transformers4 and magnetic amplifiers." In the best material presently available for these applications, a 50 pct nickel-iron alloy," the desired characteristics are achieved by aligning the preferred crystallographic directions of magnetization along the rolling direction of the tape. The objective of the present study has been to produce rectangular hysteresis characteristics in materials with inherently high saturation. Iron-cobalt alloys, exhibiting saturation values up to 24,000 gausses' appeared to offer promise for the magnetic annealing technique, because they remain magnetic to very high temperatures,8 exhibit favorable magnetostriction properties: and show zero crystal energy at 42 pct cobalt.10 Among the ternary iron-cobalt-nickel alloys,7,11 response to heat treatment in a magnetic field is unfortunately limited to alloys having rather low saturation values.' It appeared interesting nevertheless, to study a series of compositions connecting the optimum composition (50/50) of the binary iron-cobalt system with the "Perminvar" composition (30 pct Fe, 25 pct Co, and 45 pct Ni). Very recently, R. Smoluchowski and R. W. Turner," have shown that under certain circumstances magnetic annealing can produce oriented recrystallization. A combination of this technique with the domain orientation utilized in the present study might well result in further improvements. The advantages of the powder metallurgy technique in preparing magnetic alloys for study have

Jan 1, 1951