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Jan 1, 1916

By D. Muraoka

Introduction Soda ash, anhydrous sodium carbonate, is produced from underground trona deposits occurring in the Green River Basin of southwestern Wyoming. Stauffer Chemical Co. of Wyoming, a jointly owned subsidiary of Stauffer Chemical Co. and Rocky Mountain Energy Co., mines the trona and processes it into high-purity soda ash. Stauffer Wyoming has been in operation since 1962 with a current production capacity of about 1.8 Mt (2 million st) per year of soda ash. The refinery has five parallel operating trains using the monohydrate process which is a series of chemical processing unit operations described below. Screening and Crushing The mined trona is brought to the surface in two counterbalancing ore skips. The ore is initially screened with refinery feed (less than peagravel size material) entering the process. Oversize is conveyed to an outdoor stockpile. Ore is recycled from under the stockpile via cone feeders as the refinery needs require. The ore is conveyed to hammer type crushers and screened. The refinery feed enters the process and the oversize is recycled to the crushers. Calcining The first step in refining trona to soda ash is calcining the trona ore. This is accomplished in concurrent flow, rotary kilns that are direct fired with natural gas. [2 (Na CO NaHCO 2H O) Heat 3Na CO + 5H20 + CO 2 3~3~ 2 ~~2 32] The trona ore is fed to the kiln at the burner end and is intimately mixed with the hot exhaust gases from the burner. Direct contact with the flame is avoided. The ore moves down the kiln by gravity and rotation aided by the kiln's internal lifters. The exhaust gases are cleaned to 99 + % particulate removal and discharged to the atmosphere. Dissolving the Calcined Trona The calcined trona is conveyed from the kiln discharge to a rotary drum dissolver where it is mixed with water and weak solution (unsaturated solution of calcined trona in water). The calcined trona is soluble whereas the impurities, primarily shale, are insoluble. The discharge from the dissolver is a slurry containing saturated solution (about 30% dissolved calcined trona in water), some undissolved calcined trona, insoluble impurities, and organic impurities. The dissolver discharge enters a rake classifier that makes the first solid/liquid separation in the process by removing the heavy undissolved material from the saturated solution. This undissolved material is conveyed to a second rotary drum dissolver and mixed with water to dissolve any remaining calcined trona. The secondary dissolver discharges to a second rake classifier that separates the solids from the liquid. The solids are now primarily insoluble impurities with very little unrecovered calcined trona. These wastes are conveyed to evaporation ponds for disposal. The liquid from the secondary rake is recycled to the primary dissolvers' weak solution system. Returning to the primary rake classifier, the saturated solution which contains suspended insoluble muds is pumped to a thickener. Flocculant is added to aid settling of the suspended muds. The flocculated muds are collected at the bottom of the thickener and pumped to vacuum cloth filters. The adhering saturated solution is separated from the muds that remain on the filter cloth. The recovered solution is returned to the dissolvers' weak solution system. The muds are reslurried and pumped to the evaporation ponds for disposal. Saturated solution, containing some suspended insoluble muds along with the organic impurities, overflows the thickener. Filtering the Saturated Solution The saturated solution overflowing the thickener enters a holding tank where it is pumped to a bank of pressure leaf filters. The suspended muds are captured on the filter leaves while the cleaned saturated solution is pumped to polishing filters. The polishing filters are also leaf pressure type, intended to remove any suspended solids that may pass the primary filters. Organic impurities are removed with activated carbon. The purified solution is now free of insoluble muds and has most of the organic impurities removed. Crystallizing and Drying the Monohydrate The purified saturated solution is pumped to evaporative crystallizers. The solution is circulated from the crystallizer vessel through a heat exchanger. Indirect contact with steam in the heat exchanger causes the saturated solution to boil, thus crystallizing the soda ash in its monohydrate form. Slurry crystal density is maintained in the crystallizer by simulta¬neous feed of fresh saturated solution and drawoff of the slurry.

Jan 1, 1986

By Richard McCaffery

THERE has been some discussion among blast-furnace operators regarding the relative merits of tuyeres of the converging type and tuyeres designed in an attempt to produce a diverging jet of air. An article1 on Progress in German Blast Furnace Practice indicates the interest in this subject abroad. This article illustrates a diverging type of tuyere which is shown here in Fig. 1A. The design appears to be rather poor as regards known properties of air flow. The adoption of this. tuyere, the article states, resulted in a decrease of blast pressure of about 4 lb. per sq. in. and an increase of the output of the furnace. If the improvements mentioned are due entirely to the change in tuyere design, the subject of tuyere design seemed worthy of investigation and this paper is a report of such work. Because of the gain in efficiency brought about by the use of a diverging tuyere in the German plant, it was thought desirable to investigate the shape of the air streams issuing from various-types of tuyeres to ascertain whether the gain was due to the tuyere itself or to the distribution of the air in the furnace. Since it is difficult to do experimental work on a full-sized furnace, or even on full-sized tuyeres, and because of the equipment available for the work, it was decided to carry out the work on scale models of tuyeres. Therefore, in this work, single tuyeres were used and the blast discharged into the atmosphere. The shape of the air stream was determined by means of a Pitot tube suitably supported in the air stream at various positions. The air was. furnished by a Roots blower driven by a 10-hp. direct-current motor having field control, and capable of discharging 250 cu. ft. per min. with a pressure on the discharge of 4 in. of mercury. A modern blast furnace with 21-ft. hearth requires about 50,000 cu. ft. per min. of free air at from 16 to 23 lb. per sq. in. pressure, depending upon the type of burden. This pressure is the total pressure required to force the air through the burden and through the tuyeres. Upon computation the pressure drop through the tuyeres is about 1 to 2 lb. per sq. in. By making the tuyeres to a one-fifth scale, and by using a pressure of 1.5 in. of mercury, the shape of the air streams should be

Jan 1, 1931

By Harlan W. Nelson, James B. Purdy

A study of data obtained during laboratory tests to determine the suitability of bituminous coals for use in residential underfeed stokers of the clinkering type has led to the following general conclusions: 1. Performance data obtained during the test furnish useful and practical information upon which to judge the performance of stoker coals. 2. Conclusions derived from the results of evaluation tests are in general agreement with use experience of the coals in the field. The method is of practical use in this regard. 3. Few direct relationships were found between data furnished by the evaluation test and determinations by standard laboratory tests. This is particularly true with regard to coke formation and clinker formation, two of the most important factors in determining the degree of satisfaction to be obtained in applications of the small underfeed stoker. It has not been the intention in this paper to prescribe this evaluation test as the best method for the evaluation of coals for use in residential stokers. That there are other test methods having similar objectives serves to point out the necessity for full-scale laboratory tests. At the present time, a standard test procedure for the evaluation of coals for use in residential stokers is not available. For the past several years a joint committee, appointed from the membership of the Residential Stoker Committee of Bitulninous Coal Research, Inc., and from the Engineer- ing and Research Committee of The Stoker Manufacturers Association, has been working to develop a standard procedure for testing and evaluating bituminous stoker coals. This procedure has been completed to the extent that it has been drawn up in tentative form. It is now planned to install the equipment in several laboratories and to run check tests, using portions of identical lots of coal, to determine the degree of reproducibility offered by the method. Completion of this standard test procedure should greatly facilitate the evaluation of coals for use in residential stokers. Acknowledgments The cooperation of coal operators sponsoring the coal evaluation tests, in granting permission to use data and results from their tests, is gratefully acknowledged. Acknowledgment is also made to Carroll F. Hardy, Chief Engineer, Appalachian Coals, Inc., for his interest and timely suggestions on the preparation of this paper. Special thanks are due to Ralph Sherman, Assistant Director, Battelle Memorial Institute, who was largely responsible for development of the evaluation procedure, for helpful suggestions and advice. References I. H. A. Sherman: The Evaluation of Coal for Use in Domestic Stokers. Univ. of Ill., Eng. Experiment Station, Circular No. 39 (1939). 2. . Q. Shotts: The Relation of Free- swelling Indexes to Other Characteristics of Some Alabama Domestic Stoker Coals. TP 2314, Coal Tech., (Feb. 1948); Trans. AIME (1948) 177, 502. 3. . J. Helfinstine and C. C. Boley: Correlation of Domestic Stoker Combustion with Laboratory Tests and Types of Fuels 11. Combustion Tests and Preparation Studies of Representative Illinois Coals. Ill. State Geol. Survey, Re1. of Zntlestigations No. 120 (19467 ) p. 35. DISCUSSION E. R. Kaiser*—AS a former fuel engineer assigned to residential stokers at Battelle, the writer has read with considerable interest the paper by Messrs. I'urdy and Nelson. It is gratifying to note that earlier test techniques have been developed and that criteria found important in the years 1935 to 1938 are still important in judging the performance of stoker coals for residential heating. The authors have plotted a number of the primary coal data singly against performance data of the stoker in an effort to establish relationships. Unfortunately, wide scattering of points usually resulted, which did not illustrate what experience generally indicates to be the case. For example, Fig 3 indicates almost no trend in the percentage of released ash converted to clinker with change in ash-softening temperature. Other factors, such as fuel bed temperatures and zones of heat release must have influenced the results. In the present state of our knowledge, we cannot explain all of the reasons why suitable stoker coals perform satisfactorily, nor why one satisfactory coal may be better than another. It would therefore

Jan 1, 1950

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By L. L. Wyman

Previous studies1 by the writer dealing with the embrittlement of copper have been concerned with the behavior of various pure and deoxidized coppers when exposed to an oxidation-reduction cycle, and the consequent evaluation of these materials on the basis of their resistance to this action. No attention was devoted to the variations in penetration of embrittlement with time, when these copper materials are exposed to a strong reducing gas, such as hydrogen, nor to the variations in oxygen penetration, with time and temperature, into the "pure" coppers. The cause of the embrittlement is the reduction of the oxygen in the copper by the hot reducing gas, so that a consideration of time, temperature, the occurrence of hydrogen and oxygen must be given. For the purpose of differentiating some of the involved factors, the present work may be divided into two separate series of experiments. The first of these deals with the oxidation of purified coppers under various conditions and then the subjection of these to a standard hydrogen treatment. The second series concerns the reduction, under different conditions, of tough-pitch coppers of several oxygen contents. The resulting data will give the rates of oxidation, and of reduction, for the materials involved. The first series of experiments will reveal how rapidly copper may become oxidized, while the second series will indicate how rapidly embrittlement will penetrate into an oxygen-containing copper when it is exposed to hydrogen at different temperatures. Materials For the purpose of determining these variables, three types of material were selected, to cover the extremes in the ranges of materials commercially obtainable. The first class of materials is represented by an oxygen-free copper, as well as the high-purity vacuum-melted copper2 used in previous work. These materials were selected to determine the variation of oxidation with time and temperature, by oxidizing these coppers under various combinations of these factors, and noting the effect as indicated by a

Jan 1, 1934

By J. H. Henderson, J. Naar

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

By Wido Tilmann

13.6-1. Importance. In Germany there are large tertiary brown coal reserves, most of which are located close to the surface. Therefore, brown coal has been recovered for many years by means of opencast methods. By utilizing a high degree of technology, a rational operation has been achieved, and as a result, the mining techniques have become renowned all over the world. After the war, all the dredgers and overburden spreaders, as well as the means of conveyance, had to be redeveloped for adapting this equipment to the changing conditions of the deposits. Numerous auxiliary machines were adopted from the American earth moving industry and altered according to the different requirements. As a result of such technical developments, the output per man and per shift was increased remarkably in spite of the deterioration of the geological conditions. In the whole of Germany, the total reserves of brown coal amount to 100 billion metric tons, of which 60 billion tons are situated in the Federal Republic of Germany. In the latter area, 8.5 billion tons will be recover- able by opencast means, of which 3.5 billion tons are already developed. The annual output reached 102 million tons in 1965. This total figure comes from four different mining districts: Rhineland, Helmstedt (town at the border of the Soviet occupied zone), Hesse, and Bavaria. The production figures (1965) are as follows: [ ]

Jan 1, 1968

By Charles Catlett

Having had charge during the past year of the operations of the New River Coke Company, the second largest, if not the largest, coke-producer in this district, my attention was called particularly to the yield of coke from the coal as coked in a bank of beehive ovens, as the record showed that this yield, while believed to be well up with the practice of the district, was much lower than the analysis of the coal indicated it should be. The coal is well known to many members of the Institute, and the scope of this paper does not include a discussion of its occurrence and development. It suffices to say that the New River district comprises the mines working on the coals of No. XII. or the Conglomerate Series of the Rogers brothers, which are located on New river and its tributaries, and which find an outlet for their product east and west over the Chesapeake and Ohio Railway. The New river through this section carries the drainage from an extensive peneplain in which it has formed a very striking and stupendous canon, probably the most striking east of the Mississippi river. The only practical access to this territory is by means of this canon and the Chesapeake and Ohio road, and the opportunities for development by other lines may be considered as nil. If it were not for the fact that this road, farther west, reaches and develops entirely different coals, which are found in other measures, the New River district might properly be spoken of (as is now done at times) as the " C and 0. field." For fuller information on the geology of the region, those interested are referred to the ery complete monograph on the subject by Mendenhall and Campbell of the United States Geological Survey. The rocks are the same as those which carry the more widely

Jan 1, 1900

As already said Pattin's map and the later one of Evans' showed coal in several places in Ohio as early as 1750, and possibly 1748; the reference on the latter map was' to an exposure near Bolivar, in Tuscarawas County, as well as along the Hocking River. So far. as now known, it 'was not mined in either place until 1810. George Croghan, in descending the Ohio with his party in 1765, mentions an "Alum Hill" which they saw near the present site of Pomeroy, probably an exposure of saline deposits, but does not mention coal. As settlement north of the Ohio River was prohibited until 1787, no coal was mined until long after that date. In 1785 a survey of seven ranges in the Ohio country was made, the line running west from a point on the north bank of 'the Ohio River, due north of the western termination of the southern boundary of Pennsylvania. The surveyors noted, "from hence to Stoney Brook between two very steep and high Ridges; it is eight yards wide, its bottom is of Slate and Sand Stone, and in many parts of it are large pieces of excellent Coal washed by, the Rains from the Neighboring Hills."' This was the present Yellow Creek, and the coal was from some of the lower measures. The Scioto Company published a pamphlet in French in 1787, to promote the sale of their lands and emigration to them, in which was said,

Jan 1, 1942

By M. Semchyshen, G. A. Timmons

The predominant orientation in both straight-rolled and cross-rolled molybdenum is the {100} [110] texture. Upon complete recrystallization, this same texture predominates, but there is less spread about the ideal orientation. A secondary orientation about the [111] direction as the axis develops in cross-rolled sheet. Compression-rolled sheet exhibits random orientation in the plane of the sheet. Some mechanical properties were measured at varying angles to the rolling direction to determine the effect of preferred orientation on anisotropy in molybdenum sheet which had been straight, cross, or compression rolled. THE development of the arc-cast process has made available large ingots of molybdenum from which it is possible to roll sheet of considerable size. It is anticipated that such sheet will be further fabricated by spinning, drawing, stamping, or forming. Anisotropy of physical properties caused by the preferred orientation developed in the sheet during rolling may be expected to affect the behavior of the metal when subjected to these fabricating operations. To produce a sheet which will be most amenable to the fabrication of a given shape by a particular operation, consideration should be given to the directions and magnitudes of plastic deformations produced in the operation. When possible, the rolling schedule should be controlled to develop a texture which favors the required deformation. The existence of preferred orientations in rolled molybdenum sheet has been reported by Jeffries,' Konobejewsky,' Fujiwara," Goss,' and Ransley and Rooksby." None of these investigators obtained sufficient X-ray data to permit the construction of pole figures; instead, they based their conclusions upon Debye-Scherrer patterns of a limited number of positions. Ransley and Rooksby devoted some attention to transcrystalline cleavage at 45" to the rolling direction, indicating that it is appreciable in polycrystalline material only when the crystals are in the ideally preferred condition, and that this condition is only approached if the metal has been rolled successively in two perpendicular directions. In a recent paper, Custers and Riemersmao introduced the first pole figures to describe the textures of straight-rolled and cross-rolled molybdenum sheet. To increase the knowledge concerning the generation and effects of preferred orientations in molybdenum sheet, an investigation was undertaken to determine the effects of variations in rolling schedule and annealing treatments on preferred orientation, and to correlate preferred orientations with some mechanical properties. The orientations of straight-rolled, cross-rolled, and compression-rolled sheet have been determined by X-ray analysis, both as-rolled and after recrystallization. Pole figures have been constructed to describe the textures produced by these various rolling procedures. Texture of Cast Molybdenum Ingots In the arc-cast process, molybdenum powder is pressed into a vertical column which is sintered to increase its strength as it proceeds downward into a water-cooled mold, where the metal is melted in an alternating-current arc established between the end of the formed powder electrode and the metal bath at the top of the growing ingot. Since the solid-liquid interface moves continuously upward in the mold, the crystal axes are not normal to the cold surface of the mold but have the curvature shown in Fig. la. X-ray analysis reveals that the cube axis is the fiber axis and that it is normal to the cold surface of the mold; that is, the [loo] direction is parallel to the longitudinal axis of the ingot. This substantiates recent work by

Jan 1, 1953

By Alfonso Rizo-Patrón, A. M. Gaudin

PREVIOUS studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector. The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest. In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector. The results obtained indicate that a I : I ratio of collector ion to activator ion gives optimum results, and that a 2:I ratio almost fails to achieve activation and flotation. Yet, a 2:I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion. To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful. The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids; they confirm that an adsorbed coating is inescapable. APPARATUS AND SUPPLIES The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz. The flotation machine was built according to the design of D. W. McGlashan.* It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel stator, as in the Fagergren laboratory machine. The air intake is controlled by a valve, and the cell consists of a beaker. The quartz was obtained from vein quartz stored in large chunks. It was first crushed to 20 mesh, then sized on a 28-mesh screen. The 20 to 28-mesh size alone was retained for use. This size was freed of coarse iron by passage through a Ball Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used. The barium was used as barium chloride, Baker's analyzed C. P. The oleate was used as sodium oleate. It was prepared from sodium hydroxide, Baker's analyzed C. P., and oleic acid purified by R. R. de Arellano3 in the laboratories at the Massachusetts Institute of Technology. The purification procedure was elaborated from the recent researches of Brown and Shinowara.2 It consisted in: (I) saponification of olive oil with potassium

Jan 1, 1942

By R. F. Domagala, D. J. McPherson

Iodide zirconium was combined with calculated amounts of ZrO2 or master alloys and arc-melted. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat treated specimens permitted construction of the binary phase diagram from zirconium to ZrO2. Oxygen additions to zirconium raise the transformation temperature as well as the melting point. Features of the diagram include the peritectic formation of beta, the formation of alpha directly from the melt, an intermediate phase ZrOB with a' range of homogeneity, and a eutectic between alpha and Zr02. PHASE relationships in the Zr-0 system were determined in the range 0 to 66. 7 atomic pct 0 (ZrO,). Arc-melted alloys were annealed at temperature levels between 600" and 2000°C. Determination of the phase boundaries was accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to determine solidus curves, and X-ray diffraction work was employed to study the lattice parameters of the a solid solution and the phase ZrO,. Experimental Procedures Westinghouse "Grade 1" iodide zirconium crystal bar (approximately 99.8 pct pure) was employed for the investigation. This material is substantially free of the impurity inclusions characteristic of most zirconium metal. Previous work has shown it to be the most satisfactory grade for phase diagram studies. The zirconium crystal bar, as-received, was coated with corrosion product from autoclave tests by which its grade designation is determined. The bars were sand blasted lightly, pickled for 1 min in a 20 pct HN0,-5 pct HF aqueous solution, rinsed in water and acetone, and dried. The bars were rolled to about 1/32 in. strip, cut into 10 in. lengths, and pickled again. The material was sheared to approximately Y4 in. squares, cleaned with acetone, and stored for use. Two pounds of specially prepared "chemically pure," and 100 grams of spectrographic grade ZrO, were obtained for the preparation of alloys. The "Specpure" ZrO, was obtained from Johnson, Mat-they Co.. Ltd.. and Titanium Alloy Manufacturing Div. of National Lead Co. supplied the other grade of oxide. The "chemically pure" material (henceforth referred to as C.P. ZrO,) was used for the preparation of all alloys employed in the determination of phase relationships. A limited number of alloys were prepared with the "Specpure" oxide to recheck certain phase boundaries. Analyses of the two grades of oxide are given in Table I. The C.P. ZrOI was received in powder form, not suitable for arc melting. Therefore, this material was compressed to wafers 1 in. in diameter and about Vn in. thick. These were segmented and stored for use. The "Specpure" material, in the form of small granules, was suitable for use in the as-received condition. A nonconsumable electrode arc-melting furnace was used to prepare alloys. A water-cooled copper crucible and tungsten-tipped electrode were employed. The material was placed in the crucible and rapidly melted under a protective atmosphere of helium gas by striking the arc on a tungsten stud and directing it upon the charge material. Details of operation, including drawings of this type furnace, have been published.'

Jan 1, 1955

By W. R. Aufricht, E. H. Koepf

The theory, measurement, and application of capillary forces in reservoir rock have been treated ex-tensively in the various petroleum publications.1,2,3,4 These forces are of prime importance in oil production, and data on capillary properties are among the most important tools used in the study of reservoir mechanics. The principal application of measured capillary pressure data by the production and reservoir engineer is in the determination of the initial distribution and mobility of fluids in the reservoir. The distribution refers to the magnitude of the oil and interstitial water saturations under capillary equilibrium conditions and to their variation throughout the reservoir as a result of changes in rock properties and nearness to free water. The magnitude of the water (or oil) saturation, as well as the porosity, is required in volumetric calculations of oil in place. In low permeability reservoirs, where long transition zones are common, the magnitude of the oil content, even below the depth interval where commercial rates of flow of oil can be obtained, must be evaluated since this oil contains energy available to the production of the remainder of the reservoir. The mobility of the water phase is of particular importance in water-flood calculations since mobile water may condemn what would otherwise be a successful water flood. In reservoirs with predominantly small pores, high immobile water contents are possible. Conversely, reservoirs with predominantly large pores may contain mobile water even though the interstitial water contents are relatively low. This presentation reviews the distribution and mobility of interstitial water contents as determined from capillary pressure data and shows typical data for various types of carbonate reservoirs. A discussion of the variations found in different types of carbonate reservoirs is given. DISCUSSION Interpretation of Laboratory Data Fig. 1 is a typical laboratory capillary Pressure curve where water saturation as Per cent of Pore space is plotted vs capillary Pressure (psig) for an air-water system. This par- ticular curve was obtained by measurement on a sample of San Andres dolomite with intergranular-type porosity. The sample studied had a permeability of 10.0 md and a porosity of 18.8 per cent. The capillary pressure-saturation relationship illustrated is an inherent property of the rock (a function of the size and distribution of the pores) and represents the ability of this water-wet rock to retain water against the pressure differential exerted by a non-wetting fluid (oil or gas) to remove it. In the laboratory a known pressure differential is exerted from a pressure source; in the reservoir the pressure differential is controlled by the density difference between the hvdrocarbons and the water. The laboratory capillary pressure values may be converted into terms of equivalent height of water column using known values of reservoir oil and water density and measured or average values of interfacial tension

Jan 1, 1958

By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy's law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,' Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By Carl Pierce

The writer of this article has not attempted to write a technical paper; on the contrary, he has tried to express in "steel-plant English," for steel men, a viewpoint drawn from his practice and experience. It is not his thought that it shall be taken as the "last word" in the making of this class of steel, or that good rimming steel cannot be made by any other practice. The paper was written to serve as the basis of a discussion from which it is hoped much benefit may be derived. The paper deals only with rimming steel made by the open-hearth process, and with the lower carbon steels, such as sheet and tin bar, rivet stock, skelp, etc., although good rimming steel as high as 40 to 50 carbon can be made by having good open slags and giving proper attention to working and tapping temperatures. Definition of Rimmed Steel Rimmed steel is sometimes called open or effervescing steel to differentiate it from killed or partly killed steel. It is steel made by a process which permits the free escape of gases from the metal in the molds. In passing up through the metal, the gases keep it in a rolling action from the walls of the mold inward. The top of the ingot rims in as the metal chills and the walls of the ingot get thicker, the center part remaining fluid until it reaches a pasty condition when it is covered with a cast-iron cap. The Charge In making up a charge for rimming steel, clean stock of a known composition must be selected, special attention being given to the analysis of the materials. The silicon in good rimming steel must be eliminated to a trace, therefore it is advisable to have a uniform amount going into the charge. Too much silicon gives a raw melting heat from which rimming steel is unlikely to result. For this reason a charge containing not to exceed 40 per cent. pig iron and 60 per cent. scrap, with no iron ore, is preferred to the Monell type of charge in which as high as 65 to 70 per cent. pig iron is used with a proportional amount of iron ore for the removal of the excess silicon and carbon. The silicon content of pig iron varies so much from day to day in the average blast-furnace practice that there is danger of getting too much of this element in the latter mixture when

Jan 1, 1926

By H. K. Shearer

There were no important developments in the oil and gas industry in South Arkansas during 1935. Oil production, totaling 11,138,340 bbl., continued the decline that has been normal since 1925, but the decline from 1934 was only 278,600 bbl., or 2.5 per cent. The principal decline was in the Smackover field, while only the Champagnolle and Garland City fields showed notable increases. More wells were drilled than in any recent year, with a total of 123 completions. There were 44 oil wells, with a total reported initial daily production of 10,013 bbl., or an average of 227 bbl. per well. Two small gas wells were completed in Union County, where the gas is used locally for pumping and field operations. There were 77 dry holes, of which 28 were in or near oil fields and 49 were wildcats. Active drilling oper-at'ions declined from 65 at the beginning of 1935 to 41 at the end. Most of the drilling was done during the first part of the year, espr-chially (luring the flurry caused by the discovery late in 1934 of the "Taylor" sand production in the Champagnolle field, but the producing area was soon outlined. In November, 1935, the J. E. Crosbie, Inc., NO. 1 Sullivant in sec. 12, 17s. 14W., producing 560 bbl. per day at 3175 ft., opened a new sand lens in the eastern part of the field. The Camden "oil field," discovered in the last week of 1934, remained a one-well field, although four offset tests were drilled, besides a number of others in the immediate vicinity. Several interesting deep tests were drilled during the year, which added a great deal to the general knowledge of the subsurface formations and the structure of south Arkansas, but were not particularly encouraging as to prospects for the very deep production. First, the H. L. Hunt, No. 15 E. F. Gregory well in sec. 10, 17S., 14\W., in the Champagnolle field, was drilled to a depth of 6911 ft. It pene-trated red beds for 2982 ft., from 2943 to 5925 ft., mostly if riot entirely of Lower Cretaceous age. There was some anhydrite in the last 135 ft. of red beds. This was followed by 890 ft. of limestone, probahly Permian, and the rock salt was struck at 6815 ft. The salt is now generally conceded to be of Permian age. Finding salt in this well strongly indicates

Jan 1, 1936

By H. K. Shearer

There were no important developments in the oil and gas industry in South Arkansas during 1935. Oil production, totaling 11,138,340 bbl., continued the decline that has been normal since 1925, but the decline from 1934 was only 278,600 bbl., or 2.5 per cent. The principal decline was in the Smackover field, while only the Champagnolle and Garland City fields showed notable increases. More wells were drilled than in any recent year, with a total of 123 completions. There were 44 oil wells, with a total reported initial daily production of 10,013 bbl., or an average of 227 bbl. per well. Two small gas wells were completed in Union County, where the gas is used locally for pumping and field operations. There were 77 dry holes, of which 28 were in or near oil fields and 49 were wildcats. Active drilling oper-at'ions declined from 65 at the beginning of 1935 to 41 at the end. Most of the drilling was done during the first part of the year, espr-chially (luring the flurry caused by the discovery late in 1934 of the "Taylor" sand production in the Champagnolle field, but the producing area was soon outlined. In November, 1935, the J. E. Crosbie, Inc., NO. 1 Sullivant in sec. 12, 17s. 14W., producing 560 bbl. per day at 3175 ft., opened a new sand lens in the eastern part of the field. The Camden "oil field," discovered in the last week of 1934, remained a one-well field, although four offset tests were drilled, besides a number of others in the immediate vicinity. Several interesting deep tests were drilled during the year, which added a great deal to the general knowledge of the subsurface formations and the structure of south Arkansas, but were not particularly encouraging as to prospects for the very deep production. First, the H. L. Hunt, No. 15 E. F. Gregory well in sec. 10, 17S., 14\W., in the Champagnolle field, was drilled to a depth of 6911 ft. It pene-trated red beds for 2982 ft., from 2943 to 5925 ft., mostly if riot entirely of Lower Cretaceous age. There was some anhydrite in the last 135 ft. of red beds. This was followed by 890 ft. of limestone, probahly Permian, and the rock salt was struck at 6815 ft. The salt is now generally conceded to be of Permian age. Finding salt in this well strongly indicates

Jan 1, 1936

By J. Chipman, H. Towers, M. Paris

A simple radioactive tracer technique is used to measure the diffusion coefficient of calcium ion in molten slags. In a slag of 40 pct Ca0-40 pct Si0,-20 pct Al203, Dc " at 1450°C is 1.3x10-6 cm' sec-'. THE application of the principles of thermodynamics to steel and iron making problems has proved so fruitful that the kinetic approach has tended to be neglected. It seems probable that in some reactions the rate-determining step is the dif-fusivity of the reactants or of the products. But knowledge of the diffusion coefficients of the constituents of liquid slag and metal is singularly lacking. The present work was undertaken as a first step toward supplying such data for slags. Furthermore, any additional information on the physical properties of liquid slags might be expected to help in elucidating their structure. It is essentially a preliminary investigation, the course of which was determined more by the necessity of establishing a method than by the immediate intrinsic interest of the results. For example, the selection of calcium ion to be studied was dictated by the suitability of the isotope Ca45 in that it is a simple emitter with a long half-life. Of the other ions commonly encountered in slags, the isotopes of iron and manganese have relatively complex radiations as well as the normal disadvantage of requiring control of the oxygen potential of the atmosphere; Mg27 and Al29 have half-lives measured only in minutes; Si3' has a simple decay process but its half-life of 2.8 hr is too short for preliminary studies; the only useful oxygen isotope is the stable O18; and there remain only sulphur and phosphorus both of which have suitable isotopes but were rejected as being of less fundamental interest than calcium. Similarly a lime-alumina- silica slag was used in preference to calcium silicate primarily because of its low melting point and its capacity to form a glass on fairly rapid cooling. Literature Review Very few studies of diffusion in liquid silicate systems have been reported. In order to determine the origin of diopside inclusions in felspathic rocks, Bowen1 investigated the diffusion between diopside and various mixtures of albite and anorthite. Platinum crucibles were used with diopside, the heavier of the two liquids, forming the lower half of the cell and diffusion taking place against gravity. Change in concentration along the diffusion path was found by measuring the refractive index of the quenched glass. Nearly thirty years later McCallum and Barrett2 used essentially the same method to determine the diffusion coefficient of lime in lime-alumina-silica slags. In this case the interest was to find the rate-determining step in the process of slag attack on refractory materials. In an investigation of the kinetics of the sulphur reaction, Derge, Philbrook, and Goldman8 determined the diffusion coefficient of sulphur in a typical blast furnace slag by the simple procedure of melting a slag containing 2 pct S over an identical slag sulphur-free. They make no claim to a high degree of accuracy but suggest that D, is of the order of 10-6 cm2 sec-l. Other high temperature liquid diffusion studies have been concerned with metals. Holbrook, Furnas, and Joseph4 determined the diffusion coefficients of silicon, phosphorus, sulphur, manganese, and carbon in liquid iron by immersing a small carbon crucible containing pure iron-carbon alloy in a large vessel containing iron with a high concentration of the particular element. Their results were confirmed by Paschke and Hauttmann5 using a similar method. Diffusion coefficients in silicates in the glassy state have been studied by Johnson, Bristow, and Blau6 Both Na24 and Ca45 were used as tracers but only the

Jan 1, 1954

By Arthur B. Cummins

Diatomite is a siliceous rock of sedimentary origin, which may vary in degree of consolidation, but which consists mainly of the fossilized remains of diatoms. These are microscopic algae of the order Bacillaria. Diatomite is a unique form of silica, there being nothing else found in nature or produced by the manufacturing arts, that has its characteristic physical structure. There are numerous sediments which contain some diatom residues, admixed with a substantial amount of other materials-clay, carbonates or silica. While these are classified as diatomaceous silts, shales, or mudstones, they are not properly diatomite, a designation which is restricted to material of such qualities that it is suitable for commercial uses. The terms diatomaceous earth and kieselgur are synonymous with diatomite. The expressions infusorial earth and tripolite are obsolete. Diatomaceous silica is a definition best used to distinguish the basic component of diatomite, that is, the substance of the silica shell itself and is the major constituent of beneficiated diatomite or processed diatomaceous products. Some highly indurated materials, such as cherty shale, porcelanite, and opaline cherts which have resulted from diagenetic changes cannot be considered as diatomite although they may have been derived therefrom. On the other hand, diatomaceous oozes or loose sediments consisting mainly of diatom residues with or without much organic matter are source materials in process of becoming diatomite. Composition and Properties Pure diatomite is composed of opaline or hydrous silica, with small amounts of associated inorganic components-alumina, iron, alkaline earths, alkali metals, and minor constituents, all of which may occur in solid solution or as an essential part of the opal complex. Crude diatomite on the other hand may contain variable amounts of organic matter and soluble salts, and the usual contaminants of sedimentary formations-particles of rockforming minerals, sand, clay, or carbonates. As occurring in nature, diatomite contains an unusual amount of free water, which may vary from 10 to 60 pct or more. Diatomite, in the dry deposits which are characteristic of most of the important world deposits, occurs as a lightweight, comparatively light colored, "chalklike" material. The apparent density (dry basis) in situ varies from 20 to 40 lb per cu ft. The structure may be either massive or finely stratified. The earth is highly porous, usually soft and easily friable. It is nonreactive with acids and may be tentatively identified by the above characterizations. Confirmation is by microscopic examination which readily reveals the nature of the material. In deposits which contain organic matter the appearance of the material is totally different. The color may vary from light tan or gray to brown, greenish or nearly black. There is frequently difficulty in distinguishing it in the field from peatlike materials, but the difference is readily apparent after calcination. Powdered diatomite or diatomite products have an apparent density (loose weight) of 5 to 16 lb per cu ft, wet densities of 10 to 30 lb per cu ft, specific gravities 1.9 to 2.35, index of refraction 1.42 to 1.48. Diatomite is essentially micro-amorphous, but does show some tendency toward orientation in structure after a cristobalite pattern. Amorphous silica has been considered as a random association of cristobalite crystallites, the size of which are only slightly larger than a unit cell.20 The prop-

Jan 1, 1960