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By A. B. Kinzel, Walter Crafts

Inclusions of nonmetallic matter have long been recognized as objectionable in steel. A complete theory of the effect of inclusions, which is consistent with that held today, was outlined in Howe's early work on the metallurgy of iron and steel. This, by analogy with wrought iron, assumes that the observed difference in properties between specimens with and across the direction of rolling is due to slag enclosures. The fact that wrought iron shatters in ballistic test is taken as an indication of the effect of inclusions on the resistance to'shock. Since that time, the development of the metallurgical microscope has shown the discrete nonmetallic inclusions in the iron matrix. Better resolution has brought out the great number of inclusions, and the availability of good microscopes in steel mills and laboratories has constantly drawn more attention to these inclusions. This recent emphasis on inclusions has resulted in studies as to their nature, mode of formation and methods of elimination, such as the work of Wohrman, Dickenson, Herty and Schenk. In addition to the published works, many investigations which have not been published have been carried out by private laboratories and have resulted in the application of specifications intended to limit inclusions in many qualities of steel. Neverthless, a clear understanding of the quantitative effect of inclusions on the physical properties of steel has been lacking. It is the specific purpose of this study to determine the quantitative effect of inclusions on the physical properties of steel that determine its behavior under dynamic stress. The study has shown that a quantitative relation between counted inclusions and impact strength does exist in normalized steels, but that factors other than readily visible inclusions are equally important. Furthermore, the present commercial rating of inclusions is unreliable with respect to counted inclusions or dynamic tests, and this study indicates that the tensile-impact test is more reliable as a measure of quality. General Scheme The general plan of the study follows: (1) To develop or establish a satisfactory measure of dynamic strength; (2) to develop or establish a

Jan 1, 1931

By William H. Emmons

Jan 1, 1912

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By Bror Nordberg

SAND and gravel are unconsolidated granular materials resulting from the natural disintegration of rocks. The two materials nearly al- ways occur together, variably proportioned in widely available de- posits. A commercial sand comprises the fine granular material, usually less than f in. in diameter (ASTM Designation C58-28), and gravel consists of the coarse, granular material larger than sand (ASTM Designation C125-46T). Gravel falls within the range of 1/4 in. and a top size usually of 3 ½ in. Chemical definition is impossible. Sand and gravel are always of secondary origin. They were formed from various massive rocks through the action of chemical and mechanical forces; then transported, abraded, washed, sorted, and classified by streams, glaciers, waves, or winds, to be redeposited in beds as they are found. Chief disintegrating forces in the reduction of rocks into granular particles were frost, rain, the dissolving action of acid and alkaline ground waters, the mechanical action of streams and waves, and the action of glaciers. Method of formation and deposition have imparted physical properties to sands and gravels that largely determine the commercial value of the materials for particular use and influence the manner of exploitation. In the early days of the commercial industry, purchasing specifications were relatively lenient but in. the past decade much more rigid quality requirements have had to be met for acceptance by all classes of purchasers. The trend to further severity in requirements is a challenge to the industry that commands full knowledge of the nature of raw materials at hand and skillful application of processing into commercial products. Mechanical strength, the ability to resist disintegration, chemica

Jan 1, 1949

By F. I. Stalkup

Vapor-liquid phase equilibrium experiments have been conducted in a static equilibrium cell on mixtures of a light, 45 API stock- tank gravity reservoir fluid and a rich hydrocarbon gas containing approximately 55 mole per cent of intermediate hydrocarbons. Both apressure-vs-composition study of the gas and a simulated reservoir fluid, and a multiple-batch contact simulation of the condensing-gas-drive oil recovery process were performed. In the latter experiments equilibrium gas and liquid compositions were analyzed. Also, conventional, "condensing-gas-drive", long-tube displacement experiments of the reservoir fluid and gases of various richness were performed. The results of these experiments could not be satisfactorily interpreted by the conventional pseudo-ternary-diagram representation of multicom-ponent phase behavior. The results seem to be explained better by considering a bubble-point surface and a dew - point surface joined in a plait-point locus. Portions of the plait-point locus cannot be "seen" directly by the rich hydrocarbon gas because of curvature of the dew-point surface. In such a system, continuous injection of the rich gas over stationary reservoir fluid might form a zone of contiguously miscible compositions from pure rich gas to pure reservoir fluid by: (1) saturating the reservoir fluid with injected gas to the bubble-point surface; (2) creating by mass transfer with fresh injected gas a path of contiguously miscible compositions along the bubble - point surface to the plait-point locus; and (3) creating by mass transfer with additional injected gas a path of gas compositions along the dew-point surface up to the point where direct miscibility results between dew-point fluid and the injected rich gas. INTRODUCTION The use of the pseudo-ternary-phase diagram to illustrate miscible displacement phase behavior has been discussed by several authors.5,7 Such a representation of phase behavior is not rigorous, but the ternary diagram nevertheless gives a qualitative picture of what actually occurs in a miscible displacement process. Fig. 1 is a typical illustration of miscible displacement phase behavior by a ternary diagram. The multicomponent hydrocarbon system is divided into three pseudo-components: a light fraction containing methane and nitrogen, an intermediate fraction containing ethane through hexanes plus carbon dioxide, and a heavy fraction containing heptane and heavier components. A two-phase region is bounded by a dew-point curve and a bubble-point curve, which are joined at the critical point. The concept deduced from such a representation for miscible displacement by a condensing-gas-drive process is as follows: a rich gas G, which lies to the right of the limiting tie line through the critical point C, is injected into the reservoir and contacts reservoir fluid L, saturating the reservoir fluid to give bubble-point fluid L1 and equilibrium dew-point gas GI. Continued injection of rich gas changes the composition of the saturated liquid L1 through a series of liquid compositions lying along the bubble-point curve, until the critical composition C is reached, at which point direct miscibility with the rich gas is achieved. Some equilibrium gas with compositions lying along the dew-point curve from G1 to C is also formed in this process. Thus, continuous injection of rich gas forms a

Jan 1, 1966

By P. Bolsaitis, L. Skolnick

A model of metallic solutions is postulated which explains the energy of formation of alloys on the basis of changes in electron density around solute and solvent atoms and changes in pairwise interactions between atoms. The model is based on the Wigner-Seitz cell model of metals, with the electronegativities of the metals as the parameter for the electron-attracting power of the constituent atoms. In contrast to models based on the description of cohesive energy in terms of pairwise interactions only, which require an empirical, adjustable correction parameter to the Berthe-lot relations in order to predict negative energies of formation, the electron cell model accounts for both negative and positive energies on the basis of parameters of the pure components. Calculated heats of mixing based on published parameters of the pure metals are found to compare favorably to experimental values, despite the absence of any adjustable parameters in the model. THE formulation of an "exact" quantum mechanical model for the energy of cohesion of metals reduces ultimately to the many-body problem and for a complete solution would require the knowledge of wave functions and energy levels of all the particles in the system. The case of alloys is further complicated by the fact that the potential fields around the constituent atoms are different and the matching of boundary conditions in terms of the resulting wave functions is still an unresolved mathematical problem. It appears that in spite of the numerous investigations that have led to an elucidation of many properties of the metallic state, the formulation of the Hume-Rothery rules in 1931 marks the lone accomplishment toward simple, qualitative prediction of the energy of formation of alloys. More recently Friedel'' and Arafa have utilized the modern concepts of the electronic structure in metals in combination with the Hume-Rothery rules to arrive at quantitative estimates of the energy of formation of alloys with low solute contents. The relative success of the Hume-Rothery rules and Friedel's and Arafa's studies encouraged broaching the subject of formulation of a model based on realistic physical parameters and of conceptual and mathematical simplicity that could be applied to alloys regardless of concentration. On the basis of the free-electron theory, the cohesive energy of pure metals can be expressed as a function of "valence" (number of free electrons per atom), lattice parameter (or density), and the ioniza-tion energy. In addition to the electronic contributions to cohesion, one has to consider the pairwise exchange interaction energy between neighboring ion cores and the contribution from van der Waals forces. The energy changes upon alloying are viewed as resulting primarily from a redistribution of electron densities around the ions (a simplification of the more basic concept of a change of the wave functions of the electrons in the presence of a perturbing potential field). In addition there is a change in the pairwise interactions between neighboring ions which is usually the only factor taken into account in commonly used adaptations of the quasichemical theory. The electronegativities of the metals forming the alloy are used as the measure of the electron-attracting power of the ions in the alloy and the difference in electronegativities as the driving force for changes in electron energy on alloying. The interplay of pairwise interactions and electronic forces results in positive or negative energies of formation of alloys. Results obtained for systems to which the free electron model is best applicable are in good agreement with experimental values. 1) COHESIVE ENERGY OF METALS IN TERMS OF THE ELECTRON CELL MODEL The simplest physical model of a metal is that of a lattice of positive charges immersed in a sea of uniform, negative charge distribution represented by the

Jan 1, 1969

By Manuel Eissler

INTRODUCTION THE history of copper metallurgy in Japan goes back into remote ages, of this there is abundant proof, and that the working of this metal is closely connected with the artistic development of this nation is evidenced by some of the glorious monuments which have been produced by these ancient metal workers. The traveler sees to-clay in a perfect state of preservation bronze statues 150 ft. high, and over, 300 ft. in width, and 170 ft. in depth, delicately chased and beautifully marked, and when one reflects that some of them date back to the eighth century A. D., the question naturally suggests itself, how did these ancient metallurgists with their crude and primitive appliances accomplish this stupendous task? The bodies of these images are formed of bronze castings 10 to 12 in. thick, which were gradually built up and soldered together, but other pieces of magnitude, like the heads and other portions of the body are single castings. In many cases another method of construction must have been adopted. The walls of the molds were gradually built up and as the lower portion of the castings cooled, the walls were raised higher and higher and fresh metal must have been added, instead of constructing the whole mold first and then making the casting in one piece. There are still traces of substantial gilding visible on these statues, and how the pious Buddhist priests who were the constructors of them got the precious metal, is preserved in legendary tales.

Jan 11, 1914

By D. V. Doane, G. A. Timmons, W. G. Scholz

Molybdenum of high purity can be produced by direct dissociatiott of commercial molyhdenm disulfide in vacuo at 1600° to 1700°C (2910° to 3090°F). The Product is lower in oxygen than commercially available molybdenzdm powder. Analyses of ingots arc-cast from commercial molybdenum powder, hydrogen-re-cluced from animonium molybdate, and from thermally dissociated molybdenum disulfide indicate that the levels of chemical impurities in these ingots are similar. Equipment now in operation will produce 100-lb hatches of powder product. The paper describes development of processing equipment, control of processing varzahles, handling of the product, and evaluatiotl of the melal produced. MOLYBDENITE (molybdenum disulfide) can be decomposed by heat in the absence of oxygen to produce elemental molybdenum and sulfur, which is evolved as a gas. The temperatures required for the dissociation are above 1370°C (2500°F); the sulfur must be continuously withdrawn to permit the reaction to proceed to completion. This is accomplished by continuous evacuation of the thermal dissociation chamber and condensation of the gaseous sulfur in another part of the system. Cognizance of the fact that the dissociation takes place in two steps is important in controlling the process. Basically, the molybdenite dissociation process has two potential advantages as a method of produc- ing pure molybdenum: 1) The materials entering into the process contain little or no oxygen. Since the process is carried out in vacuum at high temperature, the quantities of interstitial oxygen, nitrogen, and hydrogen in the product should be very low. 2) The process is more direct than the commercia1 method of producing high-purity molybdenum. In the conventional process, molybdenite is roasted to molybdic oxide, the oxide is purified first by sublimation, then by conversion to ammonium molybdate, and finally, the molybdate is reduced in a hydrogen atmosphere (usually in two steps) to the metal lic molybdenum powder. This paper presents a description of the stages in scaling-up of the dissociation equipment and an account of attempts to evaluate the molybdenum produced by thermal dissociation, rather than a report of a fundamental study of the dissociation reaction. Since little has been written on the subject, it is appropriate, before detailing the development of the process, to review briefly the research that has been conducted over quite a period of years. LITERATURE SURVEY The first accounts of the possibility of thermal dissociation of the mineral molybdenite were re-

Jan 1, 1962

By E. D. McMurry

INTRODUCTION Before discussing the use of the free piston; it may be well to explain briefly the type of gas lift valves with which the loo] is designed to function. The gas lift valve ii nothing more or less than a small back pressure regulator. It; construction consists of an outer hous ing covering a seamless metallic bellows in such a way as in form a sealed pressure vessel or pressure dome. To the bellow* in attached a stem and to this stem is attached a .rating member. When the valve is run into the hole, a pre-delermined pressure charge is placed in the pressure dome. As shown in Fig. 1. the valve is furnished in four different major assem-blies. to accomplish good results in different types of wells. The valve is mounted on a pup joint (Fig. 2a) : the eoin-plele assembly is entered into the tubing siring at the desired location. Each valve is furnished with a revere flow check valve (Fig. 2-b) to eliminate any back wash through the mechanism. Valve action is as follows: At any time the casing pressure is allowed to exceed the pressure forces within the pressure dome of the valve, the valve simply opens and passes gas from the rasing annulus into the tubing. When the casing pressure forces arc allowed to bleed to a force less than the pressure force within the dome, of the valve. the valve closes. With this type of construction. it is possible to open and close the valve or valves at will from the surface, the medium of the gas pressure in the rasing annnlus. The cycle of operation is governed by a tine cycle motor valve, commonly referred to as a gas lift interutitter or gas life surfacr controller (Fig. 3). In actual practice. after the well is unloaded only one valve is in operation . . . all other valve.: remain in the closed position. On pre-determined time cycles, it is possible to open and close this operating valve at will, and to pass the desired amount of gas through this valve wheneler needed. This method of gas lift is widelv used and has been found In be very efficient. However, it has long been known that even greater efficiency would be obtained if it were possible to place Piston between the injected gas and the fluid head. The free piston which will be discussed here was designed to accomplish this end and has been found to do so with very satisfactory results. DESIGN AND OPERATION OF THE FREE PISTON Basically. the free piston consist- of a telescoping assembly in which are incorporated the various control and operating parts (Fig. A set of sleeve valves which are opened and closed by movement of the telescoping section is contained in the. tool. A cross section of the free piston is shown in Fig. 4-11, 'rile main body cotain- a seamless monel bellows of the same type as that generally used in pressure charged gas lift valves (Fig. 4-c), and a valve core to permit placing a pressure charge in the bellows before the free piston is placed in service. The bellows is the main control unit of the free piston and performs two function: 1. It governs the opening and closing of the sleeve valves. a.: dictated by the producing activities of the well in which the piston is operating. 2. In its normal position, it holds a rubber packer in an elongated position to permit passage of fluid between the packer and the tubing walls. The lower section of the free piston contains a hydraulic shock absorber which cushions the return of the tool to its

Jan 1, 1953

By G. S. Rice, J. A. Davis

The Péchelbronn oil field is located in the province of Alsace, in the Rhine Valley, about 30 miles north of Strasbourg. It is approximately 4 miles wide and 12 miles long, extending from the villages of Lobsann on the north to Wintershausen and Ohlungen near Haguenau on the south. (See Fig. 1.) The productive area includes about 44,000 hectares (107,680 acres). The name Péchelbronn signifies "pitch-spring" or "pitch-fountain." The first exploratory galleries were driven in from the hillside in 1735; and in 1745 the first official concession was granted by the French government and the first pit sunk to a depth of about 30 ft. Extraction by drilled wells was begun in 1879, supplementing the mining operations, and during the next 10 years 200 wells were drilled to an average depth of 172 m. (568 ft.). The bringing in of two "gusher" wells, in 1882 and 1888, respectively, was followed by the abandonment of all underground work. Underground mining, with a view to increasing the production of petroleum by recovering the oil left in the sands after drilling wells, was resumed in 1916. This mining operation started by sinking shaft No. 1 to a depth of 150 m. (495 ft.). The underground developments were pushed during 1917 and 1918 and the annual production of the Péchel-bronn field was increased to about 50,000 metric tons or 350,000 bbl. On the signing of the Versailles Treaty the province of Alsace, which had been taken by Germany as the result of the war of 1870, was returned to France, and the proprietary rights were taken over by the French Government. Concessions or leases, which embraced all the known oil-bearing territory of the field, were granted to the present operating company, Mines de Péchelbronn. This company followed both the drilling and the mining methods of the previous company.

Jan 1, 1927

By N. F. Foster

The use of piezoelectric semiconducting materials for the fahrication of ultrasonic transducers has raised the upper fundamental frequency limit for transducers from about 200 mc to above 10 kmc, Several types of semiconductor transducer configurations have been proposed and examined experimentally. Depletion-layer transducers have been made and operated at frequencies below 1 kmc hut they appear to he better suited for operation at considerably higher frequencies around 10 knzc. Diffusion-layer transducers have been made and operated in the range 50 to 1000 mc and have exhihited considerably improved conversion losses and bandwidths compared with other transducers available in the frequency range. A variety of novel structures are possible using these new types of transducers, some of which could lead to substantial advances both in research and in the fabrication of ultrasonic delay lines and memory elements. THE field of ultrasonics today spans some five decades of the frequency spectrum from the audible to the kmc range and finds applications ranging from fundamental research into the atomic structure of matter to the degreasing of machine parts. To cover this wide range it has been necessary to develop a great many types of ultrasonic trandsucers utilizing a variety of materials and physical phenomena. The first ultrasonic transducers were made during World War I for a submarine-detection system. They consisted of plates of single-crystal quartz bonded between metal plates and were one of the first applications of the phenomenon of piezoelectricity discovered nearly 30 years previously. Despite the many advances which have been made in transducer technology, piezoelectric transducers using single-crystal quartz are still used almost exclusively for application above about 30 mc. Transducers at these frequencies are normally made in the form of thin quartz plates which are then bonded onto the medium in which the ultrasonic wave is to be propagated. The crystallographic orientation and geometry of these plates determines the type of wave generated and the way in which the efficiency of the electromechanical conversion varies with frequency. Analysis of the design parameters shows1 that the frequency of maximum efficiency (the fundamental or resonant frequency) is that frequency at which the transducer is approximately half the wavelength of the ultrasonic wave in the material. As the frequency increases, the ultrasonic wavelength, and therefore the optimum transducer thickness, decreases and in practice the fabrication of quartz transducers with fundamental freauencies above 100 mc becomes extremely difficult due to the extreme thinness required. For frequencies above 100 mc quartz transducers can be used in overtone-mode operation, and for very high frequencies (500 to 24,000 me) a technique using a quartz rod inserted in a high-Q microwave cavity4 is available. These techniques, however, exhibit comparatively low fractional bandwidths and rather poor conversion efficiencies. The present trend in ultrasonics is towards high frequencies and greater bandwidth to allow the use of shorter pulses which can give increased discrimination in radar-system delay lines and greater storage capacity in computer applications. The increasing demand for more efficient transducers with greater bandwidth

Jan 1, 1964

By D. D. Pollock, D. I. Finch

PREVIOUS work' on a four-component system (Cu-Mn-Ni-Fe) resulted in the development of consistent relationships between the chemical composition and the electrical properties of these manganin-type alloys. The present study was undertaken to develop alloys with temperature coefficients of resistivity and thermoelectric properties more desirable than those of the manganin type, and to determine whether the relationships which had been found for the Cu-Mn-Ni-Fe alloys could be extended to five-and six-component alloy systems. PREPARATION OF ALLOYS The five- and six-component alloys were made from OFHC copper rod, ARMCO iron, electrolytic nickel, manganese cathode chip, and special high-purity aluminum and indium. A Cu-Mg master was used for deoxidation. The compositions of these materials are given in Table I. The alloys were melted and cast as indicated previously,' except that no cover was used and the melts were teemed. EXPERIMENTAL PROCEDURE The finished wire size of 0.0808 in. diam was again selected for the reason that the test specimens would be self-supporting, thus eliminating any extraneous effects which might have been introduced by winding smaller diameter wire on spools or forms. The following tests were performed on the finished wires: A) Chemical Analyses—All of the components of these alloys were determined by premium gravimetric methods. The principle residual impurity contained in these alloys is 0.008 pct Mg (by weight), maximum. Tables II and 111 present the mean analyses computed from at least four determinations of each constituent. B) Electrical Characteristics—The test procedures forthe determination of the thermal emf vs copper, resistivity, and the resistance-temperature relationship are given in detail in Ref. 1. It was also shown that the resistance-temperature relationship is of the form Pt = P,n + At -B/2, [1] where P, is the resistance at t C expressed in percent of a given standard resistance, P, is this per- 0 centage at 0°C, and A and B are constants for a given, properly treated, composition. The results of the electrical tests are also given in Tables II and 111. INTERPRETATION OF DATA The modified Linde2 formula, known to be valid for dilute binary solid solutions, was applied to the complex Cu-Mn-Ni-Fe type alloys. This relationship is of the form where Ap is the increase in resistivity. Zb the valence of the solute, Zn the valence of the solvent, and K and K are designations assigned by Robinson and Dorn3 to the constants for the periodic group to which solute element belongs. The units of K, are -cm per valence difference squared per at. pct; those of K2 are pa-cm per at. pct. For the sake of brevity, these units are not repeated in the following discussion. Calculations were made to determine if this formula was accurate for five-component systems. No experimental studies were made of the Cu-In and Cu-A1 binary systems. The effects of indium additions upon the resistivity of copper are given by Linde. These data, along with those of the effects of Mn and Fe, permitted the calculation of the effects of Al.

Jan 1, 1959

By R. D. MacDonald, John Dasher, A. M. Gaudin

ION exchange is a widely used unit operation in water treatment and elsewhere in chemical industries. It has occasionally been used in hydro-metallurgy for treating plating, pickling, and rayon wastes Concerning ion exchange in extractive hydrometallurgy—for treating ore leach solutions— the literature prior to the Geneva Conference has given only hints."-" Yet most of the ore leach plants now being built or completed in the last three years use ion exchange for this purpose. Most of these plants are used for extracting uranium. The overall process for leaching low grade uranium ores and the history of its development have been given in the authors' previous papers.',' The object of this paper is to discuss certain engineering aspects of the new application of ion exchange to recover dissolved values from ore leach solutions. Necessarily the illustrations will be taken from the first application—to uranium metallurgy. Although ion exchange processes have been devised in which separation of spent residue from pregnant liquor is not required, as in the RIP process,"-'I only ion exchange operation, in which the resin is contacted with a clear solution, will be discussed in this paper. Uranium exists in acid leach liquors mainly as the cation UO," and can be adsorbed completely by cation exchange resins, but the adsorption is not selective as other cations such as Fe++, Fe+++, Al+++, Mg++, Mn", and Ca++ are also adsorbed. Uranium, however, forms complex anions with sulfate, phosphate," Carbonate"~"~ and even with chloride if the solution is strong enough.15 These anions can be adsorbed by anion exchange resins. The strong base anion exchangers have a very strong preference for these complexes and hence this adsorption is very selective. In this paper, the examples concern acid sulfate leach liquors from which uranium is adsorbed as UO,(SO,),-% and UO,(SO,),". Materials and Equipment Ion Exchange Material—Ion exchange materials include natural and synthetic; organic and inorganic; cationic and anionic; and weak, intermediate, and strong varieties. They consist of fragments or beads normally in the size range —16 to $50 mesh. The newer varieties have been developed to have greater stability, chemical strength, and/or capacity than earlier varieties. The resin used for uranium recovery is a strong base anion exchanger.* To make * Such as Rohm and Haas Amberlite IRA-400 series, British Permutit DeAcidite FF. Permutit lonac SE. and Dow Nalcite SAR. this resin, styrene plus a few percent divinyl benzene are polymerized into long chains with occasional cross links. This resin in bead form is then reacted to introduce quaternary amine groups onto most of the aromatic rings.' These resins are water-avid gels of specific gravity of about 1.1, which shrink and swell by osmosis when the ionic content of the surrounding solution is changed. The beads which are shown in Fig. 1 can be broken like an onion by rapidly replacing 15 pct H,SO, with water. This organic gel can also be broken by mechanical handling as by a centrifugal pump. Otherwise it is remarkably stable. It is unharmed by fairly strong acid or alkali, oxidizing or reducing agents, and heat up to 70°C. The strong base resin when completely in the chloride form (with a chloride anion on each quaternary amine group) holds over 107 g of C1- per dry kg. As all these chloride ions can be displaced by other anions, the resin has an exchange capacity of over 3 g equivalents per dry kg. However, the resin is sold and used by moist volume. The moist resin contains about 50 pct water, weighs about 43 lb per cu ft, has 40 pct voids, and an exchange capacity of over 1 g equivalent per liter of bed volume. Ion Exchange Equipment—Ion exchange equipment used for recovery of uranium from leach solutions is substantially identical to that developed for water treatment and other applications.'" The resin beds are held in closed tanks or columns which, in the uranium plants, have been standardized at 7 ft diam and 12 ft high. The resin bed

Jan 1, 1958

By P. B. Bucky

In previous publications1 it was shown that a scalar model of any weighty structure, where the stresses produced are mainly due to gravitational forces, will behave similarly to its prototype if the model and prototype material are the same and the model is placed in a centrifugal field of force (substituted for the gravitational field) which has been increased in the same proportion as the linear model scale is decreased. This principle is now being applied to a study of the behavior of mine structures in an attempt to determine the laws that control them. The importance of using models as a means of solving mining problems has been discussed previously, yet it may be well to reiterate here that this method of research and type of solution have been productive of far-reaching results in other engineering fields, notably those of hydraulics and aerodynamics. Model research is a comparatively cheap and time-saving method of checking practical experience. Up to the present time the best guide to what will happen underground has been the judgment of the man who has observed most and been longest acquainted with the local conditions. His experimental work underground is limited by the elements of cost, time and danger, while failure is seldom permissible. In a model, as in a test tube, all elements that affect the solution of a problem are under definite control. Each element may be varied independently at hill and its effects noted. Experimental work on a small-scale model may therefore be performed at a comparatively small expenditure of time and money, instead of on a full scale in the mine, where the cost, time, and danger elements are necessarily great. The experiments described in this paper are to be considered as part of a progress report and a continuation of Technical Paper 425. One object of the research program is to make each experiment point the way for further research on that particular phase of the general problem. The results and conclusions presented here are therefore not to be considered as final, but arc to be interpreted as

Jan 1, 1934

By Rex B. McLellan

Studies of the eyuilibrzum between ferrite and austenite with gas mixtures (CO + CO2 and H2 + CHe) have been used as a means of deducing the energy and vibrational entropy of carbon atoms in dilute interstitial Fe-C solutions. A simple model for dilute interstitial solutions is given which enables a solubility equation for the equilibrium between the gas mixtures and the solid to be deduced. This solubility equation is used to estimate the partial In this work measurements of the equilibrium between dilute solid solutions of carbon in iron and gaseous mixtures of CO2 + CO and CH4 + Hp have been analyzed using theoretical solubility equations deduced from a knowledge of the thermodynamic parameters of the gas mixtures and an appropriate model for the solid solution. The solubility equations are deduced by equating the chemical potential of carbon atoms in the gas thermodynamic functions of dilute Fe-C solutions from the measured equilibrium between the solid and the gas mixtures. It is shown that the vibra-tional entropy of a carbon atom in a and y iron is smaller than the corresponding entropy 01. a nitrogen atom in solid solution inferrite or austenite and that there is little difference between the vibrational entropies of both nitrogen and carbon atoms in ferrite and austenite. and solid phases. The chemical potential of carbon in the gas is found from a simple statistical mechanical analysis of the gas mixtures utilizing spec-troscopic data while that for carbon in the interstitial solution is found from a model in which the carbon atoms act as bound oscillators distributed in a random fashion in the solution. The solid solution is dilute enough to enable solute-solute interactions to be ignored. Thus the configurational entropy of the solution is ideal but the mixing entropy contains additional excess terms due mainly to the vibrational changes occurring on solution formation. The partial excess entropies (and the partial energies) do

Jan 1, 1965

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By R. B. Full

DURING the summer of 1949, the United Nations Scientific Conference on the Conservation and Utilization of Resources met at Lake Success. As summed up by one writer, the purpose was: "That everyone will try to learn how to feed more people from an acre of land." That objective is a stimulus to the phosphate rock industry as well as other industries. Phosphate rock was mined first in the Canadian province of Quebec where it was found as an apatite in pockets. In 1863, mining began near the Rideau Canal, first in open trenches and quarries until shafts were sunk. These operations were difficult since hard rock had to be drilled and blasted. Steam was the source of power. The phosphate rock was hand-selected and recovery ranged from 6 to 10 pct, averaging 70 pct to 85 pct bpl (bone phosphate of lime). Costs, f.O.b. Montreal, were $14 a ton, and selling prices averaged $17 a ton. In 1885, about 29,-000 tons were sold on this basis, but by 1892 the output fell to 8000 tons at an average price of $15 a ton at Montreal. South Carolina Deposits Phosphate rock was first discovered in South Carolina in 1837, but a mining company was not formed until 1867. It was immediately successful, and the industry continued to develop and ship an increased tonnage of land and river rock, shipments increasing from approximately 20,000 tons in 1868 to 537,000 tons in 1890, when the shipments began to decrease. In 1892 only 350,000 tons were shipped. In this field there were two types of deposits: land rock and river rock. More land rock tonnage was mined until about 1887 when river rock production began to equal it. The land rock was mined adjacent to and in the river marshes by pick, shovel, and wheelbarrow. Each worker dug daily a space 6 ft wide, 15 ft long and 6 ft deep, which was overburden, and then loaded about 3 cu yd of phosphate rock into wheelbarrows. His helper would wheel the barrows to small steam railroads up to 250 ft distant. Water was kept from the pits by steam pumps connected to railway cars. The phosphate rock was loaded into railroad cars, hauled and dumped into a log washer to which water was added, and run over trommel screens to eliminate the clay and loose sand. Steam shovels for loading were introduced about 1891. River rock was mined by floating dipper dredges and at low tide was loaded into barges by laborers using oyster tongs, the large lumps being hand-loaded. Barges and bateaus were unloaded by wheelbarrows which were wheeled to the same type of land rock washers. The washer product was piled with stacked pine cordwood in alternate layers and fired for drying. Usually this was done under sheds along the river bank. The dried rock then was transferred to ships, usually three or four-masted schooners. Cost of production of both land and river rock, including $1 a ton royalty paid to the state for state-owned property, was approximately $4.25 a ton averaging 60 pct bpl. The selling price was approximately $7 a ton f.O.b. In 1886 the courts handed down a decision permitting anyone to mine, and many additional companies were organized immediately. As a result, the selling price was lowered to a profit margin of 50Ø or less per ton. The South Carolina mines were eventually shut down when a more profitable source of phosphate rock was discovered in Florida. Florida Deposits Phosphate rock was discovered in Florida in 1882, and in 1883 a small quarry was opened near Hawthorne. In 1886 phosphate rock of good grade was discovered on Peace River, and the Arcadia Phosphate Co. was formed. In 1888 the company began shipments amounting to 3000 tons that year. During the latter part of 1888, hard-rock phosphate was discovered near Dunnellon. Exploration extended rapidly, and deposits of hard-rock phosphate were mined over a wide area so that shortly after 1900

Jan 1, 1952

By R. F. Mehl, M. Gensamer

Although a large number of X-ray photograms of cold-rolled steel have been published, two circumstances have led to the experimental work reported in this paper. The first is that no complete study, making use of the pole-figure method of Weverl, has been made of cold-rolled low-carbon steel. Wever has published pole figures of mild steel subjected to plane parallel deformation1, 2 and undoubtedly he has applied the method to cold-rolled mild steel, but the authors have not found these data published. Kurdjumow and Sachs3 have applied the method to the study of rolling and recrystallization textures in electrolytic iron; their results will be referred to later. The reason for this dearth of papers using the pole-figure method is obvious; a greater number of photograms and more analytical work (although this work is quite simple and straightforward) are required to construct a pole figure than most investigators have felt worth while, despite the fact that no other method of which the authors are aware will satisfactorily depict the orientations of the crystallites in a polycrystalline aggregate. The second circumstance that led to the work reported in this paper was the appearance of a paper by Wayne A. Sisson4 on the same subject. In his valuable study of the factors influencing the development of preferred orientations in cold-rolled mild steel, Sisson made one observation that required confirmation; that is, that at some stage of the rolling process the type of preferred orientation changed from the type that gives a photogram characterized as a "six-point" X-ray pattern to that known as a "four-point" pattern. A similar observation had been made by Tam-mann and Heinzel5, who studied the orientations developed in the rolling of steel by the specular reflection of light from the etched surface of rolled samples. These workers also found that the type of preferred orientation changed during the rolling process. The authors had some difficulty in seeing how this behavior could be consistent with modern views on the genesis of preferred orientations, particularly with those of Wever2

Jan 1, 1936

By Earl S. Greiner, Bradley Stoughton

As a part of the systematic study of the alloys of iron under the auspices of the Engineering Foundation, and preliminary to the commencement of comprehensive work on this larger subject, the authors have undertaken an investigation of the available literature dealing with the alloys of iron and silicon. The purpose is to collect all the data in English and foreign languages and present them in two monographs, one of a more scientific and the second of a more industrially useful nature. Of course, a great deal of information upon the constitution of the iron-silicon alloys was found specificially upon the changes of phase in the equilibrium diagram and the different phases present, such as solid solution, chemical compounds (iron silicides), etc. While no extended research was contemplated in the particular study undertaken, nevertheless the data collected proved to be so contradictory in many respects that a simple study of some of the outstanding problems involved in the constitution and equilibrium diagram was undertaken. Because research was not a primary object of the work, and also because of the extreme industrial importance of the silicon alloys between 0.80 and 14 per cent. silicon, and finally because of the unsatisfactory state of knowledge existing as to these alloys, the experimental investigation was limited entirely to alloys with less than 10 per cent. silicon. Discussion oF Continuous Series It has often been said in print that the iron-silicon alloys form a continuous series of solid solutions from 0 to 15 per cent. silicon. This claim the authors are inclined to doubt: first, because the alloys from 0 to 4.25 per cent. silicon are ductile and malleable at atmospheric temperature, while those with 5 per cent. or more of silicon are comparatively hard and brittle. Furthermore, the alloys with more than 4.25 per cent. silicon are comparatively hard and low in ductility at atmospheric temperature, but become much more ductile when heated slightly. It is well known, for example, that the alloy containing 4.75

Jan 1, 1930

By Andrew Mayer

Early in 1942 National Lead Co. was requested by the War Production Board to construct and operate a plant for the Government to produce magnesium by the ferrosilicon process which had been developed by Dr. E. M. Pidgeon in the laboratories of the Canadian National Research Council. A contract with the Defense PlantCorporation was concluded in May 1942 and Magnesium Reduction Co., a wholly owned subsidiary of National Lead Co., was formed to carry out this project. The capacity of the plant was rated at I0,000,000 lb. of magnesium per year, equivalent to an average production of about 14 tons per day. The Process The process, in brief, is as follows: The raw materials are dolomite and ferro-silicon, 75 per cent grade. The dolomite is calcined, the calcine and ferrosilicon are ground and mixed and the mixture is briquetted. The briquets are charged into tubular retorts of chrome-nickel steel set horizontally in a furnace with the open ends projecting outside the front wall. The retorts are then closed and evacuated. Magnesium is liberated according to then reaction 2(MgOl CaO) + Si = 2Mg + zCaO, Si% It is distilled from the charge and con- densed on a removable sleeve in the throat of the retort. Sodium and potassium, if present, are also liberated, distilled and condensed on a "sodium condenser" in the end of the retort. At the expiration of the distillation period the retorts are discharged and the cycle of operations is repeated. For the rated daily capacity of 14 tons of magnesium there are required approximately 170 tons of dolomite, equivalent to about 85 tons of calcine, and 16.5 tons of ferrosilicon. The retort residue, a bulky powder which at present is waste, amounts to about 87 tons. Choosing the Site The investigation to select the location of the plant was conducted by the Research Laboratories of National Lead Co. This work included geologic and economic surveys of a number of districts, examination of dolomite samples by chemical, spectrographic and petrographic methods and large-scale tests of dolomite from several of the more promising localities. in the last-named tests 2-ton samples were put through the ferrosilicon process in the pilot plant of the Canadian National Research Council, under the guidance of Dr. Pidgeon. The conclusions drawn from the investigation, in regard to the quality of dolomite to be used in the ferrosilicon process, were: First, the dolomite should contain not less than 21 per cent MgO and not more than 2 per cent acid-insoluble material. Second, the dolomite should

Jan 1, 1944