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By D. A. Elgillani, S. Atak, D. A. Rice, M. C. Fuerstenau, R. B. Bhappu

Quartz and feldspar cannot be floated with sulfonate at any pH; spodumene floats over a narrow acid pH range, while beryl responds moderately over a broad pH range. After wet-grinding in a steel mill, beryl, quartz, and spodumene float well with sulfonate below about pH 7, whereas the improvement in the response of feldspar is not so marked. A mechanism by which iron can be adsorbed on these minerals is presented. Also, the responses of leached, natural, and wet-ground beryl to amine, sulfonate, and oleate flotation are shown and related to the measured zero-points-of-charge of these materials. Earlier work with leached beryl showed that good flotation could be obtained with alkyl aryl sulfonate over a rather wide pH range using a Fagergren flotation cell.' When a similar response was observed with leached quartz, it was decided that unintentional activation was being obtained from the metallic components of the Fagergren cell. To obviate this difficulty, a microflotation cell was designed, and an experimental technique was devised. These have been described elsewhere. Experiments conducted with the small cell showed that leached quartz could not be floated at any pH with any sulfonate addition,3 which is in agreement with the observations of Kraeber and Boppel.4 Similarly, it was also found that leached beryl responded to sulfonate flotation only over a narrow pH range rather than the broad range reported earlier.1 This early work,1 however, revealed the important effect that wet-grinding in a steel mill has on the flotation response of certain silicates. That is, it was found that quartz and especially beryl floated well over an unusually wide pH range after wet-grinding in a steel mill. Microcline, however, floated poorly below pH 4, even though wet-ground under the same conditions. The work of Eigeles6 on adsorption of oleic acid on leached quartz and iron-contaminated quartz at constant pH is in agreement with these flotation data. Other research has shown that ferric iron, added as a salt to the system, functions as an activator in the narrow pH range in which Fe +++ iron hydrolyzes to its hydroxy complexes.3,5 These phenomena indicate that iron functions differently in flotation systems depending on its method of introduction. The object of this paper is to determine the mechanism by which iron is adsorbed on certain minerals, the mechanism of collector adsorption after iron abstraction, and the role that Fe++ and Fe+++ assume in the selective separation of these minerals. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate, mol wt 450,7 pure potassium oleate, and pure dodecylamine were used as collectors. All other chemicals were reagent grade in quality, i.e., n-amyl alcohol as frother; HC1, H2SO4, and KOH for pH adjustment; and ferric chloride as activator. Conductivity water, made by passing distilled water through an ion exchange column, was used in the experimental work. All minerals used in the investigation were hand-picked specimens. Sample Preparation: Each of the minerals was crushed through 8 mesh, and the product was divided into two groups, one to be ground dry and the other wet. Dry grinding was accomplished with an alumina mortar and pestle. The product was dry-screened to 48 x 150 mesh, cleaned magnetically, deslimed in conductivity water, and dried. Preparation of the samples by wet-grinding involved grinding a 200-g charge of the mineral (-8 mesh) at 60% solids with natural water in a mild steel rod mill for four minutes. This charge was then wet-screened immediately with natural water to 48 x 150 mesh, dried, and cleaned magnetically. Some experiments were also conducted with leached beryl and quartz. These products were prepared by leaching the sized sample (48 x 150 mesh) with concentrated HC1 with a percolation technique until no iron could be detected in the leach liquor. Following this step, the sample was rinsed with conductivity

Jan 1, 1967

By R. E. Ogilvie, N. L. Peterson

Intevdiffusion and intrinsic diffusiorz coefficients were determined in the uranium-niobium system from diffusion couples analyzed with an electron microbeam probe. A Previously unveported intermediate phase, designated in this report as the delta phase, was found to exist along the mobium-rich side of the miscibility gap. Its composition width was determined from the concentration gradients in the diffusion couples. The presence of this phase was also confirmed by microhardness analysis and metallographic observations. THE excellent corrosion resistant properties, high-temperature strength and reasonable nuclear properties of niobium have prompted its use as an alloying element with uranium and as a possible cladding material for reactor fuel elements. Hence the formation and growth of intermetallic phases as well as diffusion data for the uranium-niobium system are of considerable practical importance to metallurgists and nuclear engineers. Diffusion zones may exhibit varying degrees of complexity dependi.ng upon the mutual solubility of the metals involved, and the intermediate phases which may form. In the simplest case where the metals exhibit a calmplete range of solid solubility, a single phase region is produced. Generally, however, the metals may react to produce a multiphase diffusion zone containing several layers of intermetallic phases. A number of investigatorsl-6 have analyzed the concentration gradients present in diffusion couples in order to investigate phase equilibria and solu- bility limits. If diffusion is the rate-controlling process in establishing a concentration gradient, the compositions at the interfaces of the intermediate phases will represent the equilibrium values expected from the phase diagram at the temperature at which diffusion has taken place. No published information is available at this time on diffusion in the uranium-niobium system. A number of investigators7-" have contributed information to the construction of the uranium-niobium phase diagram from other than diffusion techniques. There is good agreement on the high uranium side of the phase diagram, but the high niobium side of the miscibility gap still remains somewhat in doubt. The phase diagram as determined by B. A. Rogers, et al.7 is shown in Fig. 1. The present work was aimed at obtaining fundamental information about the solubility limits of the miscibility gap and diffusion in the uranium-niobium system. A Kirkendall effect, which might be expected on the basis of the rather large difference in melting points between uranium (1132°C) and niobium (2415" C), was also investigated. The concentration gradients were measured by an electron microbeam probe technique, similar to that used by Castaing,l2 Adda and philibert,13, l4 and Macres.4

Jan 1, 1961

By G. St. J. Perrot, S. P. Kinney

Consumers of metallurgical coke are agreed that the quality of their fuel plays an important part in the performance of the furnace. Less unanimous agreement is evident when the properties of a desirable coke are discussed or when consideration is made of suitable testing methods by which the worth of a coke for metallurgical purposes may be determined quantitatively. Much has been written of the importance of combustibility as a factor in determining the performance of coke in the blast furnace and it is generally believed that cokes vary widely in this respect. The usual operating data of the furnace afford little evidence as to the combustibility of the fuel. As a part of a general investigation of the properties of metallurgical coke, the Bureau of Mines has explored the hearth combustion zone in a number of blast furnaces by means of water-cooled gas sampling tubes driven into the hearth through the tuyeres. The attempt has been made to determine the difference in combustibility of cokes varying widely in physical properties. Data have also been obtained in an experimental combustion furnace at the Bureau laboratories in Pittsburgh. This paper gives the results of experiments, made at eleven blast furnaces, in which the composition of the gases was determined at various points in the hearth in the plane of the tuyeres. Further work is in progress in which the zone above the tuyeres will be explored. Factors Affecting Coke Combustibility Brassertl has defined combustibility as the rate of progression of combustion, or, in other words, the speed at which the carbon molecules

Jan 1, 1923

By S. P. Kinney, G. St. J. Perrot

Consumers of metallurgical coke are agreed that the quality of their fuel plays an important part in the performance of the furnace. Less unanimous agreement is evident when the properties of a desirable coke are discussed or when consideration is made of suitable testing methods by which the worth of a coke for metallurgical purposes may be determined quantitatively. Much has been written of the importance of combustibility as a factor in determining the performance of coke in the blast furnace and it is generally believed that cokes vary widely in this respect. The usual operating data of the furnace afford little evidence as to the combustibility of the fuel. As a part of a general investigation of the properties of metallurgical coke, the Bureau of Mines has explored the hearth combustion zone in a number of blast furnaces by means of water-cooled gas sampling tubes driven into the hearth through the tuyeres. The attempt has been made to determine the difference in combustibility of cokes varying widely in physical properties. Data have also been obtained in an experimental combustion furnace at the Bureau laboratories in Pittsburgh. This paper gives the results of experiments, made at eleven blast furnaces, in which the composition of the gases was determined at various points in the hearth in the plane of the tuyeres. Further work is in progress in which the zone above the tuyeres will be explored. Factors Affecting Coke Combustibility Brassertl has defined combustibility as the rate of progression of combustion, or, in other words, the speed at which the carbon molecules

Jan 1, 1923

By J. O. Edstrom, G. Bitsianes

Parabolic rate constants were determined for the formation of wiistite by the solid state reaction between magnetite and iron. The reaction was diffusion controlled and inert marker studies indicated that the mass transport through the wiistite layer was accomplished by means of iron migration. Relationships between rate constants and self-diffusivities are discussed. The transport capacity for iron through dense wustite layers was found to be sufficient to carry on reduction, even in gaseous reduction processes. REDUCTION of iron oxides has been the subject of many investigations. Most of the work, however, has been done on rather crude material and there have been difficulties in correlating the data on a quantitative basis. The reverse process of the oxidation of iron has been studied more thoroughly and usually by starting from the pure metal. As a result, the mechanisms of oxidation are now fairly well known.It has generally been found that the oxidation of metals follows the so-called parabolic 1aw;Q hat is, when the oxides are formed as dense layers, their thicknesses are proportional to the square root of the reaction time. This parabolic law follows directly from Fick's first law of diffusion The flux, J, is defined as the quantity of diffusing substance passing per unit time through unit area of a plane at right angles to the direction of diffusion. This flux is proportional to the concentration gradient of the diffusing substance, and the factor D, known as the diffusion coefficient, is introduced as the proportionality factor with dimensions of (length)'/time. If the flux is measured as the increase of thickness of the oxide layer (Ax) per unit time (t) and the assumption is made that the concentrations of the reactants at the phase boundaries of the layer are independent of time, Eq. 1 reduces to Integration of this expression yields the parabolic function ax = k . t. [31 The product of the diffusion coefficient and the concentration difference across the oxide layer is included in the constant k. When iron is exposed to a highly oxidizing atmosphere, the oxide phases are formed normally in a topochemical fashion, i.e., the interfaces between the phases maintain parallel positions to the original surface of the specimen. Above 570°C, the phases are orientated usually in the order of iron, wiistite, magnetite, and hematite, a condition in conformance with the requirements of the Fe-0 system. Below 570°C, the wiistite phase is unstable and has not been found as a normal constituent in the oxidation products of iron. There is a strong probability that continuous layers of the solid oxides are formed as the specific volumes of the phases increase in direct order from iron to hematite.' , ' Regarding mass transport through dense solid oxide layers, Wagner' has postulated that diffusion in oxides generally may be interpreted as migration processes of ions and electrons. There must be normally a concentration gradient across the growing oxide layer for diffusion to occur. This condition requires that there be deviations from the ideal stoi-chiometric composition of the oxide and accordingly deviations from the strict order of an ideal lattice. Such "lattice defects" include interstitial ions, cation and anion vacancies, quasi-free electrons, and electron holes and are decisive for all migration processes.' Cations, anions, and electrons all may have some mobility in the oxides but the movement of one of the particles generally far exceeds that of the others. Previous work', 1,2,7 has shown that during the oxidation of iron the migration through the wiistite layer, and probably also the magnetite layer, is confined to the movement of iron ions. Migration through hematite, however, has been found to take place by oxide ion movement. These behaviors are in direct agreement with the type of vacancies present in the respective oxides. Reduction of Iron Oxides The gaseous reduction of iron oxides, like the oxidation of iron, takes place in a topochemical fashion at distinct interfaces between the appearing phases."-'" Porosities might be expected in these reaction products, since their specific volumes are less than that of the starting material. Frank and van Der Merwe" have shown, however, that it is theoretically possible for nonporous layers to form if the degree of misfit in specific volume is less than about 15 pct. These aspects on porosity formation

Jan 1, 1956

By G. J. Wilson

Review of difficulties experienced in drilling directional wells in the offshore Grand Isle Block 43 field showed most failures of drill pipe, drill collars and casing to have been associated with excessive dog-legs. Alleviation of difficulties was approached by synthesizing theoretical and practical concepts in a planned dog-leg control program. Preventive measures necessary to control dog-leg severity and corrective measures used to reduce unacceptable doglegs are discussed. When other measures fail, deliberative measures as outlined can be employed after the probable cumulative fatigue damage to be sustained by the drill pipe has been determined. Results of a program successful in virtually eliminating problems stemming from excessive dog-legs indicate that control of dog-leg severity in directional wells is feasible and will cause no decrease in the over-all drilling rate. INTRODUCTION Prompted by an increasing frequency of drill pipe, drill collar and casing failures, a study of 50 directional wells representing 592,000 ft of hole, including 444,000 ft of deviated hole, drilled in the offshore Grand Isle Block 43 field was conducted in early 1965. A number of drill pipe washouts and six keyseating problems were recorded and a detailed review was made of 16 failures which had required fishing effort in 10 of the 50 directional wells drilled prior to June, 1965. These problem wells are exemplified by Wells G and F for which pertinent data are shown in Figs. 1 and 2. Data pertaining to all of the 16 failures are summarized in Table 1. Inspection of these data shows most of the problems to have been associated with dog-legs in excess of theoretical limits suggested by Lubinski' and excessive dog-legging is indicated to have been concomitant with whipstocking in several of the problem wells. Results of the investigation agreed with those reported by Schenck2 who had concluded that problems could be expected when dog-leg severity exceeded limits proposed by Lubinski. Since Schenck had demonstrated the desirability and feasibility of drilling directional wells without excessive dog-legging, a dog-leg control program was established in June, 1965 for wells drilled in the Grand Isle Block 43 field. This paper reviews the methods by which theoretical and practical concepts were synthesized to develop a program of preventive, corrective and deliberative measures which virtually eliminated problems stemming from excessive dog-legs in directional wells. Dog-legs of a magnitude causing no damage are referred to as permissible +1CONTINENTAL OIL CO. HARVEY, LA.

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.', In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, ' The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B'O

Jan 1, 1969

By Robert C. Mackenzie

EXAMINATION by the differential thermal analysis technique of a large number of samples of soil and other clays from various parts of the world has demonstrated that the occurrence of cold-precipitated hydrated ferric oxide (the identification of which in soil clays has previously been reported5) is not confined to any limited locality; e.g., it has been found in varying amounts in clays from Britain, France, South Africa, and Mexico. The conditions necessary for its formation have not yet been elucidated in spite of the number of samples examined, and, since this mineral is so easily prepared in the laboratory, it has been considered that a study of its constitu¬tion and of the conditions under which it could be prepared might. lead to a better understanding of the factors involved. These experiments form the subject of this short paper, and while they do not supply a definite answer to the mode of formation of this mineral in nature, they may, it is hoped, add something to our knowledge in this direction. EXPERIMENTAL WORK Materials Employed The a-Fe2O3.H2O (goethite) and B-Fe2O3.H2O (Weiser and Milligan") were obtained from the Department of Geology, University of Aberdeen, and Rothamsted Experimental Station, respectively. The beta material had been prepared by the method described by Fernelius.1 y-Fe2O3.H2O (lepidocrocite) was prepared at the Macaulay Institute for Soil Research by the method of van Schuylenborgh.6 The method employed for preparation of the cold-precipitated hydrated ferric oxide* was as follows: 1: 1 NH4OH was added (moderately fast with rapid stirring) to a solution of 5 grams FeC13.6H2O in 250 ml distilled water at room temperature (ca. 15°C) until red litmus turned blue, and then 2 to 3 drops in excess. The resultant precipitate was filtered off on a Buchner funnel and washed free from Cl- with distilled water. Previous experiments having shown that drying over P2O5 at room temperature or drying at 105°C in the oven did not significantly affect the thermogram,5 samples were nor-

Jan 1, 1952

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By W. A. Backofen, N. E. Paton

DEFORMATION twinning contributes to the plasticity of titanium and has been reported on {10i2}, {1121},{11221}, {1123}, and {1124} planes.' Twinning on {1011} has also been reported in commercially pure titanium as a result of quenching from 1000', but no reports of such twins occurring as a result of deformation alone are known to the authors. In this study single crystals grown from iodide titanium were compressed parallel to the c axis over the temperature range 25 to 800°C. From it has come evidence that (10il) deformation twins are the most common type between 400" and 800°C. Crystals about 6 mm high with a rectangular cross section measuring about 3 by 4 mm were used in the tests. Chemical analyses showed them to contain 220 to 250 ppm 0 arid 10 to 15 ppm N. The long axes of the crystals were made parallel to the c axis while the sides were parallel to (i100) and (1120), as shown in Fig. 1. The crystals were compressed between polished alumina platens with no lubrication, in a vacuum of 2 x lom5 torr. Between 25' and 300°C the predominant twinning mode was (11221, which is to be expected for this stress state. There was an abrupt change at 400°C, however, and from that temperature up to 800°C twinning took place almost entirely on (10i1 ). Twin planes were determined by the two-surface rnethd. Measurement of the crystal orientation within several (10i1) twins by means of polarized-light4 and transmission electron microscopy showed that the lattice reorientations were the same as those previously reported for the (10i l ) twinning in magnesium.' This reorientation is consistent with The calculated (10il ) twinning shear for titanium is 0.10, while that measured from surface offsets on a (1150) face, which is parallel to the shear direction, was about 0.15. Slip within the twins, or in the matrix adjacent to the twins, probably accounts for the larger measurement. Slip in both locations was judged to have occurred from observations on foils in the electron microscope.

Jan 1, 1970

By Fred E. Wright

In a recent paper1 a detailed discussion is given of the possibilities of using polarized light in the examination of opaque substances. The factors underlying the problem are there treated from the viewpoint of the electromagnetic theory of light and the presentation is necessarily mathematical in form. The practical methods resulting from the discussion are, however, relatively simple and promise to be of value in the determination of certain ores and metals when studied in reflected light under the microscope. The results of the theoretical investigation referred to may be summarized by stating that in general the optical constants, such as refractive indices and absorption indices, cannot be satisfactorily ascertained on small, random, polished sections; that the use of polarized light enables the observer ordinarily to determine whether the crystal plate is iso-tropic or anisotropic, and also to ascertain the degree of anisotropism; that for this purpose methods based either on the contrast in intensity between the two reflected components of non-polarized light, or on the amount of rotation of the plane of polarization, on reflection, of vertically incident, plane-polarized light, may be employed; that methods based on the phase difference between the two reflected components are in general of little value because of the small differences in phase which ordinarily result for a relatively large change in birefringence or biabsorption. The measurement of the optical properties of transparent minerals, even in minute irregular grains, is a simple task with modern petrographic microscope methods and is accomplished by petrologists as part of their ordinary routine work. But the determination of the optical constants of opaque substances is difficult and is rarely attempted; all observations are necessarily made in reflected light and are restricted commonly to the determination of color, of hardness, of the character of crystallization, and of the behavior of the mineral or metal plate toward reagents and abrasives. With practice, the observer becomes expert in recognizing details of this kind and determines with a high degree of certainty the different

Jan 1, 1920

By John V. W. Reynders

Our entry into the World War suddenly brought home to us in a startling way the vital importance of manganese. Since the war, much has been written and said upon the subject of manganese and a great deal of time and money have been spent in attempts to find an adequate substitute for this metal in the manufacture of steel; none has been found. It is true that ways are known by which it is possible to make small amounts of good steel without manganese, but taking into consideration the diminishing quality of iron ores and fuels as well as the increasing exaction of specifications for finished products, it may safely be assumed that, high-grade manganese ore will be more and more a necessity in the production of steel as time goes on. Taking world resources as a whole it may be well to point out that the problem of obtaining needed supplies of manganese from a strictly commercial viewpoint is now less serious than it was before the war. Formerly it was feared that world resources of high-grade manganese ore might be exhausted in a relatively short time, but, largely as a result of the stress laid upon the importance of manganese during the war, the world's available supply of high-grade manganese ore has been greatly augmented by new discoveries and fuller development of previously known deposits. Sources of Production Russia alone, of countries producing the major part of the world's stee1, has within its geographical boundaries sufficient manganese to supply its needs. The domestic production of England is inadequate and English requirements for high-grade manganese are supplied principally from India. France also draws largely upon India, as it depends upon foreign sources of supply except with respect to a small tonnage of silico-manga-nese and silico-spiegel produced in the Hautes-Pyrénées. Germany and the United States likewise depend upon foreign sources of high-grade ore, though each possesses comparatively large reserves of ferruginous manganese ore and manganiferous iron ore. At present the world demand for high-grade manganese ore is met with ease by the production of Russia, India, Gold Coast and Brazil.

Jan 1, 1927

By G. C. Weaver, G. T. Harley

BEDS or lenses of potash and magnesium salts are found in a thick salt section (Salado) overlain by Rustler Red Beds in several members of which water is present and from one of which the refinery process water used by International is obtained. Most of the holes drilled are less than 1000 ft. deep, but some wildcat holes have exceeded 3000 ft. Cable or rotary tools are used to drill down to the salt. When samples of water are desired the cable rig is used, but when this is not necessary, and where caving material is present, the rotary rig has an advantage. The rotary rig has a further advantage in that only one machine is required to drill and core the entire hole, whereas the cable rig must be moved off to make way for the core drill. Casing is placed in the upper section of the hole as required to shut off water, and a 5 3/16-in. string is set in the top of the salt before coring starts. With the rotary rig drilling is often carried to the salt with no casing, as drilling mud seals off caving ground and water-bearing strata, and a string of 4-in, line pipe or 4-in. flush-joint casing is landed on top of salt. Several types of gasoline-powered core rigs have been used in the field and all recover a 2 1/2-in. core. More recently the Sullivan Model 37 rotary rig has been tried, and a Sullivan Model N has been adapted to use a rotary bit in the upper section. Core is recovered in 20 ft. sections with a double-tube core barrel, and the bit used is a bottom-discharge type set with diamonds. The drilling fluid must be a saturated brine to prevent solution and etching of the minerals present. Blowouts are apt to occur from nitrogen gas trapped under the several polyhalite beds, and some have been strong enough to blow the tools out of the hole. Core recovery is practically 100per cent. All holes are plugged after drilling, with cement through the salt section and opposite each water horizon, and mud through the remainder of the hole. Cores are carefully logged and preserved, and in sections containing potash and magnesium minerals they are quartered and analyzed. The correlation of ore beds between drill holes is briefly described.

Jan 1, 1946

By M. J. Duggin

Structural similarities between the E, X, and iron carbides are illustrated. Experimental evidence regarding phase transformations occurring during ternpering reactions in finely divided carbides, thin-film carbides, and carbides which occur in steels is considered and possible mechanisms for the E — x and x — 9 transformations proposed. HOFER1 has shown that within the appropriate temperature ranges carbon monoxide will react with finely divided a iron to form either iron carbide or x iron carbide. He has shown that at an elevated temperature the E iron carbide will transform to the x iron carbide (Hagg carbide) which, upon further elevation of temperature, will transform to 9 iron carbide (cementite). Jack,2,3 using X-ray diffraction methods, has observed that during the tempering reactions occurring in steel the E iron carbide formed in the first stage of tempering passes into two-dimensional platelets of 0 iron carbide during the second stage of tempering. The three-dimensional form of the 0 carbide is formed during the third stage of tempering. Jack suggested2 that the two-dimensional platelets of 0 carbide could be related to the faulted x iron carbide. Okada and Arata4 investigated a Swedish steel containing 1.05 wt pct C and approximately 1.0 wt pct Mn using permeability measurements at low field strength. A Curie point of 360°C was observed in the quenched steel, which indicated the presence of E iron carbide. On tempering at 400°C the specimen developed a Curie point at 230°C, indicating the presence of x iron carbide, and on tempering at 700°C the specimen developed a Curie point at 190°C which was assigned to 0 iron carbide. The carbides were extracted electro-lytically and the use of X-ray diffraction techniques4r5 indicated the carbide with a Curie point of 230°C to be x iron carbide. The Curie points of the carbides are 10 to 22°C lower than the accepted values which is probably due to the presence of manganese in the carbides, since it has often been observed (e.g., Ref, 6) that a partial substitution of manganese for iron in cementite will lower the Curie point of this carbide. Hofer' summarizes additional evidence of the tempering reactions in steel in which E iron carbide, formed during the first stage of tempering, transforms to x iron carbide during the second stage of tempering. During the third stage of tempering, the x carbide disappears as the 0 carbide is formed. By carburizing thin iron films in a CO gas stream, ~a~akura' has been able to produce the E, X, and 0 iron carbides. He found that below 250°C the E iron carbide was formed; between 250" and 350°C the x iron carbide was formed and above 350°C the 0 iron carbide was formed. He has shown that the E iron carbide transforms to form x iron carbide at 380" to 400°C and that the x ir°n carbide transforms to form the 0 iron carbide at approximately 550" C; both of these phase transformations are irreversible. Hofer' presents a review of evidence to show that the sequence of reactions occurring during tempering processes subsequent to the formation of E iron carbide formed by the direct carburization of finely divided a iron is the same as the sequence of reactions which occur during the tempering processes subsequent to the formation of E iron carbide in steel during the first stage of tempering. It is evident from Nagakura's work that identical tempering reactions are found in thin films of iron which have been carburized to form iron carbide. The purpose of this paper is to discuss the structural similarities between the E, X, and 0 carbides and to suggest a possible mechanism by which regions of the E carbide, formed during the first stage of tempering, may transform to the x carbide during the second stage of tempering. For the finely divided or thin film carbides a mechanism will be proposed for the transformation of the x carbide to the 0 carbide during the third stage of tempering, although it will be suggested that there is evidence that such a transformation may not occur in steels. STRUCTURAL DATA OF THE E, X, AND 0 IRON CARBIDES € Iron Carbide. It is evident from X-ray diffractions and electron diffraction', investigations that the metal atoms in the E iron carbide form an hcp structure with lattice constants ah = 2.752A, ch = 4.3534, using electron diffraction, reports the lattice paramet$rs of the superlattice cell to be a = 4.767A, c = 4.354, c/a = 0.9134. He finds that the carbon atoms occupy the octahedral voids in the metal atom structure so as to form a hexagonal stacking sequence with its basal plane parallel to that of the metal atoms. Considerable long-range disorder occurs in the positioning of the carbon atoms, however, which is in agreement with the possible range of composition Fe2C-Fe3C discussed by Hofer.' Barton and ale" have made X-ray diffraction measurements on a sample of E iron carbide extracted from a catalyst in an organic process. Although there were few reflections recorded on the obtained X-ray powder diffraction pattern, they have proposed that the structure could belong to one of the three possible space groups p3m1, P63/mmc, or Pbcn if one assumed the composition to be Fe2C. Nagakura, using electron diffraction data, suggests a space group of P 6322 for a specimen of c iron carbide of apparent composition Fez.&. x Iron Carbide. The x iron carbide has been studied by Duggin and Hofer" and by Jack and wild,' who

Jan 1, 1969

By Joseph Pogue

THE prices of crude petroleum and its derivatives have shown an upward trend from 1915 to 1920, and a downward trend from 1920 to 1923, see Table 1. Over the former period, oil prices were dominated by the rapidly increasing demands and inflation incident to the war and its aftermath, while over the latter period oil prices were influenced at the outset by deflation and then by the conditions of overproduction that have characterized the past three years. The purpose of this paper is to analyze the broader features of the more recent price movements in the petroleum industry and to relate these features to basic economic conditions in the industry.

Jan 3, 1924

By W. B. Gogarty

With flow of non-Newtonian fluids in porous media, effective viscosities are needed for use in the Darcy equation. These viscosities depend on the rock parameters and flowing conditions. In this investigation, rheological and flow results were correlated to develop an expression for calculating effective viscosities. Surfactant-stabilized dispersions of water in hydrocarbon were used with consolidated sandstone cores of different permeabilities. The average shear rate in a core was related to the permeability and porosity of the core and the frontal velocity through the core. By using the correlation obtained for determining effective viscosity, experimental and theoretical values were compared for each fluid system by determining average and maximum errors. For the fluid system showing the largest average error, the correlation fit 38 experimental points with an average and maximum percentage error of 4.3 and 14.8, respectively. For the fluid system showing the least error, average and maximum percentage errors of 1.8 and 4.3, respectively, were calculated using 29 experimental points. INTRODUCTION Use of non-Newtonian fluids in the petroleum industry is not new. Fluids of this type have been used for many years as fracturing agents and drilling muds. Recently, attention has focused on the use of high molecular weight polymer solutions for secondary recovery. Results have been reported on studies relating to the flow behavior of polymer solutions in porous media.1-4 Each study gives the viscosity in the Darcy equation as a function of the rheological properties of the fluid, the characteristics of the porous medium and the pressure gradient. The functional forms of the reported expressions differ somewhat in each study. The first three studies used unconsolidated porous media while the fourth used a single consolidated core. Because of the limited information available on the flow of non-Newtonian fluids in porous media, further investigation was undertaken in this area. We selected non-Newtonian fluids that did not contain high molecular weight polymers in order to minimize core plugging. The over-all objective was to gain a better understanding of the flow behavior of non-Newtonian fluids in consolidated porous media. Specifically, our goal was to determine the relationship between the average shear rate in a core and the frontal velocity. Because of this goal, it was necessary to determine the effect of permeability on the shear rate-frontal velocity relationship. We wanted to replace the viscosity in the Darcy equation with an expression relating to the average shear rate in the core and the rheological properties of the non-Newtonian fluid. THEORY For a time-independent, non-Newtonian fluid, the apparent viscosity is a function of the shear rate. This relationship is given by µ = F(v')...........(1) With Eq. 1, a single value of shear rate determines the apparent viscosity at that shear rate. With flow in porous media, a spectrum of shear rates occurs at any average throughput. An average shear rate v' can be used to represent the spectrum of shear rates that exists within the core. By using v' and the rheological data given by Eq. 1, an effective viscosity is determined for the flowing fluid. If v' is the correct average, µe becomes the appropriate viscosity for use in the Darcy equation. Under these conditions, flow rate-pressure drop relationships can be determined for non-Newtonian fluids. HOW the correct average shear rate might be related to the frontal velocity through the core and the characteristics of the porous media will now be considered. Later, the experimental data are presented that indicate the validity of these

By Irving Cadoff, Jack Medoff

THE linear thermal expansions of oriented single crystals of zinc were measured in the range from 20" to 416°C using a Leitz HTV optical lever differential dilatometer. The single crystals, supplied by Dr. J. J. Gilman, General Electric Research Laboratory, Schenectady, N.Y., were prepared from 99.999 pct-purity zinc, and were in the form of rods approximately 2 in. long by 0.15 in. in diameter having the following orientations: x = 1.5, 12, 20, 30, 37.5, 49, 60, 73, and 82 deg where x is the angle between the specimen axis and the (0001) plane of the crystal. From the family of expansion vs temperature curves, the instantaneous expansion coefficients were calculated at 100°C intervals, and Fig. 1 shows a plot of these derived coefficients for each orientation. Coefficients were obtained from the raw data using the chord-slope method. The curves in Fig. 1 indicate a positive temperature coefficient for low x, a negative temperature coefficient for high X, and an expansion coefficient invariant with temperature, amounting to about 43 x 106, for a crystal orientation of approximately 52 deg. From the available data, it is possible to arrive at the values for the axial thermal-expansion coef- ficients a, and a, by extrapolating the curve of the expansion coefficient vs orientation to zero and 90 deg orientations. More precise values for a, and a, are obtained if the instantaneous coefficients are plotted against the square of the cosine of the orientation angle, as shown in Fig. 2. The extrapolated terminal points of the best straight line through the data points of such a plot define the axial coefficients at that temperature. The theoretical justification for the linearity of this curve comes from inspection of a rearranged form of the general anisotropic equation for expansion: ax=a, + (a, -a,)cosZx [1I in which a, is the expansion coefficient in the "c" or [0001] direction and a, the expansion coefficient in the "a" or [ll50] direction. From Fig. 2, the axial coefficients at 100°C, for example, were found to be a, = 13.9 x 10'6 and a, = 62.4 x 10"6 per "C. In the same way, the coefficients were determined for 20", 200°, 300°, and 400°C. This data is summarized in Fig. 3. It is of interest to observe the common intersection of the curves in Fig. 3, which seems to bear out the earlier observation, from Fig. 1, of a

Jan 1, 1964

By Tadeusz Cyrul

Results of a large scale compression test in situ are the subject of discussion. A cube of coal having an edge length of 1.5 meters was subjected to uniaxial compression tests in situ. At the same time both load and deformation were controlled. Deformations were measured on 60 short measurement bases, each 23 cm in length. The bases were uniformly distributed on the side surface of the cube, forming five horizontal rows and twelve columns on the development of the surface. Readings were taken from each gauge for each level of loading which was increased step by step. Due to heterogeneity of the rock, readings showed scatter. Scattered data were approximated by a plane, using the least squares method for each row separately and for the entire population of bases. Orientation of the planes are analyzed. The geometrical measure of the bending moment is introduced. It shows that the magnitude of the bending moment and the bending plane differed from row to row, thus implying that the cube was not only bent but twisted as well. This complex behaviour of the coal cube is apparently caused by its heterogeneity and vertical anisotropy. The results constitute a contribution to the verification of existing design criteria on the stability of mining pillars.

Jan 1, 1984

By C. S. Barrett

THE crystal imperfections known as faults in stacking (stacking disorder) are of importance to both fundamental and applied science and are receiving increasing attention. On the theoretical side there have been recent advances in the analysis of diffraction patterns in terms of stacking faults, and on the experimental side it has been found that certain metals develop a faulted structure on cooling through a phase transformation. Beyond this, little is known of what may be called the physical and mechanical metallurgy of faulting, although there has been no lack of discussion and conjecture as to the presence of faults in metals and the effect of faults on mechanical properties and microstructures. In the close-packed metals the nature of faults can be described very simply. Face-centered cubic (FCC) crystals consist of close-packed layers of atoms, (111) planes, stacked above each other in a definite manner. If one layer is designated as the A layer, the next must be a B or a C layer; that is, every atom of the second layer lies not above the atoms of the A layer, but nestles in the hollows between these, using the hollows designated as the B positions, or the equivalent hollows designated as C. If the sequence of layers is ABCABC...., so that layers three spacings apart are directly over each other, the crystal is FCC; if CBACBA ... it is an FCC crystal that is a twin of the former; if ABAB........or BCBC..it is hexagonal close-packed (HCP). A fault is a break in the sequence, such as ABCABABC .. . which has the effect of inserting an HCP lamella into an FCC crystal. Regularly spaced faults spaced two layers apart would convert an FCC crystal entirely to HCP, or an HCP to FCC. A fault in an FCC crystal is also equivalent to creating an FCC twin of minimum thickness; in fact, the entire crystal would be converted to its twin if faults were introduced regularly. (In HCP crystals, however, twinning does not occur on the basal plane and a fault on this plane is not identical with a thin twin). Faults are one of the possible causes for annealing twins,' for the strain markings that are brought out by etching deformed metal,'," for the altered X ray reflecting power of metal at slip bands that is revealed in X ray reflection micrographs,' for the extinction of Kikuchi lines in electron diffraction patterns, and for the hardening of latent slip planes.' Since other explanations of these effects are also available," there has been no direct proof of faults from deformation; yet it has appeared likely that they would occur. Faults resulting from phase transformations in metals, however, have been clearly revealed by diffraction in cobalt" and lithium. It is to be expected that the faulting tendency is greatest

Jan 1, 1951

By C. V. Millikan

When a flowing oil well is being drilled in with cable tools, it is difficult to determine when an additional streak of pay sand is drilled. By placing a gas meter on the gas-release line from the oil and gas separator, any increase in volume of gas that comes with oil production is recorded. In addition to the better knowledge of sand conditions, these data are a valuable aid in determining the size and depth of shots, plugging off water, and estimating ultimate production. The meter also gives a record of operation while the well is drilling in; and if allowed to remain on the well after completion will give information that may lead to a more efficient recovery of the oil from the sand. A VERTICAL cross section of any oil sand will show great variation in porosity and oil content. In some sands, the entire thickness contains oil, the variation being only the degree of porosity or oil content, but more often the pay streaks are distinctly separated by shells or barren streaks. These pay strata vary in number and may be thin or thick. The total thickness of the sand may be several tens of feet while the part containing oil may be only 1 or 2 ft. thick. The amount of production is not proportional to the thickness of the sand but rather the thickness of the pay streaks. If the total thickness of the sand or the amount that can be drilled is small, or if the initial production is small, the depth at which each stratum of pay is encountered can be determined sufficiently accurately for all present economic purposes. However, when drilling through sand of considerable thickness, giving large initial production, especially where conditions necessitate that the production go through the same gas trap with that from one or more wells already producing, it is difficult to determine the depth at which the pay strata are encountered even accurately enough to guide the placing of shots, and small pay streaks are apt not to be recognized at all.

Jan 9, 1925