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A remarkable industrial renaissance is underway in the People's Republic of China (PRC), says USBM's Dr. K. P. Wang in his recently released 96-page report on "The People's Republic of China-A New Industrial Power with a Strong Mineral Base." Dr. Wang's summary of the current mineral position of the PRC includes many insights into its future potential and trade possibilities with the West.

Jan 2, 1976

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. Introduction The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or Pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves is needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry Out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemica1 composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. The Problem At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1942

By B. A. Eaton, K. E. Brown, C. R. Knowles, D. E. Andrews, I. H. Silberberg

This paper presents the resitlts of an investigation of two-phase, gm-liquid flow in horizontal pipelines. Experimental data were taken in three field-size, horizontal pipelines, two of which were constructed for this purpose. The data were obtained using water, distillate and crude oil separately as the liquid phase, and natural gas as the second phase. Experimental pressure-length traverse, liquid holdup and flow-pattern data were collected for each set of flow rates. These data were used to develop three correlations that are presented herein. The liquid-holdup values correlated with various flow parameters without regard to the existing flow pattern. The same was true for the energy-loss factors. A new flow-pattern map is presented that appears to be quite reliable, but not required for the pressure-loss calculations. The liquid-holdup correlation and the energy-loss factor correlation are used in conjunction with a two-phase flow power balance, developed during this study, to predict the pressure losses that occur during gas-liquid flow in horizontal pipelines. A recommended calculational procedure is given, as well as a statistical analysis of the results. This procedure lends itself to computer application, since several small pressure decrements are needed to calculate a pressure-length traverse. The correlations are shown graphically, but may be curve fitted with existing curve-fitring computer programs. INTRODUCTION Due to the frequent occurrence of gas-liquid flow in pipelines and the desire to accurately calculate the pressure losses that occur in these lines, two-phase flow is of considerable interest to the petroleum, chemical and nuclear industries. In the petroleum industry, gas-liquid mixtures have been transported over relatively long distances in a common line due to the advent of centralized gathering and separation systems. Long two-phase flowlines are usually accompanied by large pressure drops which influence the design of the system. Gas-lift installations are designed on the basis of known tubing pressures at the wellheads. The horizontal flowline connecting the wellhead and the separator system must be correctly sized in order to minimize the horizontal flowline pressure losses and the wellhead tubing pressure. Practically all oilwell production design involves horizontal two-phase flow in pipeknes. All of the flow processes of oil and gas production must be studied simultaneously to insure good well design. Since the beginning of offshore oilfield development, long horizontal flowlines have been constructed. Because pressure losses greatly influence the performance of producing wells, a method is desired that can be used to predict such pressure losses and select optimum flowline size. Several types of gas-liquid flow exist, and many of these are discussed by Gouse The study of pressure gradients, fluid distributions and flow patterns that occur in horizontaI multiphase flow is made difficult by the great number of variables involved. The various flow regimes give rise to changing velocities of the fluid particles in all directions. These instabilities of the interface between the gas and liquid prohibit the determination of actual vector velocities of fluid particles in each phase. Also, it is practically impossible to arrive at correct sets of boundary conditions. Therefore, most investigators have concluded that a solution to the problem by the classical fluid dynamics approach, whereby the Navier-Stokes equationsM are formulated and solved, is far too complex. Other methods must be utilized to develop general correlations that will predict the behavior of gas-liquid horizontal flow systems. Multiphase flow studies have sought to develop a technique with which the pressure drop can be calculated. Pressure losses in two-phase, gas-liquid flow are quite different from those encountered in single-phase flow; in most cases an interface exists and the gas slips past the liquid. The interface may be smooth or have varying degrees of roughness, depending on the flow pattern. Therefore, a transfer of energy from the gaseous phase to the liquid phase may take place while energy is lost from the system through the wetting phase at the pipe wall. Such an energy transfer may be either in the form of heat exchange or of acceleration. Since each phase must flow through a smaller area than if it flowed alone, amazingly high pressure losses occur when compared to single-phase flow. Most investigators of horizontal two-phase flow phenomena have chosen to separate their experimental data into several groups of observed flow patterns or regimes.

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined in part for the sgstem Gd-Fe. Seven intermetallic compounds have been found at compositions corresponding to the following Gd-Fe ratios; 2:3, 1.2, 1:3, 2:7, 1:4, 1:5, and 2:17. The GdFe, com-pound has a congruent melting point above 18000C, whereas all of the remaining compounds melt incongruently, A eutectic exists at 13 wt pct Fe at a temperature of 860°C. ALTHOUGH an increasing amount of information is becoming available on the metallurgy of pure rare earth metals, relatively few studies have been made on alloy systems of the rare earths with the transition metals; iron, nickel, and cobalt. Even less data are extant on gadolinium alloys although it could be expected that such alloys might possess interesting structural and magnetic properties. In this paper, we report investigation of the gadolinium-iron alloy system. Studies on systems containing nickel and cobalt will be presented in subsequent papers. Previous data on gadolinium-iron compounds have been reported by Endter and Klemm1 and Jep-son and Duwez.2 Both reports agree on the existence of the GdFe2 phase, which crystallizes with the C-15type structure (face-centered cubic). This is in accord with results of the present work. EXPERIMENTAL The gadolinium metal used was prepared by met-allothermic reduction of high purity gadolinium fluoride. A typical analysis of the metal thus produced indicated the principal impurities to be oxygen, 0.24 pct, and tantalum, 0.2 pct. The iron metal used for alloying was a reagent grade material. Alloys were prepared by arc melting mixtures of the respective metals. Appropriate quantities of the two component metals were carefully weighed, blended and compacted. The compacts were then melted in an arc furnace consisting of a water-cooled copper hearth plate and a water-cooled tungsten-tipped counter electrode contained in a brass vacuum chamber. The furnace was evacuated to an absolute pressure of less than 1 with the leak rate established as being less than 20 per min. The furnace was then back-filled to a pressure of 25 mm of Hg, with a 75 pct He-25 pct Ar mixture. Arc melting at 25 v and 300 amp was maintained for about 30 to 60 sec until the entire visible area of the sample became molten, by which time surface tension had drawn the molten metal pool into a large bead. After allowing the furnace to cool, the alloy button was inverted and the melting process repeated. A series of melts was made covering entire composition ranges from 100 pct Gd to 100 pct Fe. All samples were examined metallographically in the as-melted condition. As the phase diagram became rationalized, and differential thermal analysis had given indications of temperature arrests, annealing was carried out in vacuo or in argon. Generally, compositions containing more than about 60 pct Gd were heat treated at 750°C and alloys containing less than this quantity of gadolinium were annealed at 1000°C. Prolonged annealing times were of the order of 100 to 200 hr. Metallographic examination was repeated on the annealed materials. Although little material loss was noted during alloy preparation, chemical analyses were made on all specimens prepared. The following standard, analytical techniques were used. Samples were dissolved in hydrochloric acid; insoluble material was filtered off, ignited and fused with potassium pyro-sulfate. The cold melt was leached with dilute acid and the solution thus obtained added to the main sample solution. Gadolinium was always determined gravimetri-callv as oxide from oxalate ignition. Iron was removed from an aliquot sample by electrolysis on a mercury cathode at approximately six volts. Gadolinium in the iron-free electrolyte was then precipitated as oxalate which was subsequently ignited to oxide. Iron was determined volumetrically in an aliquot solution by reduction with stannous chloride fol-

Jan 1, 1962

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. Introduction The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or Pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves is needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry Out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemica1 composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. The Problem At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1942

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman' reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser' reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,' values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,' on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.' When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

By E. S. Machlin, Morris Cohen

The martensite reaction in single crystals and polycrystals of 70 pct Fe-30 pct Ni alloys is shown to be autocatalytic in nature, producing bursts of transformation during cooling. The temperature of the first burst of transformation, called Mb, occurs below M, in these alloys. Experiments were devised to test the athermal embryo and strain embryo theories of martensite nucleation. The results indicate that internal strains, either within the virgin austenite or around existing martensitic plates, control the nucleation process in these alloys. Furthermore, the growth of martensitic plates is not limited by the attainment of an elastic balance with the austenitic matrix, but by the occurrence of plastic deformation at the martensite boundaries which interferes with the propagation mechanism. IN an investigation of the martensitic habit in single crystals of a 69 pct Fe-31 pct Ni alloy,' it was observed that about 25 pct of the austenite transformed during subatmospheric cooling within the time-interval of an audible click. This event proved quite spectacular: The shock wave sent out from the specimen freely suspended on a thread in the refrigerating liquid was occasionally sufficiently intense to shatter the Dewar container and to separate the toluene column in the immersed thermometer. The Present investigation was undertaken to determine- the kinetics and mechanism of this "burst" type of martensitic reaction. The analyses of the alloys studied are given in Table I. The composition of the single crystal specimens is designated by alloy A, while the polycrystal-line specimens were made of alloys B and C as noted in the text. The single crystals were prepared in a vacuum furnace, using a modified Bridgman technique. Most of these crystals were homogenized by holding for 24 hr at about 1300°C just after solidification. However, it may be emphasized here that the degree of homogenization was not a controlling factor in the subsequent experiments, inasmuch as specimens having different degrees of homogenization yielded the same results. All of the single crystals were fully austenitic as slowly cooled to room temperature. An illustration of the burst phenomenon is given in Fig. 1, which shows oscillograms of electrical resistivity and temperature vs. time during the continuous quenching of 1/16 in. wire specimens (alloy B) in a dry ice and acetone bath at —77°C. There are at least two observable bursts in this case, as indicated by the sharp decreases of resistance accompanying the sudden formation of substantial quantities of martensite. The thermal arrest during the quench probably corresponds to the larger burst. Usually the bursts are followed by more or less progressive transformation during continuous cooling. It will also be noted that the resistance continues to decrease after the specimen has reached the bath temperature. This isothermal change denotes the formation of martensite at constant temperature, and will be the subject of another paper. Examination of fiducial scratches on the surface of a transformed single crystal has shown2 that the scratches in adjoining nonparallel martensitic plates are usually bent in opposite directions, as though one plate forms in such a way as to relieve the matrix stresses set up by the adjacent plate. This, together with some of the results described in ref. 1, Table I. Compositions of Alloys Studied, in Percent Alloy Ni C N Mn Si P S Cr A 31±0.3 0.048 0.027 0.003 0.56 0.007 0.002 B 29.5±0.2 0.036 0.02 0.19 0.09 0.008 0.006 C 19.99 0.52 0.37 0.47 0.010 0.015 0.04 led to the tentative concept that a cooperative action exists which provides the impetus for much of the transformation that appears during the burst. The following series of experiments were performed in order to test this idea. Cooperative Nature of the Burst Two adjacent disks, Va in. thick x % in. diam, were cut from a single austenite crystal of alloy A using a jeweler's saw. One of the disks was then cut into 15 parts. Then 12 of the latter pieces and the second disk were austenitized (stress relieved) at 600°C for 30 min and water quenched to room temperature. The temperatures at which the first burst of transformation appeared were determined for

Jan 1, 1952

By Wilfred Walker

With the advent of the New Global Tectonics a coherent pattern of geology is emerging. To the economic geologist this is of vital concern because the type of mineralization in particular environments is predictable. Developments in geological reasoning now take their place beside developments in geochemistry and geophysics. Much is known of the worldwide geography of the Alpine orogenic period because it is now ending its 200 million years of existence, starting with the Jurassic, and we can see the mid-ocean rises and the down flow zones, and between them the stable oceanic and continental platforms. The concepts of mantle cells, the spreading sea floor, and continental drift have gained general acceptance. The oceanographers have demonstrated the uprises like that in the mid-Atlantic. In this paper it is suggested that down flows in the oceans are marked by island arcs, like the West Indies; and down flows in the continents are marked by orogens like the American Cordillera. The number and position of mantle cells is controversial: a total of about 16 cells is suggested in this paper. Certain cells expand, and as they carry continents with them give rise to concepts of plate tectonics. Specific types of mineral deposits are associated with the uprises, oceanic and continental platforms, and down flows. The uprises are accompanied by the currently described Red Sea and Salton Sea deposits, the oceanic parts of the platform have the nodular deposits, and the continental platforms have the post-tectonic deposits. However, most economic metal deposits are associated with the down flow zones in which the stage of geosynclinal development controls the type of deposit: (1) In the initial development stage the simatic upper mantle may be tapped and give rise to the volcanogenic massive base metal sulfide deposits and to the ophiolite suite which characteristically carries nickel, chrome, and cupreous pyrite. (2) In the early geosynclinal stage sialic crust is driven down into the simatic magma of the upper mantle and basic to acidic differentiates give rise to stocks accompanied by skarn and hydrothermal deposits. (3) The intermediate stage of geosynclinal development gives rise to tin-tungsten, lithium, and beryllium deposits as the magma chamber rises above the level of the upper mantle and there is no simatic component. (4) The late stage is one of regenerated deposits. The porphyry deposits are not restricted to stages but only by the time of generation of acid magma. As the geosynclinal system dies, the mantle is again the source of magma, giving rise to gabbro and diabase dykes and sills: in this last, post-tectonic, continental platform environment are found the Mississippi Valley type lead-zinc deposits, the Blind River and Witwatersrand type of sedimentary uranium and gold deposits, and also Sudbury's nickel. The key relationship of major ore deposits generated by downflows is depicted herein on a framework of uprises, platforms, and downflows in the Alpine orogenic period. There is evidence for nine orogenic periods, of which the Alpine period is the latest, having taken place from 3500 million years ago to the present. Each period was characterized by its own worldwide mantle cell system and associated uprises, platforms, and down flows. The cycle of geosynclinal development, including corresponding cycles of mineralization, can be precisely defined in relation to each of these orogenic periods. The development of the Alpine orogenic period therefore can be used as a guide to the study of the earlier orogenic periods which comprise well known periods: Kenoran, Hudsonian, Grenville, and Paleozoic; and less well known: Konkian, Aulian, Belomorian, and Elsonian [(Table 1)]. Each name is used for the period as a whole, and not for the main orogenic event.

Jan 1, 1973

By James W. Shaffer

Aluminum is the most abundant metallic element and forms 8% of the earth's crust. Because of its chemical activity it does not occur in nature in a metallic form but principally in the silicates, feldspar, mica, shale, and clay. Bauxitic raw materials-bauxitic clay, aluminous laterite, and bauxite-develop from these aluminum silicate sources. Bauxite and aluminous laterite are naturally occurring mixtures of aluminum hydroxides and mineral impurities, and they are the major sources of aluminum. End Uses Bauxite is the basic ore of the aluminum industry. It is refined into aluminum hydroxide and calcined for feed stock to electrolytic smelters. Over 90% of the tonnage mined is refined and smelted into aluminum. The total tonnage consumed by other industries is small in comparison, but bauxite and alumina are important for the manufacture of refractories, ceramics, chemicals, abrasives, pharmaceuticals, catalysts, cements, dessicants, and flame retardants. Some aluminum-containing industrial products are made from clays and other materials but the majority originate from bauxite directly or from aluminum hydroxide and alumina refined from bauxite. Lateritic type bauxite is also used as building and decorative stone. Geology Mineralogy and Properties Bauxite is a mineral raw material composed principally of one or more aluminum hydroxide minerals and impurities of silica, iron oxide, titania, and other elements in minor or trace amounts. The important aluminum hydroxide minerals are gibbsite, boehmite, and diaspore. Bayerite, nordstrandite, and tucanite are naturally occurring aluminum hydroxides but are rare and not commercially important. Mixtures of gibbsite and boehmite are common, boehmite and diaspore less common, and gibbsite and diaspore rare. Gibbsite is aluminum trihydroxide. Boehmite and diaspore are aluminum oxide hydroxides and have essentially the same composition, but diaspore has a greater hardness and a more tightly bonded and denser atomic structure. Although not technically correct, the commercial terms trihydrate and monohydrate are frequently used to distinguish types of bauxite. If bauxite is all or nearly all gibbsite, it is referred to as a trihydrate ore; if boehmite or diaspore or a mixture of both are the dominant minerals, the bauxite is called a monohydrate ore. If substantial amounts of both gibbsite and boehmite are present, the bauxite is frequently referred to as a mixed ore. Properties of major bauxite minerals are shown in Table 1. Silica, iron oxides, and titania are major impurities always present in deposits of bauxitic raw materials.. Silica impurities usually occur as clay minerals, micaceous minerals, or quartz, but cristobalite and feldspar are found in some deposits. The most common clay minerals are kaolins; however, illites and chlorites are often found in small quantities. Varying proportions of aluminum, iron, and clay minerals make bauxite, aluminous laterite, ferruginous laterite, and bauxitic clay deposits gradational with each other. Hematite and goethite are the common iron mineral impurities in many bauxites. Magnetite and ilmenite occur in deposits derived from basic igneous rocks. Other iron minerals associated with bauxite are maghemite, pyrite, siderite, and marcasite. The titanium minerals found in bauxites are anatase, leucoxene, rutile, ilmenite, titaniferous

Jan 1, 1983

By Reginald S., Dean

The commercial availability of electrolytic manganese has greatly changed the position of manganese as a nonferrous alloying metal. Manganese metal commercially available up to about ten years ago was reduced with either silicon or aluminum and contained substantial amounts of the oxides of these metals and other impurities. Manganese was accordingly not available as an alloy base and its addition to copper-base and nickel-base alloys was generally limited to a manganese content of a few per cent. Several special alloys like manganin contained up to 12 pct of manganese.

Jan 1, 1953

By Paul A. Bailly

“For innovative leadership in bringing about a quantitative rationality to mineral exploration; for the impact his efforts and wide respect have made on national mineral policy issues; for his effective managerial role in major mineral discoveries; and for his lecture, ‘Managing for Ore Discoveries.’”

Jan 1, 1980

By H. D. Hodges, J. K. Godbey

In order to better understand the fracturing process, bottom-hole pressures were measured during a number of typical fracturing operations. A recently developed system was used that allows simultaneous surface recording of both the bottom-hole and wellhead pressures on the same chart. The results from six fracruring treatments are summarized on the basis of the pressure data obtained. Al-though no complete analysis is attempted, the value of accurate pressure measurements is emphasized. Important characteristics of the bottom-hole pressure record do not appear at the wellhead because of the damping effect of the fluid-filled column. In four of the six treatments described, the formations apparently fractured during the initial surge of pressure with only crude oil in the well. The properties of the fluids used during the treatments are given and the fluid friction losses are obtained directly from the pressure records. This technique is also shown to be adequate for determining when various fluids, used during the process, enter the formation. INTRODUCTION Hydraulic fracturing for the purpose of increasing well productivity is now accepted in many areas as a regular completion and workover practice. Numerous articles have appeared in the literature discussing the various techniques and theories of hydraulic fracturing'. In general, three basic types of formation fractures are recognized today. These are the horizontal fracture, the vertical fracture, and fractures along natural planes of weakness in the formation'. Any one or all three of these fracture types may be present in a fracturing operation. However, with only the wellhead pressure record as a guide, it is difficult at best to determine if the formation actually fractured, and is almost impossible to determine the type of fracture induced. These difficulties arise in part because the wellhead pressure record, especially when fracturing through tubing, does not accurately reflect the pressure variations occurring at the formation. Several factors contribute to this effect and preclude the possibility of using the wellhead pressure as a basis for accurately calculating the bottom-hole pressure. These factors are: 1. The compressibilities of the fluids which damp the pressure variations. 2. The changes in the densities of the fluids or apparent densities of the sand-laden fluids. 3. The flowing friction of the various fluids and mixtures, which is dependent on the flow rates and the condition of the tubing, casing, or wellbore. 4. The non-Newtonian characteristics of a sand-oil mixture and its dependence upon the fluid properties, the concentration of sand, and the mesh size used. 5. The unknown and variable temperatures throughout the fluid column. Because of these reasons it was determined that in order to obtain a more accurate knowledge of the nature of fracturing, the bottom-hole pressure must be measured along with the pressure at the surface during a fracturing treatment. Even with accurate pressure data, a reliable estimate of the nature of fracturing is still dependent upon knowledge of the tectonic conditions. However, the hydraulic pressure on the formation is basic to any approach to a complete analysis. In order to accomplish this objective a system was developed to record the wellhead and bottom-hole pressures simultaneously at the surface. By recording both pressures on a dual pen strip-chart recorder, it was possible to greatly expand the time scale so that rapid pressure variations would be faithfully recorded. By such simultaneous recording, time discrepancies inherent in separate records are eliminated, thus overcoming one of the most difficult problems associated with bottom-hole recording systems. This paper illustrates the results obtained by using this system during six typical fracturing operations. All of these tests were taken in wells that were treated through tubing. By a direct comparison of the wellhead and bottom-hole pressures, the importance of obtaining complete pressure information during a fracturing treatment is emphasized. THE INSTRUMENTATION AND PROCEDURES The bottom-hole pressure measuring instrument consisted of a pressure-sensing element, a telemetering section, and a lead-filled weight or sinker bar. The pressure-sensing element used was an isoelastic Amerada pressure-gauge element. By using an isoelastic element, no temperature compensation was necessary in the tests described, since the temperature was believed to be well below the maximum temperature limit of 270°F. The rotary output shaft of this helical Bourdon tube element was coupled to a precision miniature potentiometer. The rotation of the pressure-gauge shaft thus changed the resistance presented by the potentiometer

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By H. W. Russell, Paul D. MILLER

IT is known that austenitic chromium-nickel steels that have free carbide in the grain boundaries are subject to intergranular corrosion. It is difficult to detect such a susceptible condition in a fabricated article because present test methods require a sample section for examination and in most cases this is difficult to obtain. The question of the nature and prevention of intergranular corrosion in austenitic stainless steels have been ably discussed by Bain and co-workers1-3 and by other investigators.4-10 The present methods of study subject samples to corrosive conditions in such reagents as the Strauss solution, a. mixture of copper sulphate and sulphuric acid. Such tests usually require at least 72 hr. to run. Various methods of measuring the degree of sensitization have been employed, such as the measurement of electrical resistivity, magnetic measurements, measurement of the degree of cracking produced on bending over a mandrel, and microscopic studies. The detection of carbides at the grain boundaries by metallographic polishing and etching methods is tedious and requires a skilled operator. A recent report on such methods of carbide detection is given by the American Society for Testing Materials Subcommittee VI of Committee A-10 11 and by Arness.12 The present investigation was undertaken to develop a simple test procedure for detecting carbide precipitation or susceptibility to intergranular corrosion. The test is designed for use in the plant and for the testing of fabricated structures. Carbide precipitation, the factor leading to susceptibility to corrosion, is produced by heating the alloy in the temperature range 800° to 1600°F., as in welding, in improper annealing or in service where such temperatures are met. The connection between such precipitation and susceptibility to corrosion has been thoroughly discussed, as has been the use of stabilizing addition elements to prevent precipitation. EXPERIMENTAL METHOD A small area of the steel under test is subjected to an anodic treatment in a cell that can be clamped onto a sample or an actual structure. The cell and electrical circuit used are illustrated in Fig. I. The cell C is lead, joined to the steel plate D and insulated from it by a short piece of rubber tubing E. The cell is forced tightly against the steel plate by a spring or clamping device. The seal formed by the rubber against the steel plate is sufficient to retain the liquid bath inside the cell. The spot treated can be made any shape desired, depending on the shape of the rubber gasket. The cell illustrated polishes a circular spot about 3/8-in. diameter. The bath consists of 60 per cent (by weight) sulphuric acid to which is added 5 ml. per liter of Glycyrrhiza extract (U.S.P.). The cell requires about 2 to 2.5

Jan 1, 1941

By R. E. Cook

This paper presents results of a study to determine to what extent errors in estimated free gas saturation affect the results of static pressure calculations from build-up curves in two-phase systems. Use is made of the method of pressure build-up curve analysis developed by Miller, Dyes and Hutchinson1 , with modifications for two-phase flow advanced by Perrine2. Cornhined fluid compressibility of gas-oil mixtures is included, with special attention given to the discontinuity that occurs in fluid compressibility at the saturation pressure and its effect on static pressure calculations from build-up curves. The sensitivity of static pressure calculations to errors in gas saturation is considered over wide ranges of formation and fluid properties and reservoir pressure conditions. It is concluded from this study that for analyses of two-phase pressure build-up curves (I) the use of under-saturated crude compressibility data, even when producing GOR's are at or near solution values, will result in very significant negative errors in calculated static pressrrre, and (2) except for large values of buildup curve .slope and/or very low crude gravities, rather large errors in calculated gas saturation can he tolerated without .significant effect on calculated static pressures. The conc1usions arc qualified as referring only to the effects of gas saturation and excludc possible errors in the nuumerous other factors that enter into the ancllysis of pressure build-up curves. INTRODUCTION As part of the analysis of basic data for several major Eocene reservoirs in the Bolivar Coastal field (Western Venezuela), it was necessary to analyze a large number of pressure build-up curves for oil permeability and static reservoir pressure. From performance data it became apparent that gravity segregation is very active in these reservoirs. As a result of this performance it was recognized that the free gas saturation within the oil leg of the reservoirs would be small but would be subject to certain errors in calculation due to the inaccuracy of relative permeability data in the low gas saturation region. Since all of the various methods of build-up curve analysis were originally derived for sin- gle-phase, constant compressibility systems, and since the presence of a small but rather indeterminate gas saturation would greatly affect the reservoir fluid compressibility, a study was undertaken to investigate the effect of gas saturation on the results of two-phase pressure build-up analyses. TWO-PHASE BUILD-UP CURVE ANALYSIS The method of analysis used in this investigation is basically that originally developed by Miller, Dyes and Hutchinson1, with modifications for two-phase flow advanced by Perrine2. Miller, et al, showed that the original equation for single-phase permeability away from the well bore, held for two-phase flow except that the calculated permeability is the effective permeability to oil away from the wellbore. This finding was acknowledged by Per-rine, who also presented the equation for effective gas permeability* as Since Eqs. 1 and 2 contain no terms influenced by fluid compressibility, no distinct problem should develop in calculating permeability from two-phase build-up curves. In regard to the calculation of static reservoir pressure from build-up curves in single-phase systems, the modified Miller, et al, method as presented by Perrine is briefly as follows. 1. From build-up curve data, PVT data for the reservoir fluid and the well spacing and sand thickness, calculate the climensionless shut-in time corresponding to the highest value of actual shut-in time (t, hrs) on the straight-line portion of a semi-log build-up curve. Dimenrsionless shut-in time is related to actual shut-in time by the relation, t- 0.000264 kt 2. From a graph of dimension less shut-in time vs dimensionless pressure difference (Fig. 1 1 ) find the value of dimensionless pressure difference corresponding to the value of 7 calculated under (1) above. Dimen-

By Kenneth L. Clifford, Thomas G. White

Many changes have occurred in lead-zinc milling in the U.S. since the 1970 Lead and Zinc Symposium. New mills have been built, novel flowsheets devised, and the use of process control techniques is increasing. The Missouri concentrators produced in 1976 more lead and zinc concentrate than those in any other state. The Tennessee mills produced nearly as much zinc concentrate in 1976 as Missouri and with some very highly developed flowsheets. Progress in the Western U.S. is centered around new operations in Colorado and Utah. New mills in New York and Missouri incorporate many of the newer control concepts. Most of the older concentrators have undergone flowsheet changes to accomodate different ore types or because of the availability of new and better equipment.

Jan 1, 1977

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By COURTNEY DE KALB

IRON ore is the cause of the present trouble in Morocco. At least three nations are interested in the outcome and private syndicates have been active. The iron deposits are found in that mountainous northern coast line known as the Rif. This is an uplift that has been cut through, by the northward drainage, representing an ancient land surface. Erosion has produced .a fiordlike coast, which circum- stance has aided contraband' traffic to the tribes dominated by Abd-el-Krim, the chief of the clan of the Beni Urriaguel, near the center of 'the north coast, opposite Alhucemas. The iron deposits are extensive in the territory of the Beni Urriaguel. They were "located," if such a term is permissible, many years ago. The first arrangements, through direct contracts with the tribal chieftains, have been reinforced by compliance with the subsequent code under the Spanish protectorate in 1914. Under those terms, the location had to be made through the Arbitral Commission sitting in Paris. These locations, or "denouncements," were made by the I-louse of Mannesmann, of Hamburg.

Jan 1, 1925

By R. L. Stephenson

IN plants casting electric-furnace ingots and converting them immediately into blooms, billets, slabs, bars or forgings, the criterion of quality performance is the soundness of the semifinished or finished product. When rejections are necessary, it is not always obvious whether the defects were caused by an unsound ingot or by improper treatment during the heating and forming operations. To evaluate the effects of the numerous factors involved, it is necessary to accumulate a large number of detailed observations and to analyze and interpret these data properly. Even after a thorough investigation has been conducted, it is impossible, in some cases, to isolate the cause of the defect and say that it is definitely the result of an unsound condition in the ingot or mistreatment of the ingot during further processing. Two factors that are extremely difficult to evaluate are the chemical composition of the steel and time from finish pour to charge in the soaking pits or "track time," and it is necessary to evaluate their combined effects before many other factors can be studied. Plain carbon, fine-grained steel in the range of 0.18 to 0.23 pct carbon, is very susceptible to cracking and the longer the elapsed time between the pouring of the ingots and stripping for charging into the soaking pits, the higher the billet rejections for cracks are found to be. Below 0.15 pct carbon and above 0.30 pct the track time

Jan 1, 1947