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By F. J. Norton

THE object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760° C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove.

Jan 1, 1932

By F. J. Norton

THE object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely, remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760° C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and sub-sequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove..

Jan 1, 1932

By James K. Hallenburg

INTRODUCTION The delayed fission neutron, or DFN technique for uranium ore body analysis uses the first down-hole method for detecting uranium in place quantitatively. This technique detects the presence of and measures the amount of uranium in the formation. DFN TECHNIQUE DESCRIPTION The DFN technique depends upon inducing a fission reaction in the formation uranium with neutrons, resulting in an anomalous and quantitative return of neutrons from the uranium. Since there are no free, natural neutrons in formation, a good, low noise assessment may be made. There are several methods available for determining uranium quantity in situ. The method used by Century uses an electrical source of neutrons. This is a linear accelerator which bombards a tritium target with high velocity deuterium ions. The resulting reaction emits high energy neutrons which diffuse into the surrounding formation. They lose most of their energy until they come to thermal equilibrium with the formation. Upon encountering a fissile material, such as uranium, these thermal neutrons will react with the material. These reactions produce additional neutrons, the number of which is a function of the number of original neutrons and the amount of fissile material exposed. The particular source used, the linear accelerator, has several distinct advantages over other types of sources: 1. It can be turned off. Thus, it does not constitute a radioactive hazard when it is not in use. 2. It can be gated on in short bursts (6 to 8 microseconds). This results in measurements free of a high background of primary neutrons. 3. The output can be controlled. Thus, the neutron output can be made the same in a number of tools, easily and automatically. There are several interesting reactions which take place during the lifetime of the neutrons around the source. During the slowing down or moderating process the neutron can react with several elements. One of these is oxygen 17. This results in a background level of neutrons in any of the measurements which must be accounted for in any interpretation technique. These elements are usually uninteresting economically. The high energy neutrons will also react with uranium 238. However, the proportions of uranium 235 and 238 are nearly constant. Therefore, this reaction aids detection of uranium mineral and need not be seperated out. Upon reaching thermal energy the neutrons will react with any fissile material, uranium 235, uranium 234, and thorium 232. At present, we do not have good techniques for seperating out the reaction products of uranium 234 and thorium 232. However, uranium 234 is a small (.0055%) percentage of the uranium mineral and thorium 232 is usually not present in sedimentary deposits. When the uranium 235 reacts with thermal neutrons it breaks into two or more fragments and some neutrons. This occurs within a few microseconds after the primary neutrons have moderated and is the prompt reaction. One system uses this; the PFN or prompt fission neutron technique. We don't use this method because the neutron population is low and, therefore, the signal is small and difficult to work with, accurately. Within a few microseconds to several seconds the fission fragments also decay with the emmission of additional neutrons. Now, with a long time period available and a large neutron population we gate off the generator and measure the delayed fission neutrons after a waiting period. These neutrons can be a measure of the amount of uranium present around the probe. Thermal neutrons are detected with the DFN technique instead of capture gamma rays to avoid some of the returns from other elements than uranium. LOGGING TECHNIQUE The exact logging technique will depend, to some extent, upon the purpose of the measurement. However, the general technique is to first run the standard logs. These will include: 1. The gamma ray log for initial evaluation of the mineral body and for determining the position of the borehole within the mineral body, 2. The resistance or resistivity log for determining the formation quality, lithology, and porosity. 3. The S. P. curve for estimating the redox state and shale content, and measuring formation water salinity, 4. The hole deviation for locating the position, depth, and thickness of the mineral (and other formations), and 5. The neutron porosity curve. The neutron porosity curve is most important to the interpretation of the DFN readings. The neutrons from this tool are affected in the same way by bore hole and formation fluids as the DFN neutrons are. Therefore, we can use this curve to determine effect of the oxygen 17 in the water. Of course, this curve can be used to determine formation porosity. It can also be used to calculate formation density.

Jan 1, 1979

By M. E. Wadsworth, A. S. Peck

Infrared spectra disclose that oleic acid will not adsorb on the surface of pure beryl unless the mineral is first activated with HF. The adsorption of oleic acid on HF activated beryl is attributed to the hydrogen bonding of oleic acid monomers to F-surface bridging sites. These sites are formed as a result of the reaction of HF with chemisorbed water or surface hydroxyl. Characteristic infrared spectra of physically adsorbed oleic acid are correlated with flotation at different pH at temperatures of 25°C and 75°C for colloidal and -60-mesh particles. The usual mode of occurrence of the beryllium mineral beryl, Be3A12Si6O18, is in granite pegmatites as pale green, white, or yellow crystals. A dark green gem variety, emerald, may be found in the wall rock of pegmatite veins or in mica schist. The most important beryl deposits in the United States are in the Black Hills District of South Dakota, and several mountain ranges of central and west-central Utah contain potential commercial sources of this mineral. Several papers have been published concerning the flotation of beryl with different conditioning reagents. Kennedy and O'Meara1 reported on the essential use of HF in the flotation of beryl from different ores. The use of calcium hypochlorite to separate HF activated beryl from feldspar after flotation with an amine collector was made by Runke.2 A report on the activation of beryl with different cations using sodium oleate collector was presented by Viswa-nathan and co-workers.3 Flotation of beryl with sulfonate collector and different activating salts was employed by Fuerstenau and Bhappu.4 The role of the surface charge or zeta potential in the flotation of beryl with different collectors and salts was also extensively investigated.5"7 Previous infrared investigations by the authors8 disclosed that the orthosilicate beryllium mineral, phenacite, reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. Thus, chemisorption is the effective mode of adsorption in the phenacite-oleate acid flotation system. In contrast, neither chemisorption or physical adsorption of oleic acid occur on the surface of pure beryl as evidenced in this study. Efforts were subsequently made to determine the mechanism of activation and collector adsorption for HF pretreated beryl. EXPERIMENTAL PROCEDURES Large, white, terminated crystals of beryl were obtained from Madagascar through Ward's Co., Monterey, Calif. The crystals were broken into -60-mesh fragments in a porcelain mortar. Part of this prepared material was ground to a powder with a Fisher Grinder using an agate mortar and pestle. The powder was transferred to a graduated cylinder and mixed with 500 ml of distilled water. After 5 min, the colloidal suspension was separated from the settled particles by decantation and used as a stock for infrared test determinations. Adsorption tests were performed by first transferring 20 ml of colloidal suspension to 50 ml glass centrifuge tubes. The solids were then centrifuged out and the liquid was discarded. Then, the solids were pretreated with one molar HC1 or one molar HF. After 15 min, the solids were again centrifuged out. The mineral solids were washed free of residual acid by repeated centrifuging and water washing operations. Then, 20 ml of distilled water was added to the solids, and the resultant suspension was used for test purposes. In the preparation of mineral for flotation tests, 1.5 g of -60-mesh beryl was deslimed by removing the colloidal fraction by three successive water washes and decantations. Then, the coarse particles were pretreated with either one molar HCl or one molar HF for 15 min. The mineral was next washed free of acid with distilled water, and 20 ml of distilled water was added to the beryl prior to collector conditioning. The conditioning of mineral with collector was performed in 50 ml centrifuge tubes to which either NaOH or HC1 was added for pH modification. One drop (6.0 mg) of U.S.P. reagent grade oleic acid or 2 ml of 0.01 molar sodium oleate was added to the pulp and stirred at about 1500 rpm for 3 min at a

Jan 1, 1968

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By Dwight H. Seely, Louis R. Records

A process for low-temperature dehydration of natural gas utilizing Joule-Thomson effect in expansion through a throttling orifice has been tested in a full-scale field installation. The results of these tests are presented in the form of performance curves from which the process may be easily evaluated. The effect of separation temperature on condensate recovery from the process is also shown. INTRODUCTION The transportation of natural gas from producing well to the consumer has always encountered the problem of hydrate prevention. This problem has become increasingly important in the past ten years due to the rapid increase in produced gas volumes, production pressures, transportation pressures and distance from producing wells to consumer. Natural gas, as normally produced from gas or gas-condensate wells, is saturated with water vapor at well-head conditions of temuerature and pressure. The solution of the hydrate problem require; but one basic process — dehydration of the gas to a water content which will result in a water dew-point below the minimum temperature to be encountered from the producing well to the point of consumption. Much of the recent development of gas and gas-condensate reserves in the Gulf Coast Area has been in locations which are accessible only by water. High well-head pressures, pipeline construction and maintenance costs and the desirability of final central gas-condensate separation facilities have stimulated the development of dehydration equipment which can be installed at each well and which will permit hydrate-free transportation of both gas and condensate in the same line to central facilities. There are four types of natural gas dehydration processes now used: 1. Adsorptive processes. 2. Absorptive processes. 3. Chemical reaction processes. 4. Refrigeration processes. The first three of these processes are indirect in that they require use of adsorbents, absorbents or reactive chemicals. These materials require regeneration and part of the total gas stream is consumed in the regenerative process. Indirect processes have a wide range of flexibility as defined by allowable operating pressure and temperature, but most are not easily adapted to automatic operation. The refrigeration process described in this paper was designed for installation at the producing well-head. It requires no regenerative cycle and with normal well-head temperatures no external source of heat. The flexibility of this process is limited only by the pressure drop which may be allowed between well-head and transportation line. THEORY There are three basic physical concepts involved in the low temperature dehydration process. These are: 1. Formation of hydrocarbon hydrates. 2. Joule-Thompson effect resulting from the expansion of gaseous mixtures through a throttling orifice. 3. The equilibrium composition characteristics of water vapor and gaseous hydrocarbon mixture.. The chemical composition and physical structure of hydrate; have been described by several investigators.3,4,5,10 Specific conditions of temperature, pressure and composition as well as the requirements for turbulence and presence of free water necessary for hydrate formation have been described by Katz.6 Natural gas hydrates, as they are found in plugged gas pipe lines, have the appearance of packed snow. The mass of these hydrates has low continuous porosity and permeability. Joule-Thomson effect. or the reduction in temperature which occurs when natural gas is throttled throusll a restrictive orifice, is the basic phenomenon which permits efficient use of refrigeration for the purpose of dehydrating natural gas. Joule-Thomson coefficients for gafeous mixture; of methane with ethane and with butane have been reported by Buder.-I~olzer, Sage and Lacey.2 Brown1 predicted temperature drops for pressure drops from enthalpy-entropy calculations. Aside from this work there were no fundamental data found which would be applicable to natural gas mixtures of varying spe-

Jan 1, 1951

By Hugh H. Waesche

Of all the military services, the Signal Corps is the most concerned with piezoelectric minerals because of its function as a supply service to the strategic and tactical military forces. Consequently this paper is written from the point of view of one associated with that organization. The Signal Corps is responsible for the research, development, and supply of communications, radar, and components to the using services of the Department of the Army and to some extent the Other branches of the National Defense Department. Their work therefore includes the study of the sources* characteristics, and application of quartz and other piezoelectric materials. These materials have become a vital consideration in strategic planning and are essential for efficient tactical operation by all the Armed Forces. The Signal Corps at the beginning of world War 11 Was respon-sible for both Army Ground and Air Force electronic equipment. Since that time this Army service organization has probably done more in the development of frequency control devices using piezoelectric materials than any other group. The U.S. Department of the Interior, Bureau of Mines, Minerals yearbook of 1945, shows that during the four war years, 1942 through 1945, 9,598,-410 Ib of quartz crystal were imported for all uses and of this total, 5,168,000 lb were consumed to produce 78,320,-000 crystal units for electronic application. Other government records confirm these data which conclusively show that approximately 53 pct of the crystalline quartz imported was consumed in the production of electronically applied quartz crystal units. It may be assumed that some effort was made to maintain a stockpile over demands for all purposes. and this would mean that the actual percentage of quartz used electronically was considerably over the 53 pct figure. These data only emphasize that electronic application of crystalline quartz was the greatest requirement, and per- haps the actual value in this application to national defense is many times greater in importance than is apparent on first inspection. Current electronic research and development programs of the Armed Forces are planned around the fundamental use of piezoelectric minerals for frequency control and this at present, at least, means quartz. Definition and Early Development The word piezoelectricity is formed from combination of the Greek word "piezein". meaning "to press," and "electricity." It is that property shown by numerous crystalline substances whereby electrical charges of equal and opposite value are produced on certain surfaces when the crystal is subjected to mechanical stress. It appears to be intimately associated with the better known property, pyro-electricity and in fact, the two may be manifestations of the same phenomeuon. This property was discovered by Pierre and Jacques Curie in quartz, tourmaline, and other minerals in 1880 while studying the symmetry of crystals. The converse effect, that is, mechanical strain in the crystal when placed in an electrical field, was predicted by the French physicist, G. Lippman, in 1881, and verified by the Curies almost immediately. As has been the case with many discoveries of similar character in the basic sciences, not much attention was paid to this property for man)- years except as an entertaining curiosity. Between 1890 and 1892 a series of papers was published by W. voigt in which the theoretical physical properties were put into mathematical form. The first practical application of piezoelectricity occurred during World War I when professor P. Langevin of France used quartz mosaics to produce underwater sound waves. The same mosaics were used to pick up the sound reflections from submerged objects which were in turn, amplified by electronic means and used to determine the distances to such objects. This device was intended for use as a submarine detector but development was not completed in time for war service although it was used later for determining ocean depths. About the same time, A. M. Nicholson, of Bell Telephone Laboratories, developed microphones and phonograph pickups using Rochelle salt crystals. A major step in the application of piezoelectric quartz came in 1921, when professor W. G. Cady, of wesleyan university, showed that a radio oscillator could be controlled by a quartz crystal; from that date, this use of quartz has increased steadily, reaching its peak in world war 11 as is shown by the figures previously given. Essentially all American electronic equipment for communication, navigation, and radar, utilized quartz crystals for the exacting frequency control required. Crystalline Minerals with piezoelectric Properties QUARTZ Hundreds of piezoelectric crystalline materials are known, most of which are water soluble. Of these, quartz appears to be without a peer for electronic frequency control. Unfortunately, the quartz must be of superior quality. It must be free of mechanical flaws, essen-tially optically clear, free of both Brazil and Dauphiné twinning and must be, for average uses, over 100 g in weight. Because of these stringent requirements, raw quartz of the quality desired is of rare occurrence. In addition to quartz, several other naturally occurring crystalline materials are known to have the piezoelectric property and could perhaps be substituted for quartz in some applications. These

Jan 1, 1950

By Joseph T. Roy

MINING revival during the last few years has brought about a considerable increase in the number of gold and silver determinations made, noticeable in all branches of the industry but especially so in the business of a custom smelter. At East Helena, solely a custom smelter the assay department found that the four assay furnaces available were inadequate to handle the increased amount of work. These furnaces were of a standard design, having duplex muffles, one superimposed on the other; each muffle was 12 1/2 in. wide, 18 1/4 in. long and 6 in. high, and could handle 72 cupels or 20 fusions. Since the heat varied considerably between the upper and lower muffles, cupellations were not ruin in both at the same time. To speed up assaying, E. A. Meale, chief chemist, had the happy idea of enlarging a muffle furnace, originally designed by the Montana Power Co., so that one muffle would acconmmodate at least as many determinations as the duplex muffles. An order was given to the Denver Fire Clay Co. for a Carbofrax muffle of the size required and the local engineering department enlarged the furnace to accommodate the muffle. Details of the

Jan 1, 1938

By B. C. Raynes

IN the early part of 1952, under the auspices of the U. S. Atomic Energy Commission, Horizons Inc. undertook an investigation dealing with the preparation of high purity thorium metal in order to develop an economically competitive production process for this metal based on a recovery of the metal by a fused salt electrolysis, since a survey of the literature of thorium chemistry indicated that electrolytic methods had not received much attention, despite the consideration that electrochemical production methods often offer attractive commercial potentialities. Thorium metal has been prepared by methods which fall into four general categories: 1) reduction of halides or double halides; 2) reduction of the oxide; 3) thermal decomposition of halides; and 4) electrolytic methods. Some of the important results obtained by various investigators since about 1900 in recorded attempts to prepare pure thorium metal are summarized in Table I. A bibliography of pertinent literature is included in this paper. Thorium is strongly electropositive and possesses a great affinity for oxygen and nitrogen. As a result the prospects for the production of high purity thorium from aqueous media or oxygen bearing compounds are remote. The most promising and profitable area of investigation for production of thorium metal lies in fused salt electrolysis. Thorium has been produced previously by this technique from halide salts in fused alkali chloride eutectic mixtures. Until recently, however, the lack of known large uses for thorium has inhibited the investigation of these methods. The basic problem in an investigation into fused salt production methods for thorium is to develop a suitable fused salt system for the economic preparation of thorium. The first portion of the work in these laboratories was a small scale investigation of the electrolysis of potassium thorium fluoride, KThF5, under a variety of conditions. High purity thorium was prepared in this manner, but the process did not appear to offer the simplest and most attractive continuous commercial operation. The work reported here relates to an all-chloride system employing thorium chloride as the cell feed. ThCL4 was produced as an anhydrous material stabilized in molten sodium chloride. This product, further diluted in NaCl, was subjected to electrolysis. The electrolytic process has been studied in cells capable of holding up to 50 lb total salt charge. Ductile, pure thorium metal has been reproducibly obtained in this operation. Considerable experimentation was carried out in the preparation of ThCL as a cell feed free from moisture, oxides, and other impurities. Thorium was cathodically deposited as a coarsely crystalline powder interspersed with residual bath salts. Aqueous procedures for separating and recovering the metal were developed. The thorium metal powder obtained has been evaluated with respect to its hardness, chemical purity, and certain other physical properties. Preparation of ThC1,—Thorium chloride, and the chlorides of some other metals (aluminum, beryllium, tantalum, zirconium, etc.) cannot be obtained from aqueous solution by direct heating and evaporation. Evaporation and heating of a solution of thorium chloride yields a hydrated salt or partially hydrated salt, and finally Tho,. Anhydrous thorium chloride is obtained by forming a hydrated ammonium chloride complex salt in acidified water solution, dehydrating this compound, and finally decomposing the double salt and subliming the ammonium chloride component. Various methods for the preparation of anhydrous thorium chloride, in accordance with this concept, were investigated as indicated in Table I1 from hydrated thorium chloride (ThCl, . 3H2O), and from thorium oxycarbonate (ThOCO,). In the method found most satisfactory for this work, thorium oxycarbonate was dissolved in an excess of concentrated HC1 to give a clear yellow solution. At least 2 mol NH,Cl were added to the solution per mol of contained thorium. Ammonium thorium chloride hydrate was crystallized from solution by cooling and saturation with HC1. The resultant complex, (NH,Cl),ThCl;xH,O, was dehydrated by evaporation at 130° to 150°C and thoroughly dried at about 250°C. The dried ammanium thorium chloride was then mixed with sodium chloride in proportions to form NaThCL or to produce a ThCL4-NaCl mixture with a given thorium content. The ammonium chloride was sublimed off at temperatures above 500°C in an inert atmosphere furnace to give an anhydrous chloride source electrolyte, essentially free of Tho, and of NKC1.

Jan 1, 1958

By Carrol M. Beeson

Reasons are given for using a Boyle's-law porosimeter in conducting core analysis for either routine or research purposes. Among other things, it is pointed out that such a porosimeter permits the measurement of all basic properties on the same sample, thereby eliminating the sources of error inherent in the use of adjacent samples. References are made to investigations of gas adsorption on various porous materials, to show that the use of helium in Boyle's-law porosimeters reduces to negligible proportions the error due to the adsorption or desorption of the operating gas. Two Boyle's-law instruments are described. which permit accurate and rapid measurements of porosity. Schematic sketches and explanation:; are included, along with derivations of equations required in performing precise determinations. Summaries of data obtained during calibration are tabulated and analyses of the data are resented as indications of the precision and accuracy of each device. Comparisons are also shown for measurements made with each of the instruments on the same test pieces and cores. INTRODUCTION An accurate porosimeter, operating on the principle of Boyle's law. is of considerable value in the analysis of cores for either routine or research purposes. This is due primarily to the fact that the measurement of porosity with such an instrument leaves the sample free of contamination by any liquid. When used in conjunction with an extraction apparatus' for determining oil and water saturations, a Boyle's-law porosimeter permits the measurement of all basic properties on the same sample. This eliminates the sources of error inherent in the use of adjacent samples, or the necessity of determining porosity after all other properties have been obtained. Large errors may result from combining measurements made on adjacent samples in order to obtain a single property. This type of error is definitely involved when oil and water are measured with one sample, and the pore vo1ume is measured with an adjacent one. Furthermore, the source of error would be present to some extent, even if the analyst could choose the samples so they were truly adjacent from a geological standpoint. The use of adjacent samples in routine core analysis also necessarily decreases the probability of correlating core properties. For example, the chance of correlating the "irreducible" interstitial-water saturation with permeability, is bound to be greatly reduced by measuring these properties on "adjacent" samples. For research purposes, amplification is scarcely required concerning the greater flexibility of a method for measuring porosity which leaves the core free of contamination by any liquid. Even under those circumstances which require that the core be saturated with a liquid, a previous measurement of porosity with a gas is useful in determining the degree of saturation that has been attained in the process. Furthermore, for comparable accuracy, porosity usually may be determined more rapidly with a gas than with a liquid. This advantage of the Boyle's-law instrument is most outstanding when the determination time is compared with that required in obtaining porosity by evacuation of the core followed by saturation with a liquid of known density. Several porosimeters which operate on the principle of Boyle's law have been described2,3,4,5,6,7 in the literature. No comparison will be attempted between those instruments and the ones described herein. Before helium gas became readily available, Boyle's-law porosimeters were subject to an appreciable error due to the adsorption of the operating gas on the surface of the core solids. There is considerable direct and indirect evidence in the literature to support the contention that the adsorption of helium on porous solids is negligible at room temperature. In discussing the use of Boyle's-law porosimeters, Washburn and Bunting2 stated that "for most ceramic bodies dry air is a satisfactory gas, but hydrogen will be required in some instances. Helium could, of course, be employed for all types of porous materials at room temperatures or above." Howard and Hulett8 obtained evidence that the adsorption of helium was negligible at room temperatures, even on activated carbon ; for the density measured with this gas was unaffected by changes in pressure or by changes in temperature from 25 °C to 75 °C. For oil-well cores, Taliaferro, Johnson, and Dewees" obtained lower porosities with helium than with air, but apparently did not study helium adsorption. From the work of these investigators, it follows that the use of helium in Boyle's-law porosimeters reduces the error due to gas adsorption to negligible proportions. This makes it possible to construct instruments which permit the determination of porosity with (1) a high degree of accuracy, (2) with great rapidity, and (3) without contamination. THE KOBE POROSIMETER The fundamental design of the Kobe Porosimeter was developed by Kobe, Inc., which firm built about 12 of the instruments during 1936 and 1937. Since that time, seven or eight more have been constructed with their permission, making a total of about 20 that have been put into operation.

Jan 1, 1950

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at '750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By J Price, M. R. Geer, H. F. Yancey

COAL mine operators recognize coal as an abrasive material, because the wear of drilling, cutting, and conveying equipment is reflected as a cost item for replacement of parts. Similarly, industrial consumers of coal experience abrasive wear on all coal-handling equipment. Operators of pulverized fuel plants are doubtless most keenly aware of the abrasiveness of coal, because under the high contact pressures developed between coal and metal in pulverizers, abrasive wear is increased many fold. Moreover, experience in operating pulverized fuel plants has demonstrated that some coals are much more abrasive than others. Hardgrove' stated that maintenance costs entailed by the wear of grinding elements is often a more important variable than the cost of the power required to pulverize different coals. Craig2 also reports that one coal may cause pulverizer parts to wear several times faster than another. It is apparent, therefore, that those concerned with pulverizing coal could profitably employ a method for estimating the abrasiveness of different coals, just as they utilize standard tests for thermal value, grindability, and ash-fusion temperature to assist in selecting the most suitable and economical coal to use in a particular plant. The objective of this investigation was to develop a test procedure that would be suitable for general use in estimating the abrasiveness of coals. However, few, if any, of the standard tests now used for evaluating the properties of coal are the product of a single investigation or the result of a single investigator's efforts. Rather, in each case, a testing procedure was devised by one investigator, used by others on a wider variety of coals, and finally refined completely as the result of the joint efforts of a number of interested people. Thus, the test procedure for estimating abrasiveness developed in the course of this work may not be refined sufficiently in its present form for general use, but it may serve as the starting point from which an acceptable test procedure can be developed. The method has been used thus far on only about a dozen coals, and there has been no opportunity to attempt a correlation between experimental results and actual plant experience. Only wider use of the procedure by other investigators and correlation with plant experience can determine to what extent the method will have to be modified to render it suitable for general application. Test Method Although the literature contains no record of an attempt to devise a method for estimating the abrasiveness of coal that could be used industrially, several investigators have tested properties of coal that are closely related to its abrasiveness. The abrasiveness of a material generally is considered to be related to its hardness, and hardness tests for coal have been employed by Heywood,' O'Neill," and Mathes. Also, the resistance of coal to abrasion, a property that presumably is related to the abrasiveness of coal, was measured by Heywooda and by Simek, Pulkrabek, and Coufalik.2 11 these investigators tested only individual pieces of coal. Since coal is a heterogeneous material having components of varying properties, tests of this type can yield results having little more than academic interest. Only a test method that utilizes a representative sample of coal can give results that are useful industrially. The abrasion tests used for various other materials have been considered for adaptation to testing the abrasiveness of coal. The tests used for metals,7-9 paving and flooring,'" and rubber," cannot be used because coal is not sufficiently abrasive.~ The present experimental work was begun before World War II and was conducted by three research fellows"'" working under a joint agreement between the University of Washington and the Bureau of Mines. After a great deal of preliminary work with a variety of apparatus and materials, a test procedure was developed which consisted of rotating a test disk 2Yz in. diam in a steel mortar containing the coal sample. The shaft carrying the test disk at the lower end and a 100-lb load on the upper end was free to move vertically. The bed of coal in the mortar was kept fluid by low-pressure air admitted through a port near the bottom of the mortar. Measurable wear on an Armco iron disk could be obtained in this test procedure, but, despite extensive efforts to eliminate them, several major disadvantages remained in this test method. First, with most coals the amount of wear on the iron disk did not exceed a few milligrams. Second, a single type of disk was not applicable for all coals. A smooth iron disk gave satisfactory results with both bituminous and sub-bituminous coals, but hardly any wear with anthracite or coke. A disk having studs or projections gave more satisfactory abrasion losses with anthracite and coke and presented no operating difficulties with free-burning bituminous and sub-bituminous coals. It could not, however, be used with caking coals because these coals formed a

Jan 1, 1952

By Arthur M. Miller

FROM the time of its establishment in 1933, the Tennessee Valley Authority has been active in the field of phosphates. Under the T.V.A. Act it has a broad Congressional mandate to guide a unified development of the resources of the region for the long-range benefit of the people. As one phase of this function, it is directed to co-operate with farmers in the experimental large-scale use of improved fertilizers and development of better fertilizer practices. Following careful study, it was concluded that the objectives of this phase could best be attained by soil rebuilding through the use of phosphatic fertilizer and lime in an improved farm management sys- tem. This activity was launched through a program of test and demonstration on farms and simultaneous technical investigations to develop new and improved phosphatic fertilizers. Phosphorus has since become a keystone of the Authority's resource development and conservation program. Human effort is being conserved by phosphate utilization on the farm, and mineral conservation has been promoted by technical developments in phosphate mining and manufacturing operations.

Jan 1, 1944

By Philip D. Wilson

FEAST and famine-or, chronologically, famine and feast-have characterized the aluminum supply program during 1943. Fortunately for the war effort the famine phase is over and aluminum production is now in the happy position of being abundantly able to supply all the requirements of the armed services plus a monthly surplus which is building up a substantial stock pile as a reserve against any contingencies. But the present condition of oversupply cannot be attributed to the super-efficiency of the aluminum production program which was designed to take care of the over-all requirements of the war with little or no margin of safety. The present more than comfortable situation is due primarily to the fact that the armed services generally have not consumed anything approaching the amount of aluminum which their requirement estimates indicated.

Jan 1, 1944

By C. K. Leith

THE outstanding fact of the mineral world today, at home and abroad, is the surplus of current production, and particularly of capacity for production, over current requirements. This is not by Any means a new condition, but never before has it loomed up in such' menacing form. - Those of us who have devoted most of our professional efforts to the discovery and development of 'new mineral supplies now suddenly find ourselves with the job apparently accomplished, waiting for some one else to find an outlet for excess mineral production before we can further. The management of the industry is in much the same boat. The psjrcho16gy of the industry has been so grooved in the direction of acquisition of, minerals that at the present moment the mineral industry confronts the new problem of surplus in more or less of a daze.

Jan 1, 1931

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By F. C. Farnham

THERE has been very little, if any, uniformity in the reference datum used for magnetometer surveys. It has been the practice to choose a base station at which the magnetic field is assumed to be normal and call the difference in field strength between a given station and this base the anomaly at the given station. For small-scale surveys latitude and longitude corrections may or may not be applied, but for large-scale surveys such corrections usually are applied. The United States Coast and Geodetic Survey maps showing lines of equal magnetic intensity are commonly used to determine the normal latitude and longitude variation by scaling values from the map for given points and computing the change per mile north and the change per mile east. This method has been quite satisfactory for isolated surveys, but when two surveys originating at different base stations were extended until they joined, difficulty arose, not only because of discrepancies between base-station values, but also because of differences between the latitude and longitude correction factors used for the separate surveys. It is the purpose of this paper to describe a reference datum for magnetometer surveys which, it is believed, will eliminate most of the difficulty arising from this source. In order to be satisfactory, a general datum for magnetometer sur-veys should be as close as possible to the observed field and still he based on some assumed distribution of magnet poles, in order that the "normal" value of any component of the field for any given point may be computed to as many significant figures as desired. Such a field has been com-puted, and a comparison of the intensity of its vertical component with the average vertical intensity for the United States as shown by the U.S.C.G.S. map of lines of equal intensity for 1935 is shown in Fig. 1.

Jan 1, 1939

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By A. H. Heim

A method and apparatus for measuring gas porosities of rocks are described. The apparatus can be assembled from commercially available components. In principle, measurements are made by volume substitution at constant pressure. The maximum error is not more than 0.3 porosity per cent. Typical results are given. INTRODUCTION Determining the porosity of rock samples is one of the most important and yet most varied types of measurement in core analysis. Among the many techniques devised are the so-called "gas porosity" methods. An old and well known example is the Washburn-Bunting method.' The U. S. Bureau of Mines2-' described and later improved the apparatus for a now widely used method generally known as the "Boyle's law" method. In the present form of the Washburn-Bunting method,' the volume of air in the pores of a rock sample at atmospheric pressure is extracted and then collected in a graduated burette at atmospheric pressure. The volume of air is read directly as the pore volume of the sample. The absolute error in reading the collected volume of gas is independent of the total volume; thus, the relative error is larger when the volume is small, as it is for rocks of low porosity. In addition, the sample after measurement contains mercury, which limits its use for other analyses. The Bureau of Mines (or Boyle's law) method measures directly the solids volume of a sample from which the pore volume and porosity are derived, using a separate measurement of the bulk volume. Gas at a few atmospheres pressure is introduced into a sample chamber of known volume containing the rock sample. The pressure is accurately measured. Following, the gas is expanded into a burette at 1 atm, and the gas volume is read directly. From the initial pressure p, and the final pressure p2 and volume v,, the initial gas volume v1 is calculated using Boyle's law; that is, p1v1 = p2v2. Volume v, minus the volume of the empty sample chamber is the solids volume of the sample. The accuracy of the method is limited, unless corrections are made, by deviations of the gas from the "ideal" gas-law behavior assumed in the simple form of Boyle's law. The purpose of the present paper is to describe a method for measuring the gas porosity of a rock which avoids many of these difficulties. Gas volumes are measured directly with the same accuracy as the bulk volumes. Pressures of at least an order of magnitude larger than those of previous methods are employed to insure rapid penetration of the gas into the sample. While special equipment may be built to apply the method, the porosimeter may be constructed as well from commercially available components. For simplicity, the apparatus described will be referred to as the "Constant-Pressure gas porosimeter". THE CONSTANT-PRESSURE METHOD Fig. 1 shows schematically the arrangement of components comprising the present Constant-Pressure porosimeter. Briefly, the method is one of volume substitution and may be considered a null measurement. Omitting (for the present) some of the operational details, the method of measurement consists of the following three steps. 1. After evacuation, the volume of the measuring system (a ballast chamber, a manifold, two gauges and their connections) up to the sample chamber is filled with gas to a high pressure (- 1,000 psi). A sample of the gas at this pressure is trapped in one side of a sensitive differential pressure gauge to serve as the reference pressure for subsequent steps. 2. The evacuated sample chamber containing the rock sample is opened to the measuring system. As the gas expands into the chamber, the resulting decrease in pressure unbalances the differential pressure gauge. 3. The pressure is restored by means of a mercury volumetric pump. The volume of mercury injected exactly equals the free or void volume of the sample chamber (volume of empty chamber minus the solids volume of the rock within). From the injected volume and the known empty chamber volume, the solids volume is obtained and the porosity calculated. The pressure and the volume occupied by the gas are the same before and after opening the sample chamber. Expansion and compression of the gas are incidental operations and do not enter into the calculation of porosity. By the pressure balancing or nulling, the free volume of the sample chamber is merely substituted by an equal and measured volume of mercury. Since the measurements are at constant pressure, there are no compressibility corrections necessary for the sample chamber.

By F. B. Plummer

PRODUCING operations abroad during 1940 were shrouded in the fog of war. Little, if any, concrete information is available, and the data that issue from the belligerent countries are too frequently distorted for military purposes, for the volume of supply of gasoline and fuel oil has become an important strategic secret. Despite this lack of information signs indicate the spread of a slow paralysis which is gripping producing operations in foreign countries. Only in the Caribbean area are developments proceeding normally and even there the destruction of the Western European market is being seriously felt. This creeping paralysis is being brought about partly by the serious shortage of materials so necessary for drilling and other producing operations such as steel, machinery, and the like-together with a scarcity of that prime munition of war-money. Markets too have been curtailed by the operation of exchange control as all exchange is needed to support war efforts. As a result, gasoline is tightly rationed in all belligerent countries. The growing casualties in shipping are fast restricting the water-borne trade in petroleum, but have had a local stimulating effect in some areas where the risk is less or where water-borne transport can be efficiently used as for instance Trinidad and Egypt. The type of product needed for war effort, particularly the great demand for aviation gasoline, has changed the schedules of .refinery operations. As a result of all these influences the world oil picture outside the United States- has vastly changed during the year.

Jan 1, 1941