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By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By E. C. Carris

THE loading of bituminous coal mechan¬ically was recognized about the year 1900, but during the following 28 years less than 5 per cent of the bituminous pro¬duction in the United States was loaded by mechanical means. During the past i6 years, however, the usage of some form of mechanical loader has had a very rapid and accelerated growth, until at present production of bituminous coal by mechanical means has reached an all¬time high of approximately 46 per cent, and is still increasing. This rapid growth in the use of the mechanical loader has been supplemented by an increase in mechanical cleaning. The importance of mechanical cleaning of coal was recognized many years before the mechanical loader was introduced, because of the impossibility of cleaning manually the sizes below 2 in., and the increasing competition from other fuels. Utilization of mechanical loaders without mechanical cleaning on the surface for at least one or more sizes is the exception, rather than the rule. One exception is a mine that employs caterpillar-mounted mobile loaders exclusively, and mines the entire seam without any selectivity, and yet loads and ships six grades of coal of the very highest quality without mechanical cleaning. Such a fortunate situation can exist only where mining conditions are ideal, where top and bottom are exceptional and there are no impurity partings, and where there is loader height. The conversion from hand loading to mechanical loading has definitely intro¬duced many problems in the preparation plant of yesterday and in the modern streamline plant as well. Many of these problems have been solved by good, sound, conscientious initiative on the part of the plant personnel, with minor expendi¬tures; the solution taking the pattern of rearranging and improving the equipment at hand. Other problems have caused, and are causing, considerable concern and difficulty. LARGE IMPURITIES The removal of large quantities of large impurities from the lump coal, and their handling and disposal, is definitely a troublesome and costly problem. The cost of manually removing the impurities from the picking table alone, based on the actual recovered lump coal, can reach a cost of 42 cents per ton or more. In the design of future plants it would be wise to give this phase of preparation considerably more time and thought, particularly if the seam of coal contains one or more heavy partings and the mining procedure is all seam. This same caution applies to seams that may not contain heavy partings but have poor and heavy draw-slate top, which falls with the coal during the mining cycle. One of the more recent of the modern preparation plants has answered this problem by installing a rock crusher under the picking table in such a manner that the impurities can be diverted by gravity directly to the crusher. This reduces the

Jan 1, 1946

By A. F. Bertuzzi, M. R. Tek, F. H. Poettmann

A method is presented for predicting pressure drop for two-phase fluid flow in horizontal pipes. A set of 267 experimental measurements randomly sampled from approximately 1,000 measurements from various literature sources was used. Pressure gradients calculated by the procedure developed and compared with the experimental values showed a bias of +0.82 per cent and a standard deviation of 20.8 per cent. The advantatges of this method over other available methods of predicting two-phase flow pressure drop are (a) its comparative simplicity of application, (b) its relative independence of flow patterns, (c) its accuracy, which on the basis of a statistical evaluation predicts pressure drop closer than other available methods, and, (d) its ability to satisfactorily correlate laboratory data from various sources while the correlations from these sources do not appear to agree with one another. The method has been reduced to a simplified graphical procedure, suitable for field use. A two-phase f factor is defined and correlated with parameters involving the flowing gas-liquid mass ratio, a Reynolds number for the gas phase, and a Reynolds number for the liquid phase. The choice of parameters allows the correlation to reduce to the usual f factor plot for the limiting conditions of (111 gas or all liquid. INTRODUCTION The mechanics and characteristics of two-phase flow systems have been of interest throughout the industry for some time. In numerous engineering installations such as pipe lines, chemical reactors, and heat exchangers, two-phase flow conditions are of every day occurrence. In oil production operations it has been desirable, in some cases, to consider transporting gas and oil together in a common pipe from oil field to process plant. The trend toward centrally located stock tank batteries in oil fields has resulted in longer gathering pipelines in which more than one fluid phase is flowing. The increase in the producing capacity of oil wells due to new production tech- niques has created the need for review and re-design of many surface gathering lines for properly handling the increased production. Optimum pipe size for the situations described above has become an important factor. The problem which is of interest here involves the ability to predict the relationship between pressure drop, fluid properties, fluid rates, pipe diameter, and pipe length. Although the literature1,5,10,13,18,19 contains various articles dealing with specific cases of the problem, Lock-hart and Martinelli17 proposed the most general solution. Their method has been later modified by Baker:1 Alves2 demonstrated that different flow patterns are possible for a flow mechanism defined by Martinelli such as gas turbulent, liquid turbulent. Baker explained deviations experienced with Martinelli's correlations on the basis that different flow patterns could exist for the same flow mechanism. Using Martinelli's method of correlatioil, Baker correlated data for each flow pattern for the turbulent-turbulent flow mechanism. Bergelin and Gazley6,7 presented a correlation for predicting gas phase

Jan 1, 1957

By R. W. Gurry

In the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and III0°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon conteDt of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched, The mean result of concordant ments-—taeats-is-^that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C .(i755°F.) and 1.89 per cent at III0°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutec-toid temperature (738°C. or I360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature II35°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. Experimental Procedure The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.' In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (I6°F.) but at a given location the temperature remained within +o.5°C. (o.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (I760°F.) and III0°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with toluene; this quickly produced on the

Jan 1, 1942

By J. B. Pullen

THE United Verde mine is in the north central part of Arizona, on the. north-easterly slope of the Black Hills, near the town of Jerome. Ore was first discovered in the district about 1875, and the first mining claims were located by M. A. Ruffner and associates in 1877. In 1888 the late Senator William A. Clark secured control of the property and under his ownership it developed into one of the country's most important copper producers. The property was sold to the Phelps Dodge Corporation in 1935, and since then has been under this Corporation's management. Except for shutdowns caused by general world-market conditions, production has been continuous from 189o to date. GEOLOGY The mineralized zone ranges in area from approximately 12 acres to less than 5 acres. All mineralization occurs in the pre-Cambrian intrusives. The first intrusion, according to geologic records, was the quartz porphyry, which later was intruded by augite diorite. Following the diorite intrusion through a series of intrusions of lesser magnitude, a pipelike mass of massive sulphide, quartz and rock was formed. The diorite forms the hanging wall of this mass, and the porphyry the footwall. Between the footwall and the sulphide a band of chlorite schist was formed, probably owing to metamorphic conditions. Commercial ore occurs along the contact of the schist and sulphide extending into the sulphide, sometimes entirely through the schist, and fingering out into the porphyry. The ore deposit was formed by replacement similar to deposits formed in limestone areas. Faulting and deformation occurred in pre-Cambrian times and again in the Tertiary period, removing approximately 2000 ft. from the top of the main United Verde ore body, forming the United Verde Extension ore body, the only other major ore body in the district. Major development work has shown that the sulphide mass extends to the 3300-ft. level, and diamond drilling below this level has indicated that the mass might extend below the 3700-ft. level, but in a diminished quantity. While many copper minerals exist in the mine, the chief commercial mineral is chalcopyrite. A plan and vertical section of the mineralized zone showing the principal geological features is shown in Figs. I and 2. GENERAL DESCRIPTION AND PHYSICAL CONDITION OF MINE After over 50 years of active production, ore still exists on almost every level of the mine. This condition is due to many causes -mine fires, which broke out as early as 1894, caused the abandonment of certain areas; subsidence and ground movements retarded the cleaning up of others. Furthermore, in the early days there was such an abundance of ore that when mining became difficult it was a simple matter to replace the production by going to a deeper level. Several attempts were made to recover the ore in the fire zone, both by glory-holing

Jan 1, 1941

By Hugh H. Waesche

High quality quartz crystals weighing more than 50 grams are required in several important industrial applications.30,31 Primarily, they are the basic raw material for precision, electronic, frequency control components; this includes oscillators and filters in both radio and telephone services. Quartz crystals are also necessary for optical lenses and prisms in special applications requiring high ultraviolet light-transmission as in spectrographs. Quartz wedges are regular components for petrographic microscopes. The application of crystalline quartz as a transducer* in ultrasonic devices has increased in recent years despite strong competition from barium titanate and magnetostrictive [f] devices. Some quartz is fabricated into delay lines for radar. Man has valued quartz for fabrication of art objects since the dawn of history. The art forms were and are painstakingly carved and polished to form intricate figurines, bowls, statuettes, and the well-known crystal balls. The largest known ball, made of perfect quartz from Burma, is now in the National Museum in Washington. It is 12 7/8 in. in diameter and weighs 106 lb 12 oz. Clear, pure quartz chips and small crystals not meeting the electronic-grade dimensional requirements are known by the Brazilian term lasca. They are used to produce fused quartz having wide application in laboratory equipment, as special glasses, for torsion suspension in scientific instruments, and as a source material for growing large artificial quartz crystals 18,35 Electronic applications far exceed all other uses in importance so any discussion of high-quality quartz crystals must be concerned almost exclusively with those functions. Historical Background Because of their ubiquitous character and natural beauty, quartz crystals have long been of interest and known to man. They have been found among early Egyptian and Chinese art forms and the Sumerians are believed to have fashioned seals, beads, and other jewelry from quartz crystals, perhaps 5,000 years ago. Also, American Indians made arrow heads and fashioned some simple objects of different kinds. The origin of the name quartz, although of Greek derivation, is uncertain. The Greeks appropriately applied their word for frozen water or ice, krustallos, to quartz. The present-day, large-scale practical applications of quartz crystals began in 1880-1881 when Pierre and Jacques Curie reported discovery of the "piezoelectric" effect. They found this effect first in Rochelle salt, a common product of grape-wine refineries, while studying crystal symmetry. Piezoelectricity is that property found in certain crystals, including quartz, whereby electrical charges of equal and opposite sign appear on opposite parts of the crystals when they are stressed. If equal and opposite forces are applied to two opposing prism edges of a single untwinned quartz crystal a positive electrical charge will appear on one edge and a negative charge on the other. The amount of the charges will be directly proportional to the force applied. This property seems to be intimately related to pyroelectricity

Jan 1, 1960

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675' and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By D. Turnbull, J. H. Hollomon

IN the most general sense, solidification refers to the formation of crystalline material from either a gas or a liquid. However, in this symposium, only the formation of crystals from liquids will be considered. Thus, in our present study the problem of solidification becomes that of determining the mechanism of the transition from a liquid to a crystalline solid, and our particular interest is in the transformation of metals from the liquid to the crystalline state. Metal liquids are seldom composed of only one kind of atom. Often solute atoms are added intentionally to make an alloy, or they may be present accidently because of incomplete purification. Furthermore, there may be small solid particles of various other crystals present in the liquid. Such small crystals may persist if their melting points are higher than any temperature to which the liquid is heated. Prior to solidification, the liquid metal usually is poured from one container to another. The second container, called the mold, usually is at a lower temperature than the container, or the crucible, in which the metal is liquified. The first solid that forms upon contact with the mold generally is of a different composition than the liquid, usually containing fewer foreign atoms or dissolved impurities. Heat is evolved upon solidification and is dissipated through the surroundings. Tree-like crystals, or dendrites, grow from the container walls and branch into the melt, enriching the remaining liquid in impurity atoms. In some alloys the remaining, relatively impure liquid continues to solidify until no liquid remains and the branches of the original crystal are cemented together. In other alloys, particles with a second type of crystal structure appear before solidification is complete. First the nature of the liquid and the solid states will be considered and then the mechanism of the initial formation of crystals from pure and alloy liquids. Later the problem of the growth of these crystals and the complexities of solidification in a mold, where the temperatures are not uniform and the composition of the melt changes continuously, will be discussed. LIQUID AND CRYSTALLINE STATES A liquid is an aggregate of atoms arranged with no apparent regularity (over distances of more than a few atom diameters). Nevertheless, any given atom generally has a definite number of nearest neighbors at definite distances, and thus order may be said to exist over a short range. In a crystal, on the other hand, a regular array of atoms continues for many hundreds or thousands of atom diameters, and a long-range order is apparent. Thus, a crystal having long-range order can be reproduced by linear translations for 10-5 cm or more of some fundamental unit possessing short-range order. A crude illustration of the difference between liquid and crystalline structures can be obtained by comparing the possible arrangements of oranges in a crate. If the oranges are simply dumped into the crate haphazardly until it is filled, the oranges will represent a static model of a liquid.

Jan 1, 1951

By F. L. Kadey

The petrographic microscope is a well known tool in nonmetallic materials research. Its utility in the study of perlite is, therefore, not surprising. Valuable information has been derived on samples smaller than those needed by most other methods of analysis. Relatively little has been written about the petrographic analysis of perlite for two chief reasons: perlite is a material of relatively new commercial interest; and the independent prospector or expander, responsible for most studies, attacks the problem from an immediately practical viewpoint. Hence, petrographic studies of perlite have been limited to academic aspects. Rapid development of commercial interest in perlite has changed the situation. Mining and expanding companies now have effective research tools; and such instruments as the petrographic microscope have added materially to practical knowledge about this mineral. Petrographic techniques employed in the search for suitable deposits screen worthless samples rapidly and inexpensively compared with large-scale expanding tests. Hence, only samples of potential quality are selected for further testing. Field appearance of perlite reveals little about its true identity and practically nothing about its commercial significance. Consequently, any method that can be used to separate the "wheat from the chaff" is valuable. In addition to the conventional thin-section and immersion methods used in evaluation of crude perlite, petrographic microscope techniques have contributed to the study of expanded perlite. When apparently similar materials behave as differently in use as perlites, the internal structure of the individual particles becomes a subject of great interest. The purpose of this paper is to discuss some of the petrographic techniques used to characterize this material. WHAT IS PERLITE AND WHERE IS IT FOUND? Perlite was at first described as a glassy rhyolite possessing a pearl-like luster and exhibiting numerous concentric cracks resembling an onion skin appearance.' Fig. 1 is an illustration of perlite in this classical sense. Recently, its definition has taken on a commercial connotation: an acid volcanic containing 2 to 5% of combined water that, when heated rapidly to the softening point of the glass, coincident with the volatilization of the combined water, expands or "pops". Fig. 2, although hardly fitting the classical description given by Johannsen, is an excellent perlite in the commercial sense. It may occur as a breccia in rhyolite, (Fig. 3) and sometimes it is associated with obsidian nodules, as illustrated in Fig. 4. The term perlite includes the expanded product also. In the United States, perlitic rocks are restricted to the western part of the country. 2 Elsewhere in the northern hemisphere, European occurrences follow a belt beginning in Iceland and extending in a southeasterly direction through Scotland, County Antrim in Northern Ireland, and through the Massif Central of France, Germany, and Hungary; thence, into Italy and Sardinia, and through some of the Aegean Islands. A general oriental belt extends from Japan through Australia and New Zealand. Rhyolitic areas elsewhere in the world undoubtedly contain perlite.

Jan 1, 1963

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675' and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

THE subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for 10 years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. I). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, nonmetallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to 100 mg. per sq. cm. per day, the corrosion rate of high-purity magnesium is 0.15 ± 0.05 mg. per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in combination, in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called "tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable. In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0.001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. While the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1941

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By Robert E. Green

Formulae are given for calculating the modes of wave propagation in a single-crystdl specimen possessing a given crystallographic orientation. Such calculations lead to determination of the orientation factor appearing in the Granato-Lucke theory for the attenuation of these waves due to dislocation damping. A detailed treatment is given for the case of an aluminum crystal possessing the orientation having a maximum Schmid fac -tor of 0.5. FOR a number of years the attenuation of ultrasonic waves propagating in metals has been used to investigate various phenomena causing internal friction.Most of the experiments were performed on polycrystalline test specimens and the waves were assumed to be propagating in an isotopic medium. However Alers 6 in 1955 and more recently Hikata et at. Chiao and Gordon,8 and Swanson and Green 10 have used measurements of attenuation of ultrasonic waves to study internal-friction changes in single crystals. These authors were concerned with the energy losses experienced by the ultrasonic waves due to dislocation motion induced by plastic deformation of the crystals. Alers measured the attenuation of 7 mc per sec ultrasonic pulses propagating in zinc single crystals before, during, and after plastic deformation. Simultaneously he measured the time-dependent plastic strain at constant stress in order to study the correlation between this strain and attenuation. The crystals were oriented in such a way that the applied stress provided a direct shear on the slip plane, thus causing the deformation to proceed by slip on this plane. At the same time the high-frequency sound pulses were sent through the crystal perpendicular to the slip plane. He found that the attenuation of transverse waves, the stress vectors of which lie in the slip plane, was very sensitive to the deformation. The polarization of the particle displacements, associated with these waves, relative to the applied static shear stress, and hence the direction of slip, had no obvious effect on the results. The attenuation of longitudinal waves was affected by the deformation only when the slip plane was not perpendicular to the propagation direction. This indicated that the attenuation was caused by dislocations introduced by the deformation and moving only in the slip plane. Hikata et al. made simultaneous measurements of attenuation, velocity changes, and stress-strain relations on aluminum single crystals deformed in tension. Both longitudinal and shear waves were used, at frequencies of 10 and 13 mc per sec. They placed emphasis on the choice of propagation modes and polarization of the ultrasonic waves, such that interactions between these waves and dislocations on selected slip systems could be investigated. They also selected specimens possessing specific crys-tallographic orientations, which allowed investigation as a function of the number of equally favored slip systems under the applied stress. They found that, for symmetrical orientations, the change of attenuation decreases with the increasing number of equally favored slip systems, i.e., in the order

Jan 1, 1964

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H'5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By Martin S. Maier, H. R. Nelson

THE diffusion of metals plays an important role in many metallurgical processes, 1,2 as, for example, the formation of alloys by the annealing of mixed powders, the homogenization of segregated alloys, and the carburization of steel. Other equally important phenomena, such as recrystallization and creep, are based on the movement of like atoms. Although much is known concerning the effects of diffusion in metals, very little is known concerning the details of the physical processes involved.1,3-5 The data that should give most information concerning the processes involved in diffusion are those on the diffusion of like atoms-self-diffusion. Very little is known concerning the rates of self-diffusion of metals because before the discovery of artificial radio-activity in 1934 there was no means of detecting the movement of the diffusing atoms through the solvent metal except in the elements possessing natural radioactive isotopes-lead, thallium and bismuth. Using the induced radioactivity of the element as an indicator, atoms can now be "tagged" so that the rate of diffusion of the radioactive isotopes of an element (tagged atoms) into the stable isotopes of the same element can be measured. As the radioactive and stable isotopes of an element differ only in nuclear structure, it is quite certain that all isotopes of an element diffuse at the same rate. Two techniques have been used to measure self-diffusion. In one, a thin layer of radioactive metal is deposited on the face of the solvent metal, and the decrease in the surface activity as the radioactive atoms diffuse into the solvent metal is measured. This method has been used to determine the coefficients of self-diffusion of lead6-10 and bismuth10 using natural radioactive isotopes, and of gold11 and copper12 using artificial radioactive isotopes. In the other technique a thin layer of the radioactive metal is deposited on one face of the solvent metal, and after diffusion has occurred the specimen is cut in thin sections to obtain the concentration-penetration curve. This method has been used to determine the coefficients of self-diffusion of gold,13 zinc, 14-16 silver,17 and copper.18 The second method was used for the work described in this paper. MATERIALS The coefficients of self-diffusion were determined in two grades of polycrystalline copper and in single crystals of copper. Commercial OFHC copper was used in the form of disks I in. in diameter by 1/8 in. thick. Samples of high-purity copper described by Phillips and Skinner19 were supplied through the courtesy of the American Smelting and Refining Co. The high-purity copper rod was used without remelting by cross-rolling to a thickness of 0.075 in., from which disks 7/8 in. in diameter were cut. A good grade of bus-bar copper was used to make the single crystals.

Jan 1, 1942

By R. W. Raymond

to same extent, the assumptions tinderlying Dr. Ilu?ley's con alusions. These amrrmptions are: that 'the loss of metal per million tons of trafffc, depends, first upon the circrtnistances under which the rail is worn; secondly, upon the proportions of its various constituents, ancl that the anlorlnt of loss is afEect~d by eacb constitnent in a cer tain ratio, so that if the circunlstances were the same for all tlie mils, the wear per nliilion tons might he upproxi91ately expre~sed by an equation of the form I + Cc + Pp + SR + Mm = R, io wtlioh I is an unknown valne, dependi~.rg on the quantity of iron (and other ingre dients not determined) in the rail, and assumed to be constant for all the rails ; c, p, s, and m are the experimentally determined quan tities of carhon, phosphorus, sulphur, and manganese, as tabulater1 in YIates VT and VII of Dr. Dudley's paper; and R is the experirnen tdlly dcterlnincd wear per million tons; while C, P, S, and M are onknown wfficients. In other words, it is assunled that the differ ence in wear is proportional to a difference in c, p, s, or m, and that the effects of a change in the amonnt of either are independent of the amount of the rest-—within the experinlental limit5 of the problem. It is also assr~med that sulphar, copper, and other ingredients, not determined, are qually present in all the rails, or at least {lo not affect the wear, since I is taken as constant. Dr. Dudley tacitly assumes the coefficient6 C, P, S, and M to be positive; and assigns certain valries to them, by means of which he redom t.he equation to the form I + Pa: = R, x being equal to cc + Es +Mm i Pp, or tjje uanjbe,. of so-called phosphorus units in the rail. But we do not have R directly given under constant circumstances. The varying weights (per engine, car, or train) and the varying epds, we must neglect for lack of data, and assume that in these rwpects the rails examined have been treated srlbstantially alike. But there remain the varying conditions as to track, which mnst he elirninsted. Dr. Dudley gives six clrlsses, four of which contain 8 rails each, and two 16 rails each. Beginning with the 6~st (tangent grade), take the mean of the figures expressing wear for that clam; and continaing tliis process through the other five, we obtain six expressions in quantity of loss 'by wear, which we assome tc, represent, in their differences, the varying conditions of the trarli, with respect to grade and direction. We now take the mean of these moans (giving double weight to the gmiip containing 16 ohwrvafieras). This general rnean is the 10 of metal per million tons of trafio for a rail of avorage constitution under mean ciroumstances.

Jan 1, 1881

By W. T. Isbell

In the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 1400O to 1500OF and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace were expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. Equipment and Its Uses Degincing Machine.—The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig 1). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.—The treating chamber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1949

By James R. I. Henagan, William O. Crego

The Mamou Field, located in Evangeline Parish, La., is an elongated anticlinal structure on the downthrown side of a major east-west fault with oil and gas production from the upper part of the Wilcox formation. Two main producing horizons occur at an approximate depth of 11,500 ft and have been designated the Morein sand and the Deshotels sand. The upper sand (Morein) had an original bottom-hole pressure of 6,788 psig, which is some 1,500 psi above the normal pressure for that depth. Oil production with high gas/oil ratios and fluid analyses giving high shrinkage factors prompted a study of the reservoir in its early stages. The results indicated a closed reservoir producing under solution gas drive with low expected ultimate oil recovery. The early study of the Wilcox formation and its contained hydrocarbons resulted in the presentation of the data to the Department of Conservation of the State of Louisiana. with suggestions for field rules and a request for permission to inject extraneous water into the Morein sand. The water injection plans eventually led to complete unitization of working and royalty interests, to the construction of a gasoline plant, and to a central tank battery installation for the field. Deshotels sand wells were reworked to the Morein sand, and the water injection system was installed and ready for continuous operation in the early part of 1949. The injection of water was started in time to arrest the bottom-hole pressure decline at or near the bubble-point pressure. This injection was calculated to increase the ultimate recovery and to conserve natural resources. Pressure maintenance, the extraction of LPG products, and the sale of residue gas (early 1950) represent an attempt to produce an oil field with utmost efficiency. INTRODUCTION The two principal Wilcox oil horizons in the Mamou Field are the Morein sand and the Deshotels sand, occurring at 11,500 ft and 11,700 ft subsea, respectively. Minor oil production has been encountered in Morein stringer sands. (Fig. 1.) This paper deals only with the Morein sand, which is blanket over the Mamou Field. It is, however, segmented by the northwest-southeast "E" fault as shown in Fig. 2. The west segment is the area involved in the water injection pressure maintenance program. To date the east segment has operated largely under the influence of a strong water drive. The paper presents (1) a brief history of field development, (2) a resumé of reservoir conditions which led to the decision to inject extraneous salt water into the principal producing horizon, and (3) a summary of reservoir analysis and performance. FIELD DEVELOPMENT The Mamou Field is located in Evangeline Parish, La. The discovery well (J. B. Morein No. 1, now Unit No. 5) was completed in December, 1945, after penetrating 200 ft into the Wilcox formation. Initial production from the Morein

Jan 1, 1951

By William R. Patterson

ACCORDING to the phase diagram for the Mn-Ni system,' the high-temperature, fcc y-manganese solid solution is stabilized to below room temperature, in the range approximately 22 to 28 wt pct Ni. However, pearson2 cites evidence in the literature showing that for manganese contents greater than about 75 wt pct the quenched phase in Mn-Ni alloys is fct. This is in keeping with zener's3 suggestion that in manganese-rich alloys the fcc high-temperature phase undergoes a diffusionless or martensitic transformation to a fct structure upon quenching. Work by Basinski and christian4 on manganese-rich compositions in the similar alloy system Mn-Cu established that in alloys of greater than about 82 wt pct Mn the y-manganese phase underwent a fee fct martensitic transformation upon quenching to room temperature. Striking evidence for this martensitic transformation was the highly twinned or banded microstructure, an example of which is shown in Fig. 1. Similar microstructures have also been found in quenched Mn-Cr5 and Mn-Au6 alloys. In the present investigation, we attempted to obtain similar evidence of a fcc — fct martensitic transformation in manganese-rich Mn-Ni alloys. Manganese alloys in the range 10 to 30 wt pct Ni were prepared by arc-melting, under argon, at atmospheric pressure. The alloys all were 50 g in size, and negligible weight loss occurred during melting. The starting materials were electrolytic manganese and nickel, both of 99.9+ pct purity. The alloys were subsequently homogenized 48 hr at 1750°F, hot-rolled 50 pct at 1700°F, annealed 2 hr at 1700°F, and water-quenched to room temperature. All heat treatment was done in purified argon. Both X-ray and metallographic techniques were used to examine the structures of the quenched alloys. X-ray diffractometer studies were conducted on powder specimens obtained from filings rean-nealed 2 hr at 1700°F in argon and water-quenched. Identification of the intensity peaks from the diffractometer counter traces showed that below about 10 to 12 pct Ni the y phase decomposed partially upon quenching to give an a- + ?-manganese structure. In the range approximately 12 to 25 pct Ni, the structure was found to be fct ? manganese with a c/a ratio approaching 1.0 at 25 pct Ni. Beyond approximately 25 pct Ni, the structure remained fcc. These results, including lattice-parameter determinations, are given in Table I. Metallographic examination. was carried out on specimens polished and etched after quenching, and also on polished specimens reannealed and quenched. In the first case, the distinctive twinning or banding so prevalent in Mn-Cu alloys was sought, while in the second, the surface relief effect generally regarded as being truly characteristic of a martensitic transformation was sought. The microstructure of representative alloys in the range 12 to 25 pct Ni is shown in Fig. 2. The structure of the Mn-15 pct Ni

Jan 1, 1965