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By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By David H. Browne, John F. Thompson

The literature dealing with the physical constants of nickel is so fragmentary and unrelated that a synopsis presents unusual difficulties. It is only within the last few years that investigators have understood the importance of placing on record not only the determinations they have made but also the composition, physical treatment, and past history of the material investigated. For this reason much of the earlier literature is valueless. Determinations have been made of the same physical constants on samples differing widely in origin, composition, and treatment, and the results differ widely among themselves. In the first place nickel is almost as flexible a term as steel. Its physical properties are widely influenced by its composition and treatment. It absorbs large quantities of gases and is exceedingly difficult to prepare in a state of chemical purity comparable to gold, silver, or copper. It is vitally affected by thermal and mechanical treatment. Hence in the following pages the recorded literature, where quoted, must be accepted with a certain reserve and used, as far as possible, as a check on later observations, in which these important factors are noted. In every case where new determinations are given, an attempt has been made to record all available information concerning the composition and treatment of the material used so that the data may serve as stepping-stones toward a wider knowledge of the properties of the metal. As this synopsis is an attempt by men of metallurgical training to do what should long before have been done by physicists, it is to be expected that certain errors may have crept in. Any corrections or suggestions

Jan 1, 1921

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10-5 cm. in size.

Jan 1, 1940

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10 5 cm. in size.

Jan 1, 1940

By Frederick N. Rhines, Robert F. Mehl

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ‡ in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Zedele and of Zedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By V. R. Garfias

Although the work on which this paper is based was carried on by the writer as Special Commissioner of the Petroleum Department of the Mexican Government, the opinions expressed are only his personal views for which the Mexican Government can in no way be held responsible. Notwithstanding that the appointment covers all phases of the so-called petroleum question, as the one question of immediate importance was that relating to taxation, it was decided to devote all the time to this phase of the work. The present report has been divided into two closely related parts, the first dealing with the production and marine transportation of Mcxican petroleum, and the second, with the Mexican taxation on petroleum and its products. The writer wishes to acknowledge the loyal cooperation rendered by Mr. M. C. Ehlen, who had charge of the statistical work, and by Miss S. Stern and Messrs. E. P. Heiles and J. E. Morrissey. The aim throughout the work has been to pave the way for a thorough understanding between the Mexican Government and the oil operators and to present a true and clear statement of facts relating to the questions at issue. Mexican Oil Fields Development The salient features in the development of the Mexican oil fields may be summarized as follows: 1901. First commercially productive well in Ebano field. 1902. Tehuantepee field came in; Diaz Government granted concession to Pearson & Son on practically all Federal lands along the Gulf of Mexico. 1907. First producing well in the Furbero field. 1908. Dos Bocas well caught fire, advertising tremendous productivity of Southern oil fields of Mexico.

Jan 1, 1921

By N. A. Ziegler

IN every research it is desirable to eliminate as many variables as possible and to leave only a few to be investigated one at a time. Metallurgical problems are no exception. Some of the variables that are difficult to control are the size, the distribution, and the orientation of the grains in a metallic test piece. It is therefore very desirable to obtain isolated metallic grains (single crystals, as they are commonly called) large enough to enable one to study their mechanical and physical properties. The present investigation is a part of magnetic research work on iron and iron alloys, undertaken to obtain, if possible, the magnetic properties of pure iron (Fe). This paper will deal primarily with the preparation of single crystals of iron and their mechanical properties, while another paper, by T. D. Yensen, now in preparation, will deal specifically with their magnetic properties. The work with "single crystals" is attracting more attention every year among the investigators in metallurgy. Van Liempt1 gives an interesting summary of the work done and the different methods used in the preparation of metallic single crystals. Briefly stated, the four principal methods used are the following: 1. The cooling of a liquid metal in such a way that the crystallization would start at one point only, causing the entire liquid to solidify as one crystalline unit. This method can be successfully applied to the majority of the metals that do not have any allotropic transformations in the solid state. It has been used and described by a number of investigators,2 but it has never been successfully applied to iron on account of allotropic transformations.

Jan 1, 1930

By G. F. Fix

Oil and gas activity reached a higher peak in Indiana during 1940 than for any like period during the past decade. Major activity, as during 1939, was in the southwestern part of the state, the Indiana portion of the Eastern Interior Coal Basin, where most of the increase was due to field drilling in previously proven areas. The amount of wildcat drilling was about the same as for 1939. No new fields of any apparent consequence were discovered during the year, with the possible exception of the College pool, in southwest Posey County. Only one well had been completed in this area at the end of the year. About 10 ft. of saturated Aux Vases sandstone was drilled in this well and the initial production was I00 bbl. of oil a day. Other discoveries during the year 1940 include: St. Thomas, in southwestern Knox County, where four McClosky wells, ranging from I00 to 300 bbl. a day initially, were com-pleted; Buff kin, in central Posey County, with 11 oil wells and 5 gas wells completed; and new developments in two old areas —Randolph County (part of the old Trenton field) and Gentryville, northwestern Spencer County, where some oil was found many years ago. The St. Thomas field proved disappoint-ing, with very spotty production from the McClosky horizon of the St. Genevieve limestone at a depth of about 1875 ft. The discovery well flowed 362 bbl. a day ini-tially. At the end of the year the field was pretty well outlined by dry holes and some inside locations were dry. The Buffkin pool also proved spotty, with production from shallow Pennsylvanian sands and from the Basal Pennsylvanian Mansfield sandstone, the latter at a depth of approximately I175 ft., with small production from the Cypress sandstone of Chester age. Oil wells in this pool are small, ranging from 25 to 75 bbl. a day. The Randolph County area, on the east side of the Trenton gas field, showed some promise for a commercial gas field, with four completed gas wells having cumulative initial flows of about 1,200,ooo cu. ft. a day. The area appar-ently was not depleted during the Trenton boom at the turn of the century, since casing pressures are about as high as the virgin pressure in the old field. Elsewhere the pressure has dropped as low as 5 pounds. The Griffin field received most of the drilling during 1940, with 163 completed oil wells. This field now covers about 3200 acres on the Indiana side of the Wabash River and is not as yet completely delimited. It produced the major part of Indiana's oil during the year—a total of 3,594,000 bbl. At the end of 1940, there were 253 producing wells in Griffin. New Harmony had five completions for a total of 24. The Rockport field, in Spencer County, continued to be actively developed and had a total of 45 gas wells and 9 oil wells at the end of the year. Oil in commercial quantities had not been found in the field previous to 1940. Total gas production for the year was 394,470,000 cubic feet. In all, 521 wells were drilled in the state during 1940, as compared to 377 for 1939. Of this number 248 were oil wells, 77 were gas wells and 196 were dry. Divided into

Jan 1, 1941

By J. F. Smith

ELASTIC constants of yttrium and eleven of the rare earth elements have been measured. This has been accomplished by measuring the propagation velocities of ultrasonic pulses. The velocity measurements were made by noting the elapsed time between an applied pulse and the appearance of successive echoes. The pulse-echo technique has become relatively common, and the basis of the measurement is outlined in several standard tests, e.g., Heuter and Bolt.1 Two important assumptions are made when using this method for the determination of elastic moduli. First, the pulse is assumed to propagate as a plane wave. To justify this assumption, the cross section of the test specimen should be large compared to the wave length of the transmitted pulse. For these measurements on the rare earth elements the minimum cross section wave length ratio was about 20. A second assumption which must be made when using polycrystalline specimens is that the grains are sufficiently numerous and randomly oriented so that the specimen may be approximated as elasti-cally isotopic. The grain size in the as-cast specimens which were used is believed to be sufficiently fine for this approximation, and the degree of preferred orientation is believed to be small. Supporting this viewpoint is the fact that elasticity measurements by the pulse-echo technique on as-cast specimens of other metals give results which are in satisfactory agreement with values obtained by other techniques. Hence, it is believed that the measured elasticity values for the rare earth elements are not apt to be seriously in error due to the assumption of elastic isotopy. The apparatus used in this determination was a modified Sperry Reflectoscope with a precisely calibrated time base circuit. Piezoelectric transducers were used both to generate the pulse and to detect the echoes. X-cut quartz crystals were used for the longitudinal modes, and Y-cut quartz crystals were used for the shear modes. Frequencies of 2.25 and 5 megacycles per sec were employed. Most of the specimens were 2.5 to 5.0 cm in length. Results Table I is a tabulation of the measured propagation velocities of longitudinal waves and of shear waves, together with densities obtained by Sped- ding, Daane, and Herrmann2 from lattice parameter measurements. The shear modulus, Poisson's ratio, and Young's modulus were calculated from the data in Table I through use of the following relationships: µ = pv32 [1] s=2-(vb/vs)2/2[1-(vb/vs)2] [2] and Y= 2µ(l+s) [3] where s is the shear modulus, Y is the Young's modulus, s is Poisson's ratio, p is the density, V0 is the longitudinal wave velocity, and v, is the shear wave velocity. The calculated quantities are shown in Table 11. Compressibility values can be computed from the relationship and the computed values may be compared with measured values obtained by Bridgman.8 Table III lists the data for such a comparison. The agreement is satisfactory, being particularly good for neodymi- um and gadolinium, poor for samarium, and intermediate for the other elements. Some variation is expected since Bridgman's measurements are isothermal, whereas the present measurements are adiabatic. In addition there may be some effect due to small variations in purity. Though most of the rare earth metals measured by Bridgman and all of the metals used in the present measurements were prepared at this laboratory, minor purity variations might exist since the samples came from different lots. Also, any imperfections such as dislocations, vacancies, voids, grain boundaries, microcracks, etc., should contribute to the volume change of a com-

Jan 1, 1958

By G. F. Fix

Oil and gas activity reached a higher peak in Indiana during 1940 than for any like period during the past decade. Major activity, as during 1939, was in the southwestern part of the state, the Indiana portion of the Eastern Interior Coal Basin, where most of the increase was due to field drilling in previously proven areas. The amount of wildcat drilling was about the same as for 1939. No new fields of any apparent consequence were discovered during the year, with the possible exception of the College pool, in southwest Posey County. Only one well had been completed in this area at the end of the year. About 10 ft. of saturated Aux Vases sandstone was drilled in this well and the initial production was I00 bbl. of oil a day. Other discoveries during the year 1940 include: St. Thomas, in southwestern Knox County, where four McClosky wells, ranging from I00 to 300 bbl. a day initially, were com-pleted; Buff kin, in central Posey County, with 11 oil wells and 5 gas wells completed; and new developments in two old areas —Randolph County (part of the old Trenton field) and Gentryville, northwestern Spencer County, where some oil was found many years ago. The St. Thomas field proved disappoint-ing, with very spotty production from the McClosky horizon of the St. Genevieve limestone at a depth of about 1875 ft. The discovery well flowed 362 bbl. a day ini-tially. At the end of the year the field was pretty well outlined by dry holes and some inside locations were dry. The Buffkin pool also proved spotty, with production from shallow Pennsylvanian sands and from the Basal Pennsylvanian Mansfield sandstone, the latter at a depth of approximately I175 ft., with small production from the Cypress sandstone of Chester age. Oil wells in this pool are small, ranging from 25 to 75 bbl. a day. The Randolph County area, on the east side of the Trenton gas field, showed some promise for a commercial gas field, with four completed gas wells having cumulative initial flows of about 1,200,ooo cu. ft. a day. The area appar-ently was not depleted during the Trenton boom at the turn of the century, since casing pressures are about as high as the virgin pressure in the old field. Elsewhere the pressure has dropped as low as 5 pounds. The Griffin field received most of the drilling during 1940, with 163 completed oil wells. This field now covers about 3200 acres on the Indiana side of the Wabash River and is not as yet completely delimited. It produced the major part of Indiana's oil during the year—a total of 3,594,000 bbl. At the end of 1940, there were 253 producing wells in Griffin. New Harmony had five completions for a total of 24. The Rockport field, in Spencer County, continued to be actively developed and had a total of 45 gas wells and 9 oil wells at the end of the year. Oil in commercial quantities had not been found in the field previous to 1940. Total gas production for the year was 394,470,000 cubic feet. In all, 521 wells were drilled in the state during 1940, as compared to 377 for 1939. Of this number 248 were oil wells, 77 were gas wells and 196 were dry. Divided into

Jan 1, 1941

By Lane Mitchell

A ceramic product or processed material is a solid composed of materials which have been subjected to heat above 875°F. The raw materials, which are blended together (or in some cases used singly), are selected and utilized for various reasons such as ease of fabrication, aid to processing, to yield desired properties after processing, lack or controllable degree of toxicity or hazard, availability, cost, and perhaps other considerations. Almost all solid inorganic, some organic, and some liquid and gaseous materials have the potential to be used individually in some ceramic product. There are several fundamental functions to be fulfilled in every ceramic product and a number of secondary functions are desirable in specified products. These functions are generally met by the most widely occurring minerals and rocks of the earth and their debris. This fact characterizes ceramics as a field utilizing the raw materials most available to man. Of course, specified products utilize synthetics, organics, and rare inorganics to produce desired results. Any solid nonmetallic product processed by subjection to temperature above a red heat may be called a ceramic product. Widely used construction materials and units, domestic utensils and units, industrial parts to facilitate manufacture, technical components, and aesthetic creations are very often of a ceramic nature because of the durability, inertness, hardness, ease of fabrication, cost, and availability of the ingredients. Often, organics or metals cannot meet desired specifications for some of these products. The rocks and minerals and mineral debris of the earth are largely siliceous. Oxygen and silicon comprise roughly 75% of the earth's crust with aluminum, iron, calcium, and the alkalies following in abundance. Silica ( SiO, ) and silicates can be melted to form glasses. Alumina (A1,0,), present in a mineral com- pound, gives greater durability, hardness, and strength, but lessens the glass-forming property. Iron, calcium, and the other alkalies flux silica and reduce melting points. Thus, sand, which is generally almost pure SiO,, and clay, which is generally hydrated alumina silicate, are the most widely used of all ceramic raw materials-principally because of the glass-forming propensities of silicates. In ceramic formulations, clay is generally a refractory filler or skeletal material, having in the raw state a plasticity derived from its colloidal grain size and its water-loving nature. On the other hand, silica sand is a glass former or nonplastic filler. Clay and silica sand in pure forms are quite refractory, i.e., not easily melted. Clay, although siliceous, is less of a glass former than pure silica and is more refractory. Natural contaminants, such as iron oxide or limestone, adulterate many clays and some sands. These contaminants act as fluxes and reduce the fusion points of the mineral or blends. Glass is made from silica sand by fluxing the sand with strong bases, usually soda ash and limestone. Red building bricks are hard and durable because the sand and clay have been partially fused with help of natural iron oxide serving as a flux. The iron oxide per- forms a dual function, serving as a pigment as well as a flux. In a blend of clay and sand and iron oxide, the sand is more susceptible to fusion than is the clay. Although silica sand and clay are the most widely used raw materials in most ceramic products, many other minerals, and some non- minerals are utilized in products where these materials can produce or aid in achieving desired results. Limestone and dolomite, feldspars, pigmentary minerals, refractory oxides or carbides, and special property producers can

Jan 1, 1975

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments. Survey: The pebble rock phosphate mining and washing operations in Florida (fig. 1) are along the river basins of the Alafia to the west and the Peace to the east. The elevation of the area varies between 40 and 170 ft above sea level. Effluents from the operations find their way into one of the two river systems (fig. 2), the Peace River which flows into Charlotte Harbor and the Alafia into Tampa Bay, both along the Gulf of Mexico. There are no major industries along these rivers below the phosphate operations. On the Peace River, the town of Arcadia, approximately 50 miles below the phosphate operations, obtains its water from the river. No other communities along the rivers use them as a source of water supply. Small communities, farms, and ranches are located along the rivers and both rivers drain vast swamp areas. Complaints had been received at the office of the Chief Sanitary Engineer, of the Florida State Board of Health,' that both rivers were turbid at various times and that fishing in the Alafia River was "not as good as it used to be." Tests made by another agency on the dissolved oxygen content of the Alafia River revealed that the oxygen content, at times, was comparatively low.= However, it was not shown that the phosphate wastes had any effect upon the oxygen content of the stream. The river waters are normally brown in color due to drainage from vast swamp areas and are very shallow, from 2 to 6 ft in depth. Turbid waters have been noted in streams coming from the present phosphate operations and also from streams along which there are no operations at the present time. It was learned from "old timers" that, when many more companies than at present were operating along both the Alafia and Peace Rivers forty or fifty years ago, no attention was paid to prohibiting the disposal of slimes along the river basins. During dry periods now in some of the river swamps where drainage ditches have been dug, it is indicated clearly that phosphate slimes were disposed of directly into the river swamps for many years past. Places have been observed where there were alternating strata of phosphate mud, leaf mold, and quartz sand. The former practice of indiscriminate disposal of wastes accounts for some turbidity, particularly after heavy rains and washouts and during clearing of land and digging of drainage ditches. During a six months' period in which a large tract of land was being cleared and drainage ditches dug, a small stream (Six Mile Creek), which previously had been clear, showed a turbidity of 600 ppm and remained turbid until the clearing was completed; after which the stream again flowed clear. An interview with the operator of the municipal water plant, which is about 50 miles below the phosphate operations on the Peace River and which used this river as a source of supply, revealed that there had been no taste in the water for the past ten years, other than that occasionally encountered from increased growth of algae. The operations of each of the cooperating com-

Jan 1, 1951

By Thomas C. Patton, Eric S. Cheney

L-D gold mine is 3 miles south of Wenatchee, central Washington. Recognition of locally mappable conglomerates, sandstones, and shales within the Paleocene (?) Swauk formation led to the discovery that the known epithermal gold mineraliza¬tion is limited to a previously unknown imbricate thrust zone of unknown displace¬ment cutting the open folds o f the area. Hypabyssal intrusions also are most nu¬merous along the trace of the thrust faults. Yakima basalt of Miocene age uncon¬formably overlies the Swauk formation, thrust faults, and the intrusions. The L-D mine is in a northwesterly trending imbricate fault block of nearly vertical strata. Microscopic native gold, electrum, and naumannite occur in quartz veins and as low¬grade disseminations in the well-silicified portions of arkosic sandstones. Fault gouge on the "footwall fissure" limits ore to the hanging-wall block of the fault. Epithermal mineralization and alteration are spatially related to the nearby intrusions. Right lateral north-south faults offset the ore a maximum of 300-400 ft along any one fault. From 1949 until January 1967, when the L-D mine closed, 1,036,572 dry tons of ore valued at $14,962,305 and averaging 0.396 oz Au per ton and 0.607 oz Ag per ton were mined. Recognition of the structural control of the mineralization and altera¬tion within the Swauk formation suggests several areas within and outside of the mine that warrant further exploration. For example, the high-angle faults, imbricate thrusts, and the intrusions of this area are on strike with similar features along the major Entiat fault zone 10 miles to the northwest. The L-D gold mine (previously called Squilchuck, Wenatchee, Golden King, Gold King, and Lovitt) is located in Squilchuck Canyon about three miles south of Wenatchee, Chelan County, Wash. (Fig. 1) on the eastern edge of the Cascade Mountains. The major stratigraphic unit in the area is the nonmarine early Tertiary Swauk formation, which is predominantly com¬posed of arkosic sandstone. The lack of laterally per¬sistent units and the paucity of outcrops heretofore have precluded all but the grossest subdivision of the Swauk.' As a result, the true significance of the open folds in the Wenatchee area was not recognized, and although the geology within the mine was known, the structural setting of the mine was virtually unknown. During the present investigation, several locally map¬pable units were discovered within the Swauk which, in conjunction with mine maps, indicate an imbricate thrust zone. The epithermal gold mineralization, most of the hypabyssal intrusions, and the zones of hydrother¬mal alteration are located within or near this thrust zone. The purpose of this paper is to: (1) to describe this structural setting, rather than the detailed mine geology already presented by Lovitt and Skerl,2 and (2) to sug¬gest that from an exploration standpoint, this struc¬tural setting may be repeated in areas inside and outside of the mine area. Stratigraphy and Structure of the Swauk Formation General: The Swauk formation contains three distinct lithologies. Typical Swauk sandstone is gray on fresh surfaces, poorly sorted, weathers tan, and is cross¬bedded; it consists of 40-60% quartz, 20-40% feldspar, and up to 10% muscovite and biotite 9 The typical shale is gray to dark brown, very soft, and interbedded with silty sandstones; sharp contacts exist between the

Jan 1, 1972

By Randolph C. Specht

A two year study was made of the waste disposal of the pebble rock phosphate industry. Solid slimes are impounded in large settling areas and the process water is re-used. Clear effluent was not found to be toxic to fish or animal life in field tests or in controlled experiments. Survey: The pebble rock phosphate mining and washing operations in Florida (fig. 1) are along the river basins of the Alafia to the west and the Peace to the east. The elevation of the area varies between 40 and 170 ft above sea level. Effluents from the operations find their way into one of the two river systems (fig. 2), the Peace River which flows into Charlotte Harbor and the Alafia into Tampa Bay, both along the Gulf of Mexico. There are no major industries along these rivers below the phosphate operations. On the Peace River, the town of Arcadia, approximately 50 miles below the phosphate operations, obtains its water from the river. No other communities along the rivers use them as a source of water supply. Small communities, farms, and ranches are located along the rivers and both rivers drain vast swamp areas. Complaints had been received at the office of the Chief Sanitary Engineer, of the Florida State Board of Health,' that both rivers were turbid at various times and that fishing in the Alafia River was "not as good as it used to be." Tests made by another agency on the dissolved oxygen content of the Alafia River revealed that the oxygen content, at times, was comparatively low.= However, it was not shown that the phosphate wastes had any effect upon the oxygen content of the stream. The river waters are normally brown in color due to drainage from vast swamp areas and are very shallow, from 2 to 6 ft in depth. Turbid waters have been noted in streams coming from the present phosphate operations and also from streams along which there are no operations at the present time. It was learned from "old timers" that, when many more companies than at present were operating along both the Alafia and Peace Rivers forty or fifty years ago, no attention was paid to prohibiting the disposal of slimes along the river basins. During dry periods now in some of the river swamps where drainage ditches have been dug, it is indicated clearly that phosphate slimes were disposed of directly into the river swamps for many years past. Places have been observed where there were alternating strata of phosphate mud, leaf mold, and quartz sand. The former practice of indiscriminate disposal of wastes accounts for some turbidity, particularly after heavy rains and washouts and during clearing of land and digging of drainage ditches. During a six months' period in which a large tract of land was being cleared and drainage ditches dug, a small stream (Six Mile Creek), which previously had been clear, showed a turbidity of 600 ppm and remained turbid until the clearing was completed; after which the stream again flowed clear. An interview with the operator of the municipal water plant, which is about 50 miles below the phosphate operations on the Peace River and which used this river as a source of supply, revealed that there had been no taste in the water for the past ten years, other than that occasionally encountered from increased growth of algae. The operations of each of the cooperating com-

Jan 1, 1951

By AIME AIME

In the uniform of his country for the second time, Harry Phillip Stolz. Chairman of the A.I.M.E. Petroleum Division, holds a commission as Lieutenant-Commander in the Naval Reserve and is attached to the office of Inspector of Naval Petroleum Reserves in California. During World War I he left his studies at Stanford University to join the Army and was granted a commission as Second Lieutenant of Infantry. He remained in the Army Reserve until 1938 when he resigned to accept a commission as a member of the Naval Petroleum Reserves Advisory Board. Born in San Francisco Jan. 29,1899, where his father had lived since 1880, he was in that city during the turbulent year of 1906 where the city was ravaged by fire and earthquake.

Jan 1, 1942

By T. Rosenqvist

From the chemical, metallurgical, and mineralogical points of view, the importance of thermodynamic data for metal-sulphides and sulphur dissolved in molten metal has long been realized. Such data will give a basis for thermo-dynamic calculations of processes such as roasting and the distribution of sulphur between molten metal and slags. Furthermore, it will help us understand the chemical forces which tie sulphur to the metal and to the melt. Thermodynamic studies of solid sulphides and the equilibria between solid sulphides and metals have been carried out in a rather large number of cases by several investigators. An excellent review of this work is given by Kelley.1 On the other hand, very little is known about the thermodynamic properties of molten sulphides and of sulphur dissolved in molten metal. The only system which previously has been investigated in this respect is the iron/sulphur system. The purpose of the present investigation was primarily to obtain further data for metalisulphur melts and the system silver/sulphur was chosen, not because this system was expected to be of special interest in itself, but because the silver/sulphur system is a typical example of a metal/sulphur system. Because of the low melting temperatures, the work could be carried out without appreciable furnace and refractory difficulties. The sulphur in this system possesses a rather high escaping tendency compared to most other metal/sulphur systems. By the method employed (reaction with hydrogen to form hydrogen sulphide) this gives ratios Ph2s/Ph2 up to 0.30, which may be determined accurately. 'rhermodynamic investigations of the heterogeneous reaction Ag2S +H2 —+ 2Ag + H2S have previously been carried out by Pelabon,2 Keyes and Felsing,3 Jellineb and Zakowski,4 Wat-anabe,6 and Britzke and Kapustinsky.6 Their results are in rather poor agreement. Experimental Part PRINCIPLE In the present invehgation the escaping tendency of sulphur from the condensed phase was determined by the reaction: S + H2 = H2S The ratio Ph2s/Ph2 is at constant temperature, directly proportional to the escaping tendency of sulphur and to its chemical activity in the condensed phase. (This ratio will subsequently be denoted by H2S/H2.) From this ratio and its variation with temperature and with change in the com- position of the condensed phase, thermodyrlamic quantities such as free energy and heat of reaction can be derived. The apparatus used is shown in Fig 1. The silver/sulphur alloy was placed in a crucible inside a refractory tube and mounted inside the furnace to the left. The tube was a part of a closed, gas-tight system in which the gas mixture could circulate until equilibrium was established. Circulation was maintained by the glass propeller to the right, driven by an external magnet, and promoted by the chimney action of the furnace. The gas passed up through the furnace, down into the crucible where it came in contact with the alloy, passed rapidly up through a narrow tube and out of the hot zone. After equilibrium was established between the gas and the condensed phase, the composition of the gas mixture was determined from its density. In its circulation, the gas mixture passed through a chamber (lower right on Fig 1) containing a buoyancy-balance, where the density of the gas was determined by magnetic balancing. From the measured density,

Jan 1, 1950

By R. H. Jacoby, M. J. Rzasa

Experimental equilibrium vaporization ratios (K values) were obtained for nitrogen, methane, carbon dioxide, ethane and hydrogen sulfide in two natural gas-absorber oil mixtures and in two natural gas-Elk Basin crude oil mixtures. For each mixture of constant over-all composition, data were obtained at 100°, 150° and 200°F and at various pressures in the range 200 to 5,000 psia. Some effects of composition on the K values were obtained to serve as a guide in choosing K's for engineering calculations on other mixtures. The pressure cell used to obtain the data is a new type and is described here for the first time. INTRODUCTION The phase equilibria of complex hydrocarbon mixtures such as natural gases, crude oils and their mixtures have been studied previously for the purpose of finding equilibrium vaporization ratios for the hydrocarbon constitutents. In a few cases, such non-hydrocarbon.: as nitrogen, carbon dioxide, and hydrogen sulfide were included in the mixture. studied because they occur. in the fluids obtained from petroleum reservoirs. The increasing occurrerce. of these non-liydrocarbon.; antl their growing economic importance. make it necessary to account for them more accurately in engineering calculation.: than is now possible using the meager published data. The available data for non-hydrocarbons may he classified into two groups: namely, binary mixtures of a hydrocarbon and a non-hydrocarbon. and mixtures containing three or more components, only one of which is a non-hydrocarbon. Amon: the former. phase analyses are available for two nitrogen-HC mixtures, tve carbon dioxide-HC mixtures and three hydrogen sulfide-HC mixtures. Data for more complex mixtures are available as follows: Nitrogen-Methane-Pentane'; Nitrogen-Methane-Hexane,'; Nitrogen-Methane-Heptane'; Carbon dioxide-Natural Gas-Natural Gasorline": Carbon dioxide-Natural Gas-Crude Oil". These data have been used generally lor engineering calculations, often with little regard for their precise applicability because data for the non-hydrocarbons in the complex mixtures being dealt with were not available. The use of K values from binary data for calculation:; involving complex mixtures is open to criticism because such K's are not a function of composition and very often show large differences from the K's for the same components in a complex mixture. Thus the effects of composition must be evaluated when obtaining K's for components in complex mixtures. Poettmann and Katz " varied the carbon dioxide content of their mixture.; from about five to ten mol per cent and found substantially no effect on the K values due to this change. This was not surprising since one might expect that changing a minor com-ponent by * three mol per cent would have little effect. It is more important to find the composition change which have the largest effect on the K values. For example. varying the methane or heptanes — plus compositions over a wide rangr may have a large effect on the K'. of all components in the mixture. Interesting data to this effect were obtained by Eilerts and Smith." It was toward these problems that the experimental data presented here were directed. EQUIPMENT The pressure cell used to obtain the data i:. somewhat dif-ferent from those which have been described in the past. Photographs of the equipment are shown in Figs. 1 and 2. Fig. 1 Shows. the front panel: from a .rated position at the right the

Jan 1, 1952

By W. R. McMillan, E. A. Gulbransen, K. F. Andrew

Annealed and electrolytically polished pure iron was oxidized between 650° and 850°C at oxygen pressures of 0.1 to 2 microns Hg. Electron optical studies showed that oxidation occurs discontinuously over the surface and orients crystallographically with the substructure of the metal grains. IN previous papers', " the authors described the formation of oxide films on high purity iron at norrnal pressures and at temperatures below 300°C. Electron optical studies showed that the oxide film consisted of many individual oxide crystallites having nearly random orientation on each metal grain. The size of the oxide crystallites depended upon the temperature and upon the extent of oxidation. In these studies the crystallite size varied from 250 to 1800Å. Recently, Bardolle and Benard3 studied the crystal habit of the oxide crystallites formed on Armco iron between 650" and 850°C in what might be defined as a "poor vacuum" atmosphere in which the pressure could be varied between 10-1 to 10-3 mm of Hg. Their results showed that, at 850°C and a vacuum of l0-2 to 10-3 mm of Hg, a few well oriented nuclei of oxide were formed on the metal grains. At pressures between l0-1 to 10-2 mm of Hg, many oriented nuclei of oxide were formed. At 750°C the metal surface was bright although an oxide was present. Unfortunately, the extent of oxidation, the oxygen pressure, and the influence of carbon in the metal were not determined, and it was, therefore, impossible to give a theoretical interpretation to the very beautiful light micrographs. Bardolle and Benard used the light microscope to determine the crystal habit of the oxide and X-ray diffraction to determine the orientation relationships. It was believed that the use of controlled amounts of oxidation at high temperature is an important method for the study of the initial stages of oxidation of metals at high temperatures. This paper presents the first results of an electron optical study of this problem for iron. Since the electron microscope and electron-diffraction methods using stripped oxide films and surface replicas yielded finer details of the crystal habit and structure of oxide film, these methods were used in this study. Two types of iron having different carbon contents were used: Puron and Armco* iron. A com- parison of the results for these materials made possible a study of the influence of the surface oxide-carbon reaction on the initial stages of oxidation. Before discussing the experimental results, the thermodynamic equilibria of 1—the oxidation reaction, 2—the surface oxide-carbon reaction, and 3—the solubility of oxygen in iron, will be considered. In addition, it is important to consider the kinetic-theory predictions on the rate of collision of oxygen with the iron surface. Thermodynamic and Kinetic-Theory Calculations Only one type of reaction is usually considered in the oxidation of iron at normal pressures at high temperatures: Fe(a) + 1/2O2(g) = FeO(s) 3Fe(a) + 2O2(g) = Fe3O4(s) 2Fe(a) +3/2O2(g) = a-Fe2O3(s). [11 However, two other reactions may occur: FeO(s) + C (solid solution in Fe) + Fe(a) + CO(g) [2] and Fe(a) + O2(g) e Fe(a) (solid solution of 0,). [ 3 ] In addition, iron will react with the higher oxide at certain temperatures to form FeO. For a complete interpretation of the oxidation of iron at low pres-

Jan 1, 1955

By R. Ruka, E. A. Gulbransen

ONE of the interesting questions in the understanding of the reaction of iron with oxygen is the kinetics and the mechanism of the crystal structure changes occurring in the formation and breakdown of the oxide film. In a recent work' the electron diffraction method was applied to the study of the solid phase reactions occurring internally in the oxide film on iron above 570°C and under vacuum conditions. The higher oxides which form under oxidizing conditions are reduced internally by the diffusion of iron into the oxide leaving the bulk of the oxide FeO (wüstite). This paper will ask and consider three questions. These are: (1) What is the nature of the depressed transformation temperature for the Fe3O4 + Fe ? 4Fe0 reaction in very thin oxide films?; (2) What is the mechanism of the forward transformation of Fe3O4 to FeO at or near 570°C?; and (3) What is the nature and mechanism of the slow reverse transformation of FeO to Fe3O4 and Fe below 570°C?. The composition of the oxide as well as its electrical, magnetic, mechanical, and chemical properties depends upon the kinetics of these reactions. Literature Survey The composition of the oxide film on pure iron at temperatures up to 570°C has been studied extensively by the electron diffraction method. Nelson,' Jackson and Quarrell,3 and Gulbransen and Hick-man4 have shown that Fe3O4 and a-Fe2O8 are formed in the temperature range of 225" to 570°C, while y-Fe,O, is most likely formed below 225°C for long oxidation times. In very thin films FeO (wüstite) is found to form at temperatures as low as 400°C, and its existence depends essentially upon the extent of initial oxidation. FeO is not found in the formation of thick films below 570°C. On the other hand X-ray5 and micrographic8 studies show that Fe3O4 may exist as the main com-ponent in thick films up to 650°C, well above the equilibrium temperature for the reaction Fe3O4 + Fe ? 4FeO. The kinetics of the forward and reverse trans-formations of the reaction Fe3O4 + Fe ? 4FeO have not been studied in oxide films. However, analysis of the data of Gulbransen and Hickman4 on the heat-ing and cooling of iron oxide films of known thick-nesses in high vacua shows that the forward reac-tion proceeds rapidly even for a 4000 A film at temperatures of 575" to 600°C. The reverse reaction or decomposition of wüstite (FeO) occurs at tem-peratures below 450°C. Thus, there appears to be a slow process in the decomposition which is in marked contrast to the rapid forward reaction. The decomposition of a bulk sample of FeO free from the metal has been studied extensively by Chaudron, Benard and coworkers using the micro-graphic, X-ray diffraction, and thermomagnetic methods. Chaudron7,8 first observed that the de-composition of FeO (wüstite) below 570°C occurs by the reaction 4FeO ? Fe3O4 + Fe. Later work by Chaudron and Forestier5 showed that the rate of de-

Jan 1, 1951