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By B. W. Gandrud

WET-PROCESS coal-washing tables as we know them today have been in use in this country for approximately 25 years. The literature records only a few table installations worthy of note prior to adoption of the present-day differential-motion table. According to Phillip,1 six Campbell bumping tables were being operated by the St. Bernard Coal Co., Earlington, Ky., in 1893. As late as 1923, according to Richardson, 2 such tables were in operation in the Rosedale washery of the Cambria Steel Co., at Johnstown, Pa. Bumping tables probably were not used to any considerable extent except in the plant at Earlington, and at two or three plants in Pennsylvania, but they may be considered as. forerunners of the present-day coal-washing table. The transition from bumping tables to the type of tables now in use signalized a revolutionary change in table design. The advantages of the new design over the old were so outstanding as to make its adoption inevitable. BUMPING TABLES Bumping tables, as the name implies, utilized a bumping action for conveying the refuse and discharging it over the refuse end. The tables were hung from rods attached to overhead supporting beams. A shaft and cam arrangement at one end of the table served as the actuating mechanism and imparted to the table an endwise, back-and-forth, swinging motion. A bumping block was fixed in the proper position at the shaft end, so that the table would strike against it at the end of each backward swing. The hanger rods or stirrups were so adjusted as to give the table a slight uphill slope toward the refuse end; that is, the end next to the driving mechanism. The feed box was near the upper end of the table and designed to spread the mixture of coal and water over the width of the table. Wash water was added a short distance below the feed box. With the table in motion and coal mixed kith water being fed to it through the feed box, a certain amount of stratification took place, depositing heavy refuse at the bottom of the bed in contact with the surface of the table. Constant bumping and a certain amount

Jan 1, 1950

By John P. Bryant

Plant nutrients are obtained by plants from both the air and the soil. Carbon dioxide, a gaseous form of carbon and oxygen, supplies the carbon which usually makes up 50% or more of plant structure. Plants are capable of absorbing carbon dioxide directly from the air. Most of this nutrient comes from the air, although some carbon dioxide is absorbed by soil water and taken into the plant as liquid. Growing plants use more water than any other substance. Plant nutrients in the soil dissolve in soil water; soil water entering the plant carries nutrients into the plant structure. Water is then given off into the air as the plant breathes or transpires. The inorganic or mineral portion of the nutrients which plants require comes from the soil. Inorganic or mineral composition of plants is usually less than 5% of their weight, and this mineral requirement, usually lacking in the soil, must be provided by fertilizers. Proper fertilization of a soil to improve its mineral level and productivity is the basis for the fertilizer industry (Thomas, 1960). There are 13 essential plant nutrients which often must be added to soils or plants and are generally considered as fertilizer minerals. These nutrients are divided into the categories: primary minerals (nitrogen, phosphorus, potassium); secondary minerals (calcium, magnesium, sulfur); and micro or trace minerals (boron, iron, manganese, copper, zinc, molybdenum, chlorine). Further, cobalt is often added to fertilizers. Although it is not considered to be an essential plant nutrient, it is essential to animal health and is often applied to forages as a fertilizer constituent. One point of major significance to the fertilizer industry is that not all nutrient carriers supply that nutrient in a chemical form which will be available to the plant. Thus, a product which may be considered a fertilizer mineral may require substantial processing or treatment before it becomes useful as a nutrient carrier. Fertilizer Industry Scope Until about 1900 demands for higher crop yields were met simply by bringing new agricultural lands into cultivation. Since that time great progress has been made in increasing yields through fertilization and improved varieties and cultural practices. The importance of the fertilizer industry to the economy and welfare of the U.S. is widely recognized. [Fig. 1] illustrates the relationship of lime and fertilizers to crop yields. In terms of tons of fertilizer products, the growth of the industry has been phenomenal, particularly between 1950 and 1970. Table 1 shows the increase in fertilizer usage. Primary Plant Nutrients in Fertilizers Primary minerals (nitrogen, phosphorus, potassium) are designated as such because of their significance to plant growth. Practically all soils are deficient in both nitrogen and phosphorus, and most of them are also deficient in potassium. Consequently, these nutrients

Jan 1, 1975

By John Wulff

IN a previous paper Burwell and Wulff1 have shown by electron diffraction studies that allotropic transformations can be induced in 18-8 stainless steel by polishing to a depth of about 5 X 10-5 cm. The development of a successful etching technique, which removes accountable amounts of metal from the surface without pitting and without changing the root-mean-square profile as measured with an Abbot profilometer, led to the application of the whole technique and material to an investigation of various mechanical methods of surface preparation, such as grinding, lapping, superfinishing and cold-rolling. Ideally suited to such a study is 18-8 of low carbon and nitrogen content. The material can be heat-treated to produce a coarse-grained single-phase structure. On cold deformation there occurs not only a reduction in grain size but, at regions of maximum stress, a change of face-centered material to body-centered material, provided the metal is worked below about 200°C. When worked between 200° and 415°C., diffraction studies evidence a reduction in grain size without the appearance of any new body-centered ferrite. Ferrite, which can be referred also to strains induced by carbide precipitation, is evident when the material is worked at temperatures between 415° and 800°C. Stainless steel is advantageous because the usual surface-finishing operations do not readily oxidize it to any appreciable depth. In order to produce detectable oxide films on the surface of austenitic 18-8 in a time equivalent to that required to produce, for example, a fine ground finish on ½ sq. in., the sample must be held in a furnace or oxygen stream above 600°C. By using longer heating times, it is possible to achieve measurable oxide films on samples whose surface temperatures exceed only about 250°C. EXPERIMENTAL PROCEDURE The apparatus, material, and technique described in the previous paper1 were employed in this investigation. Samples of 18-8, 1 by 1 cm. by 4 mm., were carefully annealed in the austenitic range to produce a coarse-grained structure. They were then quenched and pickled to remove scale. On a lapping machine of the Graton2 type, both sides of each sample were polished to a flatness of 1/6 a wave length of sodium D light. Thereafter they were electrolytically etched to remove at least 1 X 10-3 cm. of the surface, a depth that is well below that of any deformations induced by surface preparation. Samples of this material, carefully mounted in steel holders, were then sent to various industrial organizations known for special finishing techniques. In the instrument shops at the Massachusetts Institute of Technology check samples were finished by the same methods, as far as they were available. Abbot profilometer3 readings were made on all the samples, which were then carefully degreased in double distilled benzine and alcohol, dried in a hot-filtered air blast, and kept in a desiccator. Suc-

Jan 1, 1941

By P. Greenfield, P. A. Beck

RECENT work by J. Darby, Jr. in this laboratory has shown that the reported vanadium-rich limit of the s phase in the Co-V system at 1200°C is in error. The appearance of a second phase in s actually is restricted to alloys containing over 68 atomic pct V. The error in the original value is due apparently to a reaction that takes place along the numerous cracks in the s specimens between the alloy and the impurities present in the He + 8 pct H atmosphere in the annealing furnace. Such a reaction and the consequent appearance of a second phase can be suppressed if the alloys are sealed under vacuum in Vycor tubing. The new value of 68 atomic pct V for the vana-dium-rich limit of the s phase in the Co-V system effects slightly the s compositions calculated from average values of N, and N,. for various s phases. The standard deviation between experimental mean compositions and those calculated from the assumption that s is characterized by a constant number of 3d + 4s electrons per atom (N,), is slightly reduced from 9.1 to 8.8 pct. The maximum divergence for the V-Mn s phase is reduced from 15.5 to 14 atomic pct. The standard deviation calculated from constant electron vacancy numbers given by N.. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2(Fe) + 1.71(Co) + 1.6(Ni) is now greatly reduced, as the maximum divergence for this correlation previously occurred in the V-Co system. This maximum divergence is reduced from 7.6 to 2.3 pct, and the standard deviation for all s- phases is reduced from 4.1 to only 2.9 pct. The correlation for electron vacancy numbers given by N. 5.66 (V when with Ni or Co) + 4.88 (V when with Mn or Fe) + 4.66 (Cr + Mn) + 3.3 (Mn) + 2.66 (Fe) + 1.71 (Co) + 0.61 (Ni) is made slightly worse, and the standard deviation increases from 2.8 to 3.9 pct. These changes, however, do not affect the conclusions of the paper.' The deviation between calculated and experimental s compositions is much less for either one of the electron vacancy correlations than for the correlation with the number of 3d + 4s electrons.

Jan 1, 1955

By Louise Barton Freeman, Iley B. Browning, Coleman D. Hunter

During 1942, production of oil in Kentucky reached a total of 4,169,163 bbl. of which 1,807,809 bbl. came from eastern Kentucky. This was more than a million barrels less than in 1941, owing partly to the low price of crude oil, which almost eliminated wildcatting, and partly to spacing regulations, which limited the number of wells drilled in small, shallow pools where the pressures are not sufficient to maintain maximum recovery in widely spaced wells. In eastern Kentucky much of the oil was produced from outliers of the Mauch Chunk series at the disconformable contact of the Mississippian and Pennsylvanian. Although wells producing from this horizon, known as the Maxon, are sprinkled over the entire area, the greatest concentrations are in Martin, Floyd, Knott and Pike Counties. A new 30 to 40-bbl. well has been completed in this formation in ,Pike County, where the carbon ratio is so high that ordinarily oil would not be expected. Pike County is one of the largest producers of Maxon gas, and the offset well to this oil well produced gas. Of the 412 gas wells drilled in Pike County, 12.2 per cent produced gas from the Maxon horizon. During 1942, the old Menifee " Cornif-erous" field, the Mariba-Denniston field, was redrilled between old wells, and although it did not produce any large amount of oil it did contribute 2018 bbl. In the oldest oil field in eastern Kentucky, the Ragland pool, operators are cleaning out abandoned wells and are using this oil for fuel oil. There is a possibility that some of this may be used in the future as distilled fuel oil. Eight wells were completed in 1942 in the Jackson County gas field. The development of Jackson County, which was started in 1934 and in which commercial quantities of gas were encountered at a depth of 1100 to 1200 ft., has become of importance in 1942 with the completion of eight wells, making a total of 24 commercial producing wells with an average rock pressure of 140 lb. At this time the gas is not being marketed. In the last year it has been found that these wells, which produce from the Niagaran dolomite ("Cornif-erous"), respond to acidizing and the production has been thus greatly increased. There has been less development in Estill and Lee Counties than for several years. Two wells were drilled in Greenup County, one of which had a show of oil in the Berea sandstone. One deep test, drilled by the Owens-Libbey-Owens Co. in Lawrence County, was dry. This well was drilled to a depth of 4975 ft. into the top of the Clinton shale sequence. Of the 202 wells completed in Floyd, Martin, Knott and Pike Counties, 187 were gas wells, 3 oil wells and 12 dry holes. In Floyd County 66 per cent of the gas production was from the Devonian-Mis-sissippian black shales, 53 per cent in Martin, 79 per cent in Knott and 65 per cent in Pike. This is probably the largest continuous gas field east of the Mississippi

Jan 1, 1943

By Iley B. Browning, Louise Barton Freeman, Coleman D. Hunter

During 1942, production of oil in Kentucky reached a total of 4,169,163 bbl. of which 1,807,809 bbl. came from eastern Kentucky. This was more than a million barrels less than in 1941, owing partly to the low price of crude oil, which almost eliminated wildcatting, and partly to spacing regulations, which limited the number of wells drilled in small, shallow pools where the pressures are not sufficient to maintain maximum recovery in widely spaced wells. In eastern Kentucky much of the oil was produced from outliers of the Mauch Chunk series at the disconformable contact of the Mississippian and Pennsylvanian. Although wells producing from this horizon, known as the Maxon, are sprinkled over the entire area, the greatest concentrations are in Martin, Floyd, Knott and Pike Counties. A new 30 to 40-bbl. well has been completed in this formation in ,Pike County, where the carbon ratio is so high that ordinarily oil would not be expected. Pike County is one of the largest producers of Maxon gas, and the offset well to this oil well produced gas. Of the 412 gas wells drilled in Pike County, 12.2 per cent produced gas from the Maxon horizon. During 1942, the old Menifee " Cornif-erous" field, the Mariba-Denniston field, was redrilled between old wells, and although it did not produce any large amount of oil it did contribute 2018 bbl. In the oldest oil field in eastern Kentucky, the Ragland pool, operators are cleaning out abandoned wells and are using this oil for fuel oil. There is a possibility that some of this may be used in the future as distilled fuel oil. Eight wells were completed in 1942 in the Jackson County gas field. The development of Jackson County, which was started in 1934 and in which commercial quantities of gas were encountered at a depth of 1100 to 1200 ft., has become of importance in 1942 with the completion of eight wells, making a total of 24 commercial producing wells with an average rock pressure of 140 lb. At this time the gas is not being marketed. In the last year it has been found that these wells, which produce from the Niagaran dolomite ("Cornif-erous"), respond to acidizing and the production has been thus greatly increased. There has been less development in Estill and Lee Counties than for several years. Two wells were drilled in Greenup County, one of which had a show of oil in the Berea sandstone. One deep test, drilled by the Owens-Libbey-Owens Co. in Lawrence County, was dry. This well was drilled to a depth of 4975 ft. into the top of the Clinton shale sequence. Of the 202 wells completed in Floyd, Martin, Knott and Pike Counties, 187 were gas wells, 3 oil wells and 12 dry holes. In Floyd County 66 per cent of the gas production was from the Devonian-Mis-sissippian black shales, 53 per cent in Martin, 79 per cent in Knott and 65 per cent in Pike. This is probably the largest continuous gas field east of the Mississippi

Jan 1, 1943

By Robert L. Kidd

ONE time or another placer mining attracts the attention of a large number of people, because of the possible low initial investment, low operating cost, and quick returns. Much has been said about sampling and operating placer deposits but many are still inclined to jump at a property without giving much, if any, consideration to proper sampling. This statement does not apply to experienced mining engineers but I am hoping that readers will tear out this article and pass it along where it will do the most good and thus help to preserve the reputation of legitimate mining. It would appear that some people have an ability to sink test pits in high-grade gravel that is positively uncanny. One pit showing high-grade values proves to some property owners and promoters that the entire property will do the same. This is

Jan 1, 1937

By F. B. Harris

MINE surveying and engineering at the various properties of the United States Smelting Refining and Mining Company has developed and increased in importance steadily as mining methods have changed and expanded, both in the development of ore bodies and in the methods and styles of stoping. Most important to satisfactory engineering practice, and secondary -only to accuracy and precision, is the preservation of all data relative to surveys and calculations so that it is readily available for use at all times and in -such form that it is permanent, easily found, and usable. The first consideration for a proper, accurate, and practical start for surveys and efficient engineering at any property is an accurate triangulation net and system of co-ordinates. This has been our practice and the first step seas to select a base line, readily accessible and easily measured, situated preferably on an even grade where the difference of elevation between the two -end monuments was not too great and -the distance was long enough for practical use. Permanent concrete monuments were built for these base-line points so constructed that they could be easily recognized and were visible. Precise levels were run on this base 'line and the elevation (sea level datum) if possible was established at each end monument. The distance was carefully measured many times, back and forward, by using a tape that had been standardized by the National Bureau of Standards. The tape was supported at ,each 25-ft interval on stakes which had been brought to grade between each measuring point. All conditions were

Jan 1, 1948

By J. H. Lightfoot, Stuart E. Buckley

DEEP drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.1 The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen4,5,6 and by others,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems.9-17 It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 lb. per sq. in. Thus, at pressures of 2500 lb. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 600°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduction. The combined effects of pressure and temperature on condensation and vaporization of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpretation of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate systems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21.22 it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has

Jan 1, 1941

By Arch J. Alexander

Coal is produced, in commercial quantities, in thirty-five of the fifty-five counties of West Virginia. Oil and gas are produced, commercially, in forty-two counties. So, you may readily see that coal, oil and gas arc closely related as to production areas. Many of the West Virginia coal mines are studded with oil and gas wells, as drilling has been done in thirty-two of the coal bearing counties. When the drilling of oil and gas wells was placed under the regulatory control of the Department of Mines on June I, 1929, it was estimated, by the State Geological Survey, that 64,000 wells had been drilled in West Virginia and that 34,000 wells were then being operated as oil and gas producers. No records of many of these remaining 30,000 abandoned wells exist and some of them remain a standing menace to safety as our coal extraction continues. Of a total of 13,100 new wells drilled since June 1929, approximately 5200 have been drilled through coal measures. Approximately 7000 wells, which were drilled through coal measures, have been abandoned in the same period of time. Many of these wells were drilled prior to the enactment of the oil and gas laws. Prior to the enactment of the Oil and Gas Law, which established the Oil and Gas Division of thc Department of Mines in 1929, there had been several mine ex-plosions attributable to cutting into un- charted wells and the improper plugging of other wells. The most serious explosion was that of Mines No. 47 and No. 49 of the Consolidation Coal Co. in Marion Co., when one of the so-called plugged wells leaked or seeped through some 80 ft of strata to the coal bed elevation, filling the mine with gas, the gas being ignited, killing a good many men and wrecking two coal mines. Legislation, to combat well hazards to coal mines, was slow in coming. In 1928, R. M. Lambie, then Chief of the Dept. of Mines, got sufficient support from coal, oil and gas interests to get the legislature to pass our present oil and gas laws. These statutes not only protected the coal industry but went a long way toward conserving the oil and gas resources of our state. Before drilling for oil or gas on any tract of land, known to be underlaid with one or more workable seams of coal, the well operator is required to submit a map of the area showing the location of the proposed well, and to send a copy to the Dept. of Mines and a copy to the coal operator. If no objections to the location of the proposed well are made by the coal operator within ten days, a drilling permit and a number for the well are then issued and work may proceed. If, however, the location of the proposed well is objected to by the coal operator, on the grounds that the location of the well will interfere with present mine operations, projected workings, or otherwise cause a dangerous condition, the operator may file a written objection with the Dept. of Mines.

Jan 1, 1949

By Arch J. Alexander

COAL is produced, in commercial quantities, in thirty-five of the sty-five counties of West Virginia. Oil and gas are produced, commercially, in forty-two counties. So, you may readily see that coal, oil and gas are closely related as to production areas. Many of the West Virginia coal mines are studded with oil and gas wells, as drilling has been done in thirty-two of the coal bearing counties. When the drilling of oil and gas wells was placed under the regulatory control of the Department of Mines on June I, 1929, it was estimated, by the State Geological Survey, that 64,000 wells had been drilled in West Virginia and that 34,mo wells were then being operated as oil and gas producers. No records of many of these remaining 30,000 abandoned wells exist and some of them remain a standing menace to safety as our coal extraction continues. Of a total of 13,100 new wells drilled since June 1929, approximately 5,200 have been drilled through coal measures. Approximately 7,000 wells, which were drilled through coal measures, have been abandoned in the same period of time. Many of these wells were drilled prior to the enactment of the oil and gas laws. Prior to the enactment of the Oil and Gas Law, which established the Oil and Gas Division of the Department of Mines in 1929, there had been several mine explosions attributable to cutting into un- charted wells and the improper plugging of other wells. The most serious explosion was that of Mines No. 47 and No. 49 of the Consolidation Coal Co. in Marion Co., when one of the so-called plugged wells leaked or seeped through some 80 ft of strata to the coal bed elevation, filling the mine with gas, the gas being ignited, killing a good many men and wrecking two coal mines. Legislation, to combat well hazards to coal mines, was slow in coming. In 1928, R. M. Lambie, then Chief of the Dept. of Mines, got sufficient support from coal, oil and gas interests to get the legislature to pass our present oil and gas laws. These statutes not only protected the coal industry but went a long way toward conserving the oil and gas resources of our state. Before drilling for oil or gas on any tract of land, known to be underlaid with one or more workable seams of coal, the well operator is required to submit a map of the area showing the location of the proposed well, and to send a copy to the Dept. of Mines and a copy to the coal operator. If no objections to the location of the proposed well are made by the coal operator within ten days, a drilling permit and a number for the well are then issued and work may proceed. If, however, the location of the proposed well is objected to by the coal operator, on the grounds that the location of the well will interfere with present mine operations, projected workings, or other- wise Cause a dangerous condition, the operator may file a written objection with the Dept. of Mines.

Jan 1, 1948

By N. A. D. Parlee, E. M. Sacris

OVER 55 years ago, Sieverts and Hagenacker1 and Donnan and shaw2 made determinations of the solubility of oxygen in liquid silver, over a rather short range of temperatures (973° to 1125°C), using quartz bulbs, mainly at 1 atm. From the results of their investigations, Mizikar, Grace, and parlee3 plotted % O vs 1/T and obtained the following straight-line equation for solubility at 1 atm: log % O = 723.7/T - 1.0949 Recent work on the kinetics of the Ag-O2 system394 indicated there might have been some error due to reaction with the direct heated silica bulbs. Thus it became important to redetermine the solubility with the silver contained in a better refractory such as alumina, and by induction heating where the walls of the container were not so strongly heated. It was also desirable to extend the temperature range. A modified Sieverts apparatus of fairly standard type was used except that a special type of reaction tube was employed, Fig. 1. Dried argon with a guaranteed purity of 99.9 pet, and dried medical-grade oxygen with a guaranteed purity of 99.6 pet containing a little nitrogen, were the gases used. The measuring system consisted essentially of a manometer and a water-jacketed 100-cc gas buret with an open-end vertical tube parallel to the buret. This tube has the same diameter as the buret in order to give the same capillary effect on the mercury. A screw leveling device was used with the buret leveling bulb to help provide accurate pressure readings. A 2-mm ID capillary line connected the buret to the reaction chamber, helping to reduce the dead volume, which was determined with argon. The heating medium was a 2.5-kw output induction furnace. The induction coil was made of a 3/16-in. copper tubing with eight turns and an inside diameter of 4 cm. The reaction bulb was made of a quartz tube 18 cm long and 3 cm in inside diameter, Fig. 1. Inside the quartz tube were two alumina crucibles (Mor-ganite Triangle RR, XN10 and XN5) one inside the other. Below these two was an alumina disk. The disk prevented the corners of the outer crucible from expanding against the quartz tube. The solid sample (99.994 + pet Ag), which had been previously cleaned by air oxidation and repeated removal of scum, was placed inside the inner crucible. An alumina disk with a hole at the center covered the two crucibles. In order to decrease the dead volume, an evacuated quartz "filler" tube was placed on top of the crucible cover. The part of the reaction tube above the spherical joint was made up of Pyrex glass with a flat glass top. It was here that a prism was placed to facilitate the use of an optical pyrometer, previously calibrated at the freezing point of silver. This type of reaction bulb and furnace assembly was specially designed for this work, and used in preference to the relatively new water-

Jan 1, 1965

By Luther Wagoner

HAVING given in a former paper1 the results of assays of sea-water, bay-mud, dredgings from San Francisco bay, etc., and' believing it might be interesting to extend the work to include' some deep-sea dredgings, I procured from the Smithsonian Institution six samples taken by the U. S, steamer Albatross, and marked as follows

Jan 9, 1907

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By M. A. Steinberg, J. Wulff, R. Kamm

In a previous paper1 from this laboratory, the development of a lead grid method for exploring the distribution of strain and density within metal powder compacts was described. In that work thin lead foil with rectangular holes cut at regular intervals was inserted with the powder fill, the arrangement pressed and then radiographed to permit measurement of the deformation of the lead grid. Densities at each grid element obtained in this manner were plotted as a function of the die dimensions. From such plots it was found that the densest part of a compact pressed from one side (the top) is at the top outer region and the least dense at the bottom outer region of the specimen. The axial density maximum occurs more often nearer the bottom than at the top. As a result of such exploratory measurements, it appeared reasonable to conclude that variations in density could be attributed in the main to die wall friction. Thus compacts of large diameter appeared relatively uniform in density except where the die fill had been uneven. Finally it was found that lubrication of the finely finished die cavity contributed more to magnitude and uniformity of density within the compact than interparticle lubrication. Since publication of the above results, it was found that circular-hole grids could be more accurately made and, when deformed within the powder, more readily measured and analyzed. Much of the former work was repeated and new results which include the effect of lubrication, compact height, pressure, speed of pressing and vacuum pressing are reported in the present paper. Circular-hole Grids and Analyses OF Radiographs Commercial lead sheet 0.008 in. in thickness was used in all the work reported. The 0.0938-in. diam holes were punched in the sheet on 1/8-in. centers to an accuracy of 0.001 in. The finished grid used contained eight or more holes in a row and from I to 24 rows. The lead sheet was clamped between two pairs of brass strips bolted to a small milling machine table which was itself bolted to a bench in correct position near a vise which held the punch. Travel of the lead grid in two dimensions was controlled by two steel lead screws calibrated in 0.001-in. divisions. A stripper plate was used on the punch to avoid distortion of the lead foil. A high carbon-high chromium (chrocar) one-piece steel die was used throughout the work. The die cavity was 1.125 in. in diam and the clearance between plungers and die wall was 0.001 in. The die was also used for pressing from both ends with two long plungers. Finally, lapping of die and plungers gave a surface whose rms value On an Abbot profilometer was 5 micro-in. The die walls and plungers were, except where otherwise noted, lubricated with a stearic acid suspension in benzene. This was put on in multiple layers and allowed to dry before filling the die.

Jan 1, 1949

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By T. H. Dunn, P. L. Menaul

This paper discusses the results of an investigation made to develop a method of combatting corrosion of subsurface oil-well equipment caused by brines containing hydrogen sulphide. Carbon monoxide, aldehydes, and certain cyanide compounds were found by laboratory tests to effectively inhibit corrosion of steel by sulphide brines. Experiments were made for one year in eight wells in West Texas fields using formaldehyde as an inhibitor. It was found that the inhibitor treatment successfully prevented the severe corrosion previously experienced in these wells, and effected important net savings in operating costs. Introduction Corrosion of oil-field equipment has long been a problem in areas producing sour crudes. These areas include the major fields of Arkansas, Western Kansas, West Texas and New Mexico. Corrosion in these fields is caused primarily by the chemical action of hydrogen sulphide in the presence of water and by electric currents entering the wells through flow lines. Hydrogen sulphide is noncorrosive to iron or steel in the absence of water but under the usual conditions prevailing in oil wells where more or less water is present, hydrogen sulphide is very corrosive. This type of corrosion occurs over the pH range below 9, which includes all natural oil-field brines. If air is present in addition to hydrogen sulphide and water, corrosion proceeds at an extremely rapid rate. It was reported several years ago that a string of oil-well tubing was literally dissolved within 50 days where an air lift was used on a well producing considerable water and hydrogen sulphide. Air is generally absent in wells producing sour crude. After hydrogen sulphide corrosion starts, it proceeds with increasing severity and its correction becomes progressively more difficult. This characteristic of sulphide corrosion has been attributed to the formation of galvanic couples between the iron and steel equipment on one hand and the products of corrosion on the other.' Severe corrosion of subsurface oil-well equipment leads to a multitude of troubles. In addition to destruction of costly equipment, producing sands often are damaged by flooding with water leaking through corroded casing; bad mechanical conditions may develop in a well due to obstructions caused by corroded equipment lost in the hole, or partly collapsed casing; pumping operations are interfered with, and severe emulsification problems may result from the homogenizing action of corroded balls and seats.% A typical case of severe corrosion caused by hydrogen sulphide was reported in Howard County, Texas, where it was necessary to pull tubing once a week to repair leaks after the tubing had been in use for only one year. On one well in this area a string of tubing was pulled 11 times in 8 months; 11 joints of tubing being replaced because of leaks. In Ector

Jan 1, 1946

By Edward B. Hughes, Frank G. Norris

OXIDATION is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the most recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a, compound such as C02-or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct, method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is introduced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steelmaking," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath. A recent article12 reviewing the current

Jan 1, 1948

By AIME AIME

EVEN in the choice of his birthplace and parents, Donald B. Gillies indicated clearly the trend of his professional career. He was born on Nov. 4, 1872, at Bruce Mines, in Ontario. His father and mother came from the Isle of Skye, Scotland, to Nova Scotia, moved from there to Canada, and finally settled in the copper country in the northern peninsula of Michigan, where the senior Mr. Gillies followed mining as an occupation. Donald's early education was in the public schools and he graduated from Linden Lake (Mich.) high school in 1890. Following the family interest in mining he entered the Michigan Mining School, now Michigan College of Mining and Technology. There he was the rare student who excelled both in athletics and scholastic work. On the athletic field he was a crack football player and track roan. As early as 1890 lie established a record of 10 sec-

Jan 1, 1938

By R. C. Edwards, T. G. Kirkland, Will Mitchell

A scrubber of new design has been invented for the beneficiation of glass and chemical sands. The machine is described and its capacity and metallurgical efficiency compared with the performance of other sand cleaning devices. THREE years ago, when the Process Research Laboratory at Allis-Chalmers Manufacturing Co. sought a remedy for the increasing cost of disposing of great quantities of spent sands from foundries, R. C. Edwards developed a continuous inclined paddle scrubber which removed a substantial amount of the charred coatings from the grains with a surprisingly small amount of degradation of the sand itself.' The satisfactory results obtained on foundry sand, using this piece of equipment in conjunction with classification, suggested that a similar procedure could probably be applied to the cleaning of other sands, such as those required by the glass and chemical industries. This paper describes the flowsheet and the results of tests performed on impure natural sands. The four materials tested were silica sands obtained from widely separated geographical areas. Three of the sands tested contained various amounts of iron oxide and the fourth an excessive amount of calcareous bonding material. The iron oxide was present predominantly in the form of grain coatings, which were scuffed by the paddle scrubber, and in all cases a product was manufactured which would meet one of the sets of specifications imposed by the glass industry.' The Edwards paddle scrubber used in these tests consists of a rubber-lined steel cylinder 18 in. in diam and 48 in. long, mounted on a frame so that its slope can be varied 5" to 35" from horizontal. This variable slope permits controlled flow of material through the machine. Rubber paddles rotate inside the cylinder and are secured to a center shaft 2 in. square, which extends through the entire length and is turned at both ends so that it can be supported by sleeve bearings centrally fixed in the end plates of the shell. At the upper or feed end it extends through the bearing on the end plate into a sheave, to which the motor drive is connected by means of Texrope transmission. The four sets of paddles mounted on the shaft, two in each set, are made of rubber belting, 1/4 in. thick, 9 in. wide, and 16 in. long. The two paddles in each set are secured on opposite sides of the square shaft, but in the same longitudinal position along the shaft axis. In other words, the two paddles in the set operate 180" apart. Each successive set is mounted 90" from the preceding one. One end of each paddle is bolted to the square shaft and the other weighted by a steel bar, lx1 1hx9 in. long, which is attached about Yz in. from the outer tip of the paddle. By centrifugal force at proper shaft speed, these weights force the paddle surface to rub smoothly against the rubber lining of the cylinder. During operation, the sand forces its way between the paddle face and the surface of the cylinder, providing the necessary abrading action as the pulp flows by gravity down the length of the cylinder. The capacity of the machine is limited by the amount and the hardness of the coating material and by the quality of product desired. The degree of scrubbing is governed by the retention time in the scrubber, which in turn may be changed by varying the feed rate, water content of the feed, and

Jan 1, 1953