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By Joseph J. Becker

RECENTLY the "oriented growth" hypothesis of recrystallization textures has been receiving considerable attention. According to this view, "whenever a new generation of grains is growing in a highly oriented matrix . . . one may assume . . . that from among available nuclei of a great variety of orientations those with suitable orientation relationship with respect to the matrix have by far the highest rate of growth (oriented growth) and will, therefore, predominate."' This statement includes primary recrystallization of single crystals and of polycrystalline materials showing strong deformation textures as particular cases. While the phenomenon of oriented growth undoubtedly does operate, and may be of importance in coarsening or secondary recrystallization, the writer feels that its extension to primary recrystallization is a different matter. Several aspects of this phenomenon may be pointed out which are difficult to rationalize on the basis of oriented growth. In recrystallizing deformed single crystals of alpha brass, Maddin, Mathewson, and Hibbard2 found that the twin composition planes of the recrystallized grains were parallel to the three operative slip planes they observed, and not to the fourth octahedral plane. The writer's current work seems to indicate further that when only one or two slip systems can be seen to operate, the recrystallized grains are aligned only with those slip planes actually observed. This behavior could hardly be accounted for by oriented growth, because on the latter basis the recrystallized texture of a deformed single crystal should certainly have the same symmetry as the crystal itself. Growth rates could not be expected to distinguish between crystallogra- phically equivalent directions, unless the presence of a visible slip system vastly increases the growth rate in the appropriate direction. This seems unlikely. These relationships were observed by the writer only when considerable care had been exercised before annealing to etch away the effects of cutting out the centers of tensile specimens with a jeweler's saw and to etch off the ends of compression specimens. When these.precautions were not taken, nu-cleation inevitably appeared to occur at the saw cuts or at the ends, and the resulting orientations never showed a [111] rotation but appeared quite random. The provision of many nuclei of many orientations did not enhance the correlation, but destroyed it. Recrystallization textures are sometimes strongly dependent on annealing temperature, which would imply that the anisotropy of growth rates is a suddenly varying function of temperature. This might be regarded as unlikely. Recrystallization textures can be strongly dependent on the degree of deformation. If textures are to be explained by selective growth from among nuclei of all orientations, it is difficult to see how the recrystallization process could have any dependence whatever on the manner or degree of deformation. It is felt that the above points should be considered before the oriented growth hypothesis is applied to primary recrystallization, with the necessary complete divorce of the mechanism of recrystallization from the details of the deformation process. References 1P. A. Beck and H. Hu: Reply to discussion of their paper on Recrystallization Texture and Coarsening Texture in High Purity Aluminum. Trans. AIME, 188, 1057; Journal oF Metals (Aug. 1950) TP 29083. 'R. Maddin, C. H. Mathewson, and W. R. Hibbard, Jr.: The Origin of Annealing Twins in Brass. Trans. AIME, 185, 655; Journal of Metals (Sept. 1949) TP 26763.

Jan 1, 1952

By Carle R. Hayward

This work was first undertaken in the metallurgical laboratory of the Massachusetts Institute of Technology in 1907 by L. A. Dickinson, E. Phelps, and V. S. Rood, under the author's direction. They attempted to determine the diagram for the system Cu2S-MiS, but several inexplicable results were obtained. The following year, P. H. Mayer with Mr. Dickinson carried on some experiments with nickel sulphide and found that the molten material slowly lost sulphur until it reached a composition corresponding to the compound Ni3S2, established by Bornemann.l At this point the composition remained stable. The freezing points of the mixtures gradually fell off with the loss of sulphur. Since the above facts seemed to explain the erratic results obtained in the first experiments, Mr. Mayer with F. Jaeger attempted in 1910 to establish a correct equilibrium diagram for the Cu2S-Ni3S2 series. They prepared pure Cu2S and Ni3S2 and determined the cooling curves for various mixtures. The fusions were made in a platinum resistance furnace and the temperatures were measured with a platinum-iridium thermocouple connected with a Sullivan galvanometer. The curve was established for mixtures containing more than 40 per cent. Cu2S, but they were unable to determine certainly the direction of the curve beyond that point. Nothing further was attempted with this series until the present year, when the work was carried to a successful conclusion with the assistance of A. Butts, Jr., and E. H. Weil. The results of this work are given in the following pages. Preparation of Cu2S.—A piece of cathode' copper from the Buffalo plant of the Calumet & Hecla Co. was cut into shavings by a shaper and converted into sulphide by heating in boiling sulphur. A porcelain casserole was used for the purpose, the heat being furnished by a Bunsen burner. It was found that after boiling in the sulphur for an hour the copper shavings were completely converted into sulphide. The liquid sulphur was then poured off, leaving the solid sulphide in the casserole in

Jan 1, 1915

By Roy E. Thomas

Soon after the Waelz p1an.t for the fire concentration of low-grade zinc ores was put into operation in the early part of 1929 at Katowice, it was found that the conveyor equipment for transporting the hot residue from the furnace dust chambers was inadequate. Hand tramming with water cooling was used for a time, but that method was injurious to the workmen as well as costly. The problem was to find some practical mechanical means of conveying flue dust at temperatures of from 450" to 600°C. as it was drawn from the dust chambers. After considerable preliminary investigation it was decided to install pneumatic equipment for conveying the hot materials to a central mixing plant, where it would be mixed with slime and from which it would be returned to the furnace feed hoppers. The first pnenmatic equipment was installed in 1930, and has been in successful operation since that time. The pneumatic method of transportation has shown a considerable saving in operating costs over the former methods of dust handling and a decided improvement in working and hygienic conditions at the plant, through the elimination of the dust hazard. Additional pneumatic equipment mas installed in 1933 for conveying the furnace fume from the baghouses to the roaster plant. At the same time pick-up lines were provided for collecting the cleanings from the vertical and horizontal cooling pipes that are between the furnace dust chambers and the baghouses. The latter installation has practically eliminated a dusty and costly hand-tramming operation. A third extension was made to the pneumatic system in 1938 for conveying 'the zinc-lead-cadmium fume from the roaster-plant baghouses and flues to a new re-treatment plant for secondary products. The success of pneumatic conveying at the Waelz plant was the determining factor in the decision to install another pneumatic unit at the Saeger zinc-roasting and sintering plant. The new unit at Saeger was installed early in 1938 for the transportation of flue and Cottrell dust, small amounts of flotation concentrates to the sinter machines, and

Jan 1, 1944

By Arnold Hague

At the Buffalo meeting, October, 1888, Dr. Raymond presented a paper entitled: "Soaping Geysers" (p. 449 of the present volume), in which he called attention to the use of soap by tourists to cause eruptions of several of the well-known geysers in the Yellowstone Park. Incorporated in this paper appears a communication received from me, written from camp in the Park, in reply to some inquiries on the subject. The letter discussed somewhat briefly the means employed by visitors to the Park to hasten the eruptions from hot springs and reservoirs of hot water, which remain dormant for days, or even weeks or months, at a temperature near the boiling-point, without any display of geyser-action. As the paper has called forth considerable comment, I desire to elucidate one or two points in relation to the temperature of the springs, and to answer some inquiries about the composition of the thermal waters. In the summer of 1885, a Chinaman, employed as a laundryman for the accommodation of the tourists at the Upper Geyser Basin, accidently discovered, much to bis amazement, that soap thrown into the spring from which he was accustomed to draw his supply of water produced an eruption in every way similar to the actual workings of a geyser. Tourists with limited time at their command, who had travelled thousands of miles to look upon the wonders of the Yellowstone, soon fell into the way of coaxing the laundryman's spring into action, to partly compensate them for their sore disappointment in witnessing only the periodical eruptions of Old Faithful. Successful attempts upon this spring soon led to various endeavors to accelerate action in the dormant and more famous geysers. In a short time, so popular became the desire to stimulate geysers in this way, that the Park authorities were compelled to enforce rigidly the rule against throwing objects of any kind into the springs. In connection with a thorough investigation of the thermal waters of the Yellowstone Park and the phenomena of the geysers, I undertook a number of experiments to ascertain the action of soap upon the waters and to determine, if possible, those physical conditions of various pools and reservoirs which permitted the hastening of an

Jan 1, 1889

By R. F. Stahl, W. A. Martin, R L. Huntington

A marked gravitational segregation of liquid has been observed to take place in a number of volumetric fields toward the later stages of their oil-producing periods. This phenomenon has been pronounced in thick, highly permeable sand formations such as those of the wilcox zone in Oklahoma City. This observation has prompted considerable research directed toward the semiquantitative determination of the equilibrium saturation distribution of oil vertically throughout a formation at final depletion. In this paper, data are also presented showing the transient distribution of liquid at different stages of the depletion period. Other experimental results show the effect of temperature on the drainage rates of water, Wilcox crude oil, and a close-cut heptane fraction. Intermittent drainage of liquid produced saturation gradients that might well be expected from the flow theories involved, Yields of the various liquids varied from 50 to 75 per cent of the original fluid content of the sand-packed (4 in. by 8 ft.) vertical tube. Introduction In certain volumetric Oil fields the performance of the reservoir during the latter part Of its producing life is governed to a large extent by the downward movement of liquid due to the force of gravity. This is especially true of formations having thick or tilting beds of uniformly high permeability, free of shale breaks. Laverett4 and Katz3 have presented original data and discussed the theory relating to the capillary and gravitational forces acting On liquids contained in a sand body. These investigators have pointed out the importance of such studies in the estimation of future reserves as well as the original fluid content of a reservoir. In this previous work, no data have been reported showing the history of saturation distributions during the drainage period. Since a knowledge Of these transients is helpful in obtaining crude Oil from such a reservoir, the authors have obtained these data during this investigation. Experimental Apparatus The drainage tests were carried out in two vertical tubes, 8 ft. high and consisting of 2-in. and 4-in. standard wrought-iron pipe, respectively. Each tube was equipped with a water jacket, which could be kept virtually isothermal ( ± 1.0ºF.). A diagrammatic sketch of the 4-in. tube and its auxiliaries is shown in Fig. 1. At 6 in. above the base of the tube, and at every foot above this point, core nipples were inserted through the water jacket. These nipples were closely fitted with steel-plug inserts during each drainage run. At the end of the run, these inserts were removed so that cores could be obtained from the sand-packed tube.

Jan 1, 1943

By R. F. Stahl, W. A. Martin

A marked gravitational segregation of liquid has been observed to take place in a number of volumetric fields toward the later stages of their oil-producing periods. This phenomenon has been pronounced in thick, highly permeable sand formations such as those of the wilcox zone in Oklahoma City. This observation has prompted considerable research directed toward the semiquantitative determination of the equilibrium saturation distribution of oil vertically throughout a formation at final depletion. In this paper, data are also presented showing the transient distribution of liquid at different stages of the depletion period. Other experimental results show the effect of temperature on the drainage rates of water, Wilcox crude oil, and a close-cut heptane fraction. Intermittent drainage of liquid produced saturation gradients that might well be expected from the flow theories involved, Yields of the various liquids varied from 50 to 75 per cent of the original fluid content of the sand-packed (4 in. by 8 ft.) vertical tube. Introduction In certain volumetric Oil fields the performance of the reservoir during the latter part Of its producing life is governed to a large extent by the downward movement of liquid due to the force of gravity. This is especially true of formations having thick or tilting beds of uniformly high permeability, free of shale breaks. Laverett4 and Katz3 have presented original data and discussed the theory relating to the capillary and gravitational forces acting On liquids contained in a sand body. These investigators have pointed out the importance of such studies in the estimation of future reserves as well as the original fluid content of a reservoir. In this previous work, no data have been reported showing the history of saturation distributions during the drainage period. Since a knowledge Of these transients is helpful in obtaining crude Oil from such a reservoir, the authors have obtained these data during this investigation. Experimental Apparatus The drainage tests were carried out in two vertical tubes, 8 ft. high and consisting of 2-in. and 4-in. standard wrought-iron pipe, respectively. Each tube was equipped with a water jacket, which could be kept virtually isothermal ( ± 1.0ºF.). A diagrammatic sketch of the 4-in. tube and its auxiliaries is shown in Fig. 1. At 6 in. above the base of the tube, and at every foot above this point, core nipples were inserted through the water jacket. These nipples were closely fitted with steel-plug inserts during each drainage run. At the end of the run, these inserts were removed so that cores could be obtained from the sand-packed tube.

Jan 1, 1943

By V. H. Wilhelm

The outstanding event in the California petroleum industry during 1931 was the continuance of curtailment of crude oil production, which directly reduced drilling and well repair activities. Although all objectives were not attained, a very close balance between supply and demand was maintained during the period of maximum requirements, but the decline in intercoastal and export shipments caused an overproduction during the last half of the year, which indicated that California production would necessarily suffer further curtailment after the end of the year. A new peak in potential crude oil production of 1,187,600 bbl. per day was reported in August and at the close of the year the California potential was 1,069,000 bbl. per day, the shut-in light oil amounting to practically 425,000 bbl. per day and the shut-in heavy oil amounting to about 150,000 bbl. per day. Fig. 1 depicts these conditions and also shows the production and curtailment situation since the inception of proration in California. The December, 1931, potential figure of 1,069,-000 bbl. per day was arrived at after the most careful deliberation by a number of committees, selected to check the potential of practically every well in the state. Continued overproduction in the first three months of 1931 and the inadvisability of building more storage, together with the inability to obtain the proper amount of curtailment in town-lot fields, such as Long Beach, Santa Fe Springs and Playa del Rey, prompted the major oil companies to inaugurate a price reduction in crude oil. This cut caused prices to reach the lowest levels since 1915, and instigated the formation of an oil sales agency, composed of independent operators, which is known as the Oil Producers Sales Agency. The purpose of this organization is to procure a market for its members at reasonable prices, advise them of market conditions and aid them in controlling the amount of oil available for sale. Marketing of oil produced by members began on June 1 and independents controlling" about 160,000 bbl. per day of production had become members by the end of the month.

Jan 1, 1932

By R. M. Treco

THE thermal expansion of pure beryllium was first investigated by Hidnert and Sweeneyl in 1925 on a single cast specimen stated to be of 98.9 pct purity. A study of the coefficients of expansion by X-ray methods has recently been made by P. Gordon' on powder obtained from the Brush Beryllium Co. assaying 97 wt pct beryllium with about 2 wt pct oxygen as an impurity. The present work pertains to about the highest purity metal obtainable from the Brush Beryllium Co. This metal was in the form of lumps which were remelted and cast in a high-vacuum induction furnace. Expansion data in this paper deal with beryllium extruded into bars of rectangular cross-section 4x1/2 in. and the anisotropic expansivity of a large cast single crystal. Analysis of the cast metal after extrusion indicated a beryllium assay of 99.28 pct. Impurities were 0.170 pct Fe, 0.140 pct Al, 0.014 pct Mg, 0.086 pct Si, 0.020 pct Cu, 0.020 pct Mn, 0.007 pct Ni, 0.007 pct Ca, 0.080 pct C, 0.179 pct 0, (as BeO). Part I—Extruded Metal Thermal expansion measurements were obtained with a fused quartz-tube differential type dilatom-eter3 on specimens cut from the extruded sections in longitudinal and transverse directions. Specimens were machined to a diameter of 0.250 in. and a length of 3.000 in. One sample from each direction was vacuum annealed for 1 hr at 800°C. The dilatometer tube was placed in a vertical tube furnace having a uniform temperature zone which was twice the length of the sample. Average time for a complete thermal cycle to 500°C was 18 hr. Temperatures were observed with two chromel-alumel thermocouples attached to the sample about 1 M in. apart. The accuracy of temperature measure-ment was ± 0.25°C. An argon gas atmosphere sur-rounded the specimen to prevent oxidation of the beryllium. Samples were identified as shown in table I. Results - The original plan included measuring expansion up to 1000°C, but the first two runs on sample No. 5 showed that a permanent contraction occurred from

Jan 1, 1951

By John E. Carr

A bewildering variety of continuous thickeners and clarifiers are used in mineral industries and other heavy industries. General topes arc: ? Conventional thickeners ? Thickeners with flocculating feedwells ? Solids contactors ? Tray thickeners ? Lamellas ? Conventional thickeners with Lamellas ? High flow, fluid bed thickeners These units must be adapted to varied applications. They must provide operating flexibility to meet process needs. Such factors multiply the decisions which must be made prior to the selection of a thickener. The seven types of thickeners listed above, with their variations, share design concepts which limit their application and which can be used to evaluate their performance. Some of these arc: ? Feed velocities must be limited and/or controlled. ? Natural or reagent flocculation is necessary. ? Horizontal settling area is the basis for capacity. ? Overflow velocities must be limited and. or controlled. ? A controlled underflow is necessary. Thickener selection is the application of these needs to the basic process concepts. The basic function of a thickener, in the minerals industry, is the separation of a thickener sludge containing fine solids from water. In addition to this primary separation function, others include: ? Separation of solids from water ? Separation of flocculated solids from slimes ? Storage of solids ? Control of percent solids ? Storage of water ? Process control by absorbing fluctuations in feed ? Process control by increase in head clue to the depth and percent solids of the thickened sludge. Most thickener designs, suitable to minerals applications, are based on the separation of minus 65-mesh, 2.7 specific gravity solids containing slimes. These designs are routinely adapted to coarse and or denser materials. Materials of lower specific gravity such as coal, wood, char, some chemical precipitates and organics act Hike slimes if a thickener is used. Perhaps the most conservative approach to sizing and application is the use of comparative data from similar plants or similar industries. Thickeners are-routinely used in a great number of industries from which there is good historical information available. In the minerals industry, thickeners are used in: clay sizing, coal refuse, heavy media, copper concentrates, copper tailings, gold flotation concentrates, and countercurrent decantation for cyanidization in gold and CCD in uranium. Concentrate and tailings thickeners are used in iron ore plants, and concentrate and tailings units in lead-zinc plants. In addition, there arc thickeners designed to handle lime mud; limestone concentrates and tailings; phosphoric acid; potash; and rutile concentrates. Thickeners are, in addition, widely used in gravel plants for water reclamation. This gives excellent data on clay settling in some cases. Thickeners are used extensively for slurries generated by flue dust from wet scrubbers. Thickeners in flue dust applications are operating with considerable variations, treating blast furnace dust. BOF flue dust, and wood char. Similar applications are met in the power industry with fly ash and SO2 scrubber systems. Even though field data is preferred, such data has limitations as listed: ? Flowsheets are seldom identical. ? Data is often incomplete or limited. ? Ores vary significantly. ? Operating needs are changing. For these reasons, mathematical and theoretical methods are needed for application of field data to a specific project. In addition, laboratory data for similar projects and, if possible, laboratory data on a representative sample should be used to specify the thickener. There is a great volume of thickener literature. The references for this paper, along with their references, and past AIME papers provide excellent background. Older literature can be reviewed in light of current methods. It is interesting to note that the requirements for higher flow rate designs, more extreme flocculation systems, etc., can be logically introduced by reading Gaudin's Sections on Flocculation and Thickening, which was written before field installations could illustrate all of his ideas. The problem, then, is to select hardware which will take into consideration the functions of flocculation, separation of the solids, water clarity, control of the underflow, and control of the overflow. Reliable operation and simple control are customary.

Jan 1, 1979

By Valentin R. Garfais

The world's petroleum production in 1928 is estimated at 1,322,896,-000 bbl., an increase of about 62,000,000 bbl. over 1927, as compared with an increase of over 133,000,000 bbl. in the previous year. The daily average was close to 3,600,000 bbl., of which the fields on the American continent produced about 84 per cent. The most important development during the year has been the partial success of the attempts to temporarily control production without appealing to legislation and, as a consequence, the increasing realization that, in order to reach a permanent cure for this situation, some form of legislation is necessary to' make possible the conservation of the oil supply and the stabilization of the industry. The importance of such a control over American production is not merely local but worldwide, as the American oil supply is now and for years to come will be the controlling factor of the industry. United States.—Production in the United States, which in 1927 increased about 15 per cent. over the previous year, remained practically stationary in 1928, the total being estimated at 902,000,000 bbl., or 68.2 per cent. of the world's output. This uniformity in production during the last two years was due primarily to the curtailment of output from wells already drilled, it being estimated that the available or shut-in production at the end of the year was close to 500,000 bbl. per day, or equivalent to the combined production of Venezuela and Russia, the countries ranking second and third. Venezuela.—With a production estimated at 106,000,000 bbl., Venezuela has trebled its output in the last three years. The increase in 1928 was 43,000,000 which placed this country as second in rank, a position which it should easily maintain for years to come. The output could have been considerably larger had not the oversupply in the United States made it advisable for Venezuelan operators to enter into tentative conservation agreements. Russia.—In Russia, production has doubled in the last five years, and reached a new peak in 1928 with an output estimated at 87,800,000 bbl., or an increase of 10,000,000 bbl. over the previous year. Difficul-

Jan 1, 1929

By L. C. Morganroth

Discussion of the paper of L. C. MORGANROTH, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 475 to 481. DAVID B. REGER, Morgantown, W. Va.-I notice in the third paragraph of the first page of the paper, that in mentioning the clays of the Pottsville series, the author says: "The bed of clay found in the latter formation is unique in that flint clay is practically restricted to it. (A variety of flint clay is occasionally found in these upper deposits but this is in such small amounts as to be negligible."). If the author wishes to confine himself to the fire clays of Pennsylvania, as the title seems to indicate, I have nothing to say, but if he wishes to include a discussion on fire clays of the adjoining States which the. subsequent paragraphs of his paper seem to indicate, then I wish to call attention to the fact that there are large and extensive deposits of fire clay in the Allegheny series, immediately overlying the Pottsville in the northern counties of West Virginia. These fire clays have been studied carefully, and described in several reports of the West Virginia Geological Survey, first in the report on Ohio, Brooke, and Hancock Counties, in the northern part of the State; described later ,in the report on Monongalia, Marion, and Taylor Counties, and in the report on Preston County, which followed. In these latter counties (Monongalia, Marion, Taylor, and Preston) there are some beds of fine fire clay, varying in thickness from 6 to 10 or 12 ft., with a content of only 2 or 3 per cent. of fluxing ingredients, and these are of the typical Savage Mountain appearance and also have the typical Savage Mountain fracture. They have been prospected, but not mined a great deal. Several of them have been tested in blast furnaces and furnaces for other purposes, in glass-manufacturing plants, also for firebrick, arid have been found to be very good. They are simply awaiting development, and I merely want to call attention to the fact that there are plenty of them in the Allegheny series still above the Pottsville in West Virginia. There are two or three valuable seams which I have seen in person and have had analyzed in our laboratory.

Jan 5, 1916

By R. C. Mahon

THE Homer iron-ore mine is at Iron River, Mich. Because it covers a large area, 400 acres, and because there was a considerable depth of water in the glacial drift above most of the ore bodies, this mine has presented a number of unusual and often difficult operational problems. The purpose of this paper is to discuss a few of the most important problems encountered. SURFACE WATER Mining on this property was started on one 40-acre tract. The ledge in this area was the highest on the property and, although it was a real problem, water could be handled by underground pumping. During the first period of mining, drifts were driven just under the ledge and holes were drilled through to the surface material. In later years these drifts have been extended wherever possible. Although these drifts assisted in the drainage problem, it was evident they would not be sufficient alone. Before mining on a large scale could be started on this property, the water problem had to be solved. A number of test holes were put down to the ledge, and showed that there was an average 150 ft. of water-saturated glacial drift above the ledge over the rest of the mine. The upper 70 ft. was gravel and sand and the lower 80 ft. clay and hard pan, with some narrow seams of sand and gravel. It was evident that the water above the clay seam could not be drained off through openings in the ledge and for that reason it was decided to install surface drainage wells. This method of drainage was entirely new at that time and was pioneered at the Homer mine. The sinking of the first well was started in June 1929. Immediately following the first well a number of wells were sunk, but only to the top of the clay seam. This was done with the idea that a greater capacity could be obtained in a shorter time from gravel seams where the water flowed more freely and that the cost of pumping the water above the clay seam would be considerably less than if the wells had all been sunk to the ledge at once. Before the drainage of surface water was started, 1200 gal. per min. against a head of 800 ft. was being pumped from the mine. By March of 1932, with five surface wells in operation, the mine pumping had been reduced to 150 gal. per min. At this time we were pumping 5000 gal. per min., under an average head of 110 ft. from the surface wells. The total pumping costs were 30 per cent less than in 1929 because the greater capacity was being pumped at a much lower head. From 1932 to 1936 the mine was idle and all surface pumping was stopped. Since 1936, 10 new wells have been added with a total pumping capacity of 8000 gal. per min. at the present time. The water level has been lowered 70 ft. since surface pumping was started in 1929, and it is now approximately at the top of the clay. To remove the water below the clay seam, 11 of the 15 wells were sunk to the ledge.

Jan 1, 1945

By R. V. Mrazek, F. E. Block, S. B. Knapp

The mixed homogeneous and heterogeneous kinetics of the thermal decomposition of tungsten hexacarbonyl were studied by employing a batch reactor. The system was such that a sample of tungsten hexacarbonyl could be injected into the preheated reactor, and the progress of the reaction followed by a simple pressure measurement. Both the homogeneous and heterogeneous reactions were found to be first order, and approximate activation energies were determined for each reaction. It is shown that the dis-proportionation of carbon monoxide to give carbon and carbon dioxide cannot be the source of carbon in tungsten deposits prepared by this reaction. The kinetics of the thermal decomposition of tungsten hexacarbonyl have been investigated as part of a continuing study by the U.S. Bureau of Mines on the decomposition of organometallic compounds. Reactions involving the thermal decomposition of metal carbonyls have a potential application in the preparation of pure metals and fine metal powders. Indeed, it was these applications which provided the impetus for much of the early work involving the carbonyls of nickel1 and iron.' The relative lack of study of other metal carbonyls can be traced to the comparative difficulty in synthesizing these compounds. The most common use for tungsten hexacarbonyl has been as an intermediate in vapor-phase plating.7'8 However, attempts to obtain a carbon-free deposit of tungsten by this method have not been successful, and some investigators have taken advantage of the carbon contamination and used this process to form tungsten carbide deposits.lo Other investigators have studied the thermodynamic properties11"14 and molecular structure of tungsten hexacarbonyl. However, very little is known about the kinetics of this thermal decomposition, the mechanisms involved," or the source of carbon in the resulting plate. In contrast, studies have been made of the kinetics of the thermal decomposition of nickel tetracarbonyl, iron pentacarbonyl, and molybdenum hexacarbonyl.'l It has been found that these thermal decompositions occur by a mechanism which is partially heterogeneous in nature. Information available on the equilibrium constants for the decomposition of tungsten hexacarbonyl was used to determine a temperature range, 500" to 560°K, in which the reaction could be expected to be essentially complete. APPARATUS The apparatus used allowed the injection of a sample of tungsten hexacarbonyl into a preheated batch reactor and the use of a simple pressure measurement to follow the progress of the reaction in the sealed reactor. The pressure was sensed by means of a pressure transducer (Consolidated Electrodynamics Corp., 0.3 pct)* capable of operating at the *Reference to specific products is made to facilitate understanding and does not imply endorsement of such brands by the Bureau of Mines._______ reaction temperature. This type of sensing element was chosen to avoid the problem of condensation of the sublimed carbonyl in the capillary tubing leading to any type of remote pressure-sensing device. stirring was provided by rotating the entire apparatus. Glass beads placed in the reactor provided a pulsating agitation. To minimize thermal gradients in the reactor walls, the reactor was constructed of aluminum. The support tube which held the reactor in the furnace was thin-walled stainless steel to minimize heat conduction out of the reactor. As a result of these measures, a nearly uniform temperature (°C) was maintained throughout the reactor. Fig. 1 is a schematic diagram of the apparatus. The small gear motor rotated the entire apparatus at about 200 rpm. The bearings shown at the ends of the air cylinder were perforated to allow air to be fed to the charging piston and to allow inert gas to be fed to the reactor during the preheating period. The sample was simultaneously injected and sealed inside the reactor by operation of the air piston. Fig. 2 shows a cross section of the air cylinder and the adjoining portion of the support tube leading to the reactor. The sample carrier is shown in place at the right-hand end of the injection rod extending from the air piston. The piston is shown in the retracted position, as it would be prior to the start of an experiment. The small Teflon gasket which encircled the sample carrier at the end of the injection rod sealed the reactor when the sample was injected. This seal was maintained throughout the test by maintaining air pressure on the piston. The sample carrier was a 2-in. section of thin-walled, -in.-diam nickel tubing with an internal blank about 1 in. from the base and with the base end sealed.

Jan 1, 1969

By B. M. Bird

ONE of the problems studied by the U. S. Bureau of Mines in cooperation with the University of Washington has been the re-treatment of table middlings. Hydraulic classification has given the best results. Instead of using the classifier to prepare the feed to the tables, as has been the practise for many years in ore dressing, it is used to separate part of a middling product that cannot be re-treated successfully on the table. Middlings are desirable in a table plant because the separation according to specific gravity is incomplete; that is, in the products of the table there is always an overlapping of free particles of coal and refuse that can be distinguished with heavy liquids such as are used in the float-and-sink test. The causes of this overlapping may be divided into two groups, those outside the table separation itself and those inherent in the table separation. The first of these groups includes, among other causes, the following: (1) poor adjustments of the table, (2) overloading or underloading the table, (3) irregularities in the quantity and quality of the feed, (4) irregularities in the power and water supply, and (5) a vertical danc-ing motion of the table deck due to weak foundations. These causes of overlapping are largely unnecessary in a properly designed and constructed plant; but whenever they are present they materially affect the character of the middling product, and hence the problem of re-treatment. The other group includes three additional causes: (6) small differences in specific gravity between coal and impurities, (7) a size-specific-gravity relationship of the coal and refuse particles in the table feed such that the sizing action of the table opposes the separation according to the specific gravity, and (8) shapes of particles that prevent a separation. The sixth, small differences in specific gravity, may be a very important reason for an incomplete separation. The change in specific gravity from coal to shale is always gradual and the designation of one part as coal and another part as refuse is arbitrary. If some specific gravity, such as 1.45, is chosen as the dividing point between washed coal and refuse,

Jan 1, 1928

By H. E. Stauss, E. I. Salkovitz, F. W. von Batchelder

EXISTING information regarding the structure of a spherulite in nodular cast iron is based on optical studies. According to these data, a nodule consists of an aggregate of graphite crystallites radiating from the center, with the closely packed basal planes at right angles to the radii. The c axes lie along the radii. This view faces some uncertainty in the fact that the c axis does not represent the accepted direction of fastest growth in graphite. To supplement the optical information, X-ray studies have now been made. The principle used was to screen the nodule in greater part from the X-ray beam and expose only a minor cap. As successively larger portions of the nodule were introduced into the X-ray beam, any differences in the X-ray patterns could be observed. Such photographs have been taken with chromium radiation and a Laue camera. The graphite nodule itself, about 0.010 to 0.025 in. in diam, was mounted with vaseline on a micrometer screw for control of the linear motion. The nodule rotated about 45" each time that it was translated linearly. The nodules were obtained from magnesium-treated hypereutectic iron by electrolytic solution of the iron in hydrochloric acid. In Fig. la is shown the pattern of the thinnest cap examined. In Fig. lb is shown the pattern of the same nodule moved 0.003 in. farther into the X-ray beam, and rotated 45" at the same time. Figs, la and lb indicate incomplete circles for graphite (the two outer circles arise from graphite) with the side arcs much weaker than the top and bottom ones. The arcs obtained are themselves not continuous in intensity but vary with maxima of intensity some 15" and 30" apart. The structure of the nodule that would give rise to such a pattern can be explained as follows. Basically the nodule consisted of small crystallites. The discontinuous character of the diffraction rings demonstrates that the nodule was not composed of randomly oriented crystallites. The strong vertical reflections and the weak lateral reflections show that the reflecting planes were roughly normal to the radii. The absence of sharp reflection spots suggests that the nodule did not contain large crystals. The sharpness of the diffraction rings in their radial direction shows that the variations in intensity along the arcs were not the result of line broadening resulting from extremely small crystals. In the diffraction patterns two rings corresponding to graphite were found. The third and inner ring in the figures originated in the vaseline. The graphite rings correspond to the a and ß lines reflected from the basal planes, showing that the radii of the nodules are the [0001] direction normal to the basal planes of graphite. The picture of the structure that is formed is, therefore, one of aggregates of crystallites. Within each aggregate the c axes of the crystallites tend to align themselves in the radial direction of the nodule, although these axes deviate somewhat in direction by a continuous variation of angle. Correspondingly the basal planes of the graphite crystallites are generally normal to the radii. It is a pleasure to acknowledge the assistance of M. C. Bloom and R. P. Dunphy of this laboratory.

Jan 1, 1952

The authors of T.P. 4179 have conducted a large number of experimental water floods, and the data are reported in a very clear manner. These data show significant variations of residual oil saturation with changes in wettability, interfacial tension, flooding rate, and oil-water viscosity ratio. Furthermore, some of the data obtained cover a range of variables not previously reported in the literature. It is our opinion that at least some of the observed variation in oil recovery can be obtained only in floods made under conditions identical with those used by the authors. There are other systems which may be said to have the same wettability, but which exhibit an entirely different qualitative dependence of oil recovery on the experimental variables. In this regard, we would like to direct attention to several items which we feel are not given sufficient consideration in the paper. The first of these items has to do with wetting equilibrium. A survey of the current literature will reveal that little is known, and even less is understood, about wetting equilibrium. This is particularly true of the relation between contact angle measurements made under static conditions, and the wettability existing under the dynamic conditions of floods carried out at relatively high rates. We feel that this is a very important consideration, particularly in the floods the authors performed under what they consider to be "water-wet" conditions. It is our opinion that wetting equilibrium did not exist in these floods, except possibly at the very lowest rates. This opinion is in part based on some flooding tests we have made which are very similar to some of those described by the authors. These floods were made in unconsolidated cores, 6 in. long and 13/4 in. in diameter, made up of carefully graded glass spheres of the approximate size of the sand grains used in the subject paper. The cores were mounted vertically, and distilled water was used to displace a refined oil equivalent to the authors Soltrol C. The glass spheres had previously been carefully cleaned so that they were strongly wet by the water. The floods were made with and without an interstitial water saturation. When interstitial water was present, the solid surfaces were mostly covered with water prior to injecting the flooding phase. Consequently, a condition very near wetting equilibrium existed throughout the flood. The data in Fig. A show that under these eircumstances, rate had no influence on residual oil at flood-out, over the range of rates studied. On the other hand, in the absence of interstitial water, the surfaces are all covered with oil before the displacement. To achieve wetting equilibrium the injected water must displace the oil from the surfaces themselves. This is not a fast process. Therefore, the effective dynamic wetting condition in floods of this type must depend upon the flooding rate. When the flood rate is very low, compared to the rate at which wetting equilibrium is attained, the residual oil saturation at flood-out is essentially the same as the residual obtained when interstitial water is present. This is shown in Fig. A, and occurs because the dynamic wetting conditions are the same in both cases. However, at moderately high flooding rates, the rate has an important bearing on the amount of oil recovered because in this case the attainment of surface equilibrium is the slow step. We believe that, in the absence of an interstitial water saturation, oil recovery varies with rate because of the reasonably slow approach to wetting equilibrium which occurs during the displacement. In fact, as the rate is increased, the oil recovery performance indicates the core is becoming progressively less water-wet. At the highest rate there is even considerable simultaneous production of oil and water after breakthrough. This does not occur at the lower flooding rates, nor is there appreciable simultaneous oil and water produc-

Jan 1, 1957

By A. D. Hoagland

The Flat Gap mine is located on Copper Ridge in the Appalachian Valley of East Tennessee. Large zinc orebodies occupy zones of solution and collapse breccias in Lower Ordovician Kingsport limestone and dolomite. The principal ore mineral is sphalerite and the principal gangue is dolomite. The ore-bearing horizons are considerably more than 95% covered by thick residual clay. Geochemical prospecting under these conditions is an effective exploration technique which played an important role in the discovery and exploration of the Flat Gap mine. The Flat Gap mine, an important zinc deposit of the Appalachian type, is located in the Copper Ridge Belt in the Valley of Tennessee approximately 30 miles northeast of the Mascot-Jefferson City zinc district (Fig. 1). The ore is found in large stratigraphically linked deposits in solution and collapse breccias of the Kingsport, Longview and, to a minor extent, Mascot formations of Lower Ordovician age. The principal ore mineral is sphalerite and the principal gangue minerals are dolcrmite and accessory pyrite. There is local minor galena and very rare barite and fluorite. The ore-bearing horizons are covered by about 20 to 100 ft or more of residual clay except where active streams have exposed bedrock. Considerably less than 5% of the favorable host rocks are exposed in outcrop, and this nearly complete soil cover creates a serious obstacle to exploration. Comprehensive surveys of the base metal content of soils furnish a useful substitute for outcrop geology, and under favorable conditions, this technique is a very valuable prospecting tool. The analysis is carried out by a titrametric dithizone method modified after the procedure described by E. B. Sandell.' This method detects

Jan 1, 1962

BIRINGUCCIO was born in Siena in 1480, the son of Paolo and Lucrezia di Bartolommeo Biringuccio.* He was baptized on October 20 of that year with the given names Vannoccio Vincenzio Austino Luca. His father appears to have been an architect, for in 1504 he was paid 600 scudi for his work on the walls of the Communal Palace and at the same time he was superintendent of streets for the city. The course of Biringuccio's life followed closely the checkered fortunes of the Petrucci family of Siena. A warm supporter of Pandolfo Petrucci, Biringuccio did not falter in his allegiance to the family and their party during his lifetime. It was probably to the protection and patronage of this lord that he was indebted for the opportunity to travel widely through Italy and into Germany during his early years and so to lay the foundation for the extensive knowledge of the subjects he was to describe in the Pirotechnia. In 1507, as he himself indicates (p. 48), he was 'in Friuli and. Carnia in northern Italy after having traveled in Germany,, and he also visited the, brass, works in Milan. After returning to Siena; he was sent by Pandolfo to direct the iron mines in near-by Boccheggiano. When Pandolfo died in 1512 (in which year Biringuccio's s father also died), Biringuccio continued to support the Petrucci family in the person of Pandolfo's son, Borghese, who succeeded, to the rule. Under his patronage, Biringuccio was appointed to a post in: the Armoury of the Siena Commune in 1513. In ISIS a popular uprising forced Borghese and his followers, including Biringuccio, to flee from Siena. Biringuccio and the goldsmith Francesco Castori, head of the mint, were accused of having debased the coinage alloy with the knowledge and consent of Borghese. When he failed to appear in 1516 to answer these charges-which may well have been invented by the opposing political faction-Biringuccio was declared a rebel and was exiled as a traitor to the Republic. He then traveled about Italy, was in Rome and Naples, and visited Sicily in 1517.

Jan 1, 1942

By T. H. Watkins

COAL is the basis upon which the activities of the industrial nations of the world rest today. In order that the coal industry may bee restored to a reasonably healthy condition, it is essential that both the operator and the miner should understand that they are directly concerned and that their selfish interests demand that they take an active, intelligent, self-sacrificing view of the entire situation and do their part in restoring and repairing the economic structure. Foreign credits, foreign debts, unstable exchanges, destroyed markets, and inability through lack of credit to carry on as before, all require our attention and cooperation. DEEP CONCERN AS TO FUTURE There is deep concern as to the future and a realiza-tion on the part of some of these leaders of industry that they will have to sacrifice their personal time, away from their desks and the details of business, in order to cooperate with other groups in studying the situation and endeavoring to find the best method of utilizing their knowledge in improving conditions and averting further disaster. It is most unfortunate for the country and for labor itself that the labor chiefs are blind to these necessities, and hostile to every effort to secure their cooperation in rebuilding prosperity.

Jan 2, 1922

By F. W. McQuiston

Idarado Mining Company's mill and surface plant are at the portal of the Treasury tunnel at elevation 10,625 ft, 12 miles south of Ouray, Colo. In 1943 and 1944 this tunnel was extended in a westerly direction to tap the Black Bear vein, and, together with the recently completed 1100-ft inclined Treasury raise, provides access to the Black Bear mine. In 1945 a 250-ton mill was placed in operation to process development ores containing much needed copper, lead and zinc for war requirements, and to serve as a pilot testing unit for larger scale milling operations. In the years 1902 to 1927 some 329,000 tons of ore were produced from mine workings on the Black Bear vein that extended downward from elevation I2,325 ft at the Black Bear tunnel portal to elevation 11,618 ft, the lowest level of the mine. The ores were taken to the Cascade and Smuggler-Union mills near Telluride over two aerial tramways. Gold bullion, a copper-lead concentrate, and a zinc concentrate were produced. Ores The Black Bear is a compound fissure vein that has undergone several stages of mineralization. The first important stage is represented by complex ores of copper. lead and zinc in a quartz gangue. Precious metal content in this stage is low. The galenn is argentiferous and varying amounts of tetrahedrite, freibergite and bornite tend to increase the normal copper content represented in chalcopyrite. The zinc occurs as a true sphalerite with little or no iron. Later re-openings of the fissure took place more or less co-extensively with the successive introduction of (I) abundant quartz gangue containing minor amounts of chalcopyrite, galena and sphalerite; (2) free gold in a fluoritic quartz gangue; and (3) barren, low-grade quartz with minor amounts of pyrite as the only important sulphide. The sulphides show practically no oxidation and little mineralogic inter-growth. Because of the common overlapping of these successive stages of mineralization within a given mining area, considerable dilution of the base-metal content takes place, thus lowering the average mill-head grade. Plant Practice Metallurgical testing was started shortly after the Black Bear vein was encountered on Treasury tunnel level in 1944. Laboratory tests showed good flotability of the minerals in the ore and indicated an economic separation could be made of the copper, lead and zinc minerals into their respective concentrates. The success of the separation is close reagent control to maintain a balance between promotion and depression of the sulphides. To maintain this balance reagent consumption for the three metal separation is considerably higher than in ordinary lead-zinc flotation.

Jan 1, 1949