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M. AlbERtson, Chairman. Production Engineer, Shell Petroleum Corporation, Houston, Texas. R. P. McLaughlin, Associate Chairman. General Manager, Burnham Exploration Co., Los Angeles, Calif. Eugene A. Stephenson, Secretary-Treasurer. Professor of Petroleum Engineermg, Missouri School of Mines and Metallurgy, Rolla, Mo. Ezecutive Commillee M. Albertson, Chairman. C. E. Beecher, Empire Oil & Refining Co., Bartlesville, Okla. L. L. Foley, Petroleum Engineer and Geologist, Tulsa, Okla. R. B. Kelly, Division Manager, Pure Oil Co., Fort Worth, Texas. Hallan N. Marsh, Production Engineer, General Petroleum Corporation of California, Los Angeles, Calif. R. E. Somers, Geologist, The Gulf Companies, Pittsburgh, Pa. Production Engineering T. V. Moore, Vice-chairman. Charge Production Research Division, Technical Service and Development Dept., Humble Oil & Refining Co., Houston, Texas. Joseph Chalmers. De Bataafsche Pet. Maatschappij, The Hague, Netherlands. M. L. Haider, Petroleum Engineer, Carter Oil Co., Tulsa, Okla. Emile HUGUENIN, Deputy State Oil and Gas Supervisor, Los Angeles, Calif. Carl E. Reistle, Jr., Petroleum Engineering Dept. Humble Oil & Refining CO., Houston. Texas. Produclion J. Terry DUCE, Vice-chairman. Geologist, The Texas Company, New York, N. Y. Basil B. Zavoico, Associate Vice-chairman. Consulting Geologist, Houston, Texas. Engineering Research R. L. Huntington, Vice-chairman. Associate Professor, Petroleum Engineering, University of Oklahoma, Norman Okla. Economics Sidney A. Swensrud, Vice-chairman. Assistant to the President, Standard Oil CO., Cleveland, Ohio. Refinery Engineering Walter Miller, Vice-chairman. Vice-president, Continental Oil Co., Ponca City, Okla.

Jan 1, 1937

By K. D. Jacob, W. L. Hill

Fluorine recovery in the United States has been restricted chiefly to manufacture of ordinary superphosphate and wet-process phosphoric acid. However, there is an expanding use of fluorine by industry in the form of hydrofluoric acid. Improved methods for recovering fluorine from phosphate rock would yield an adequate supply of fluosilicates and a substantial contribution to the hydrofluoric acid requirement. THE bulk of natural phosphates is comprised of calcium phosphates, which are usually apatites;' calcium aluminum phosphates such as pseudowavel-1ite; and aluminum phosphates, which occur in extensive deposits, notably on Grand Connetable Island." Nearly all deposits of current commercial value are apatite, often with admixed material of other classes. In the trade coarsely crystalline material, mainly fluorapatite of igneous origin, moves as apatite, whereas the fine-grained material of sedimentary origin is marketed as phosphate rock. The latter classification includes the phosphate shales in western North America. Although several genetic varieties of phosphate rock are recognized, most known reserves are of marine origin. Calcium phosphate is concentrated from Florida land pebble and Florida hard rock deposits and from Tennessee brown rock deposits. Phosphate Rock as a Fluorine Carrier: More than two decades ago Reynolds and Jacob surveyed the fluorine content of commercial phosphate rock from various parts of the world. Later these samples were re-analyzed by a new and more reliable method of determining flourine. The revised results with interim additions of new samples, published a few years ago in a brief summary," are shown in Figs. 1-3. Through the points representing the respective varieties of rock medial straight lines are drawn. In some instances the lines are well defined by the points; in others, where scattering renders the position of the best line uncertain, the greater weight is given points near the end of the covered range. Wherever distinct varieties are not recognized among regional deposits the custom is to identify the sample with the geographical location of the deposit. Although all rock varieties cannot be classified with certainty, the plotted results exhibit three distinct types of rock in which the F to P2O5 ratio diminishes, remains sensibly constant, and increases, respectively, as the grade of rock increases. Existence of two types of Florida land pebble, Fig. 1, is supported by additional results recently supplied by a producer." Generally speaking, phosphate rock from continental deposits carries considerably more fluorine, and apatite and insular phosphates less, in proportion to the phosphorus content than is required by the formula for fluorapatite. Exceptions to this are apatite from Canada and certain samples of Florida waste-pond phosphate. The manner in which excess fluorine is held and the nature of the carbonate in carbonate apatite are discussed in recent articles. High-grade calcium phosphates with F to P2O5 ratios less than 0.05 have been found in Curacao, Christmas Island," Mexic,13 and elsewhere. The calcium aluminum phosphates and aluminum phosphates aften carry notable amounts of fluorine. The F to P2O, ratio for one sample of pseudowavel-lite concentrate was 0.05." Aluminum phosphate from Grand Connetable Island is very low in fluorine, whereas some aluminum phosphate minerals" carry as much fluorine as highly fluorinated phosphate rock. Fluorine in Domestic Phosphate: The curves shown in the figures permit interpolation of the F to P2O5 ratio corresponding to the midpoint of selected ranges in grade of any one of the several varieties of phosphate. Multiplication of the interpolated ratio by the mid-range grade (P2O5) yields a figure for the percentage of fluorine in this grade. Then, with the use of the mid-range grade, the amount of fluorine held in phosphate reserves can be estimated, see Table I. Accordingly, on Jan. 1, 1950, the fluorine complement of known domestic reserves exceeded 420,000,000 long tons of the element. A previous figure," deduced in 1940 by a simpler procedure

Jan 1, 1955

By P. Beardmore, A. H. Holtzman, M. B. Bever

Specimens of the alloy CU3AU in the ordered and disordered states were subjected to explosive loading at shock pressures in the range from 160 to 475 kbars. The resulting changes in the resistivity, stored energy, microhardness, and microstructure were determined. By comparing the effects of explosive loading on ordered and disordered specimens a separation of structura1 and configurational changes has been made. In the pressure range from 290 to 370 kbars, representing a small increment of strain, the degree of long-range order in the ordered alloy decreased sharply. This change is attributed to the generation of shear stresses in excess of the theoretical shear strength of the alloy. Disordered CU3AU under explosive loading behaves in a manner considered to be characteristic of fee solid-solution alloys generally. The response of metals to high-velocity deformation and, in particular, to explosive loading has attracted much interest in recent years.' In general, metals are substantially strengthened by the passage of shock waves although the permanent strains are small. Explosive loading induces this strengthening by causing the metal to undergo rapidly a transient strain in a narrow region, first in the shock front and then in the rarefaction wave, which releases the pressure. The transient strain is given by e = 4/3 In V/Vo, where Vo and v are the specific volumes in the uncompressed and compressed states.2 The process produces many defects, which account for the strengthening. For the investigation reported here, an ordered alloy was chosen because it was expected to give sensitive indications of the near-neighbor effects produced by shock waves. The ordered alloy CU3AU was of special interest because of past work on the effects of conventional deformation on this alloy.314 The disordered alloy was included as a standard for comparison and as an alloy typical of a solid solution containing short-range order. The effects of explosive loading were followed by measurements of the resistivity, stored energy, and microhardness, and by metallographic examination. EXPERIMENTAL PROCEDURES Preparation of Specimens. Part of an ingot of the alloy Cu3Au prepared previously4 was cold-rolled with several intermediate anneals in vacuum to a final thickness of 0.042 in. Specimens of dimensions 2.0 by 1.0 by 0.042 in. were machined from this strip. After a recrystallization treatment of 1 hr at 565oC, half of the specimens were disordered by heating in evacuated Pyrex capsules for 1 hr at 460°C and quenching into water. Although they contained short-range order, they will be referred to as 'disordered" to indicate the absence of long-range order. The rest of the specimens were cooled slowly from 380°C to induce long-range order. The grain size of the ordered and disordered specimens was 0.012 mm. Explosive Loading. This was carried out at the Eastern Laboratory, Explosives Department, E. I. du Pont de Nemours & Co., by a driver-plate procedure described elsewhere.2 Two ordered specimens were stacked alongside two disordered speci-

Jan 1, 1964

By D. T. Peterson, T. Carnahan

The diffusion coejTicients of carbon, nitrogen, and oxyget were determined in $ thorium over the tempernilcre range 1440" io 1715°C. The diffusion coyfiicir?zls are given by: D = 0.022 exp (-27,000/RT) jor carbo)~, D = 0,0032 exp(-l7,00Q/RTj for nitrogen, and D = u.0013 expt(-11,UOU/RT) for oxygen. Cavl~orz was found to increase the hardness of thoriunz nearly linearly with concentration over the range 100 to 1000Ppm carbon. ThORIUM has a fcc structure up to 1365°C and a bcc structure from this temperature to its melting point at 1740°C. Diffusion of carbon, oxygen, and nitrogen in bcc thorium was of interest in connection with the purification of thorium by electrotransport.' In addition, it was possible to measure the diffusion of all three of these interstitial solutes in the same bcc metal. Only in niobium, tantalum, vanadium, and a iron have all three interstitial diffusion coefficients been measured in a given bcc metal. Diffusion coefficients have been measured for carbon and oxygen in a thorium by Peterson2, 3 and for nitrogen by Gerds and Mallett.4 Activation energies for diffusion are reported by the above authors to be 38 kcal per mole for carbon, 22.5 kcal per mole for nitrogen, and 49 kcal per mole for oxygen. Values of the diffusion coefficients of carbon and nitrogen in 3 thorium have been reported by Peterson et al.' However, these were secondary results of their investigation of electrotransport phenomena in thorium and it was hoped that the present study could provide more precise data. EXPERIMENTAL PROCEDURE The specimens used in this study were the well-known pair of semi-infinite bar type. The couple was formed by resistance butt welding two 0.54-cm-diam by 3.0-cm-long bars of thorium together under pure helium, the concentration of the solute being greater in one cylinder than that in the other. The finished couple then contained a concentration step at the weld interface and diffusion proceeded only along the axis of the rod. The thorium used in this study was prepared by the magnesium intermediate alloy method.5 The total impurity content was less than 400 ppm. The major impurities were: carbon, 100 ppm: nitrogen, 50 ppm; and oxygen. 85 ppm. The total metallic impurity content was less than 150 ppm. The high solute concentration portions of the diffusion couples were prepared by adding the solute to the high-purity thorium in a non-consumable electrode arc melting procedure. Carbon and nitrogen were added in the form of spectroscopic graphite and nitrogen gas while a Tho2 layer was dissolved by arc melting to add oxygen. High-purity thorium formed the low concentration portions in the carbon and nitrogen couples. The low oxygen portions were obtained by deoxidizing high-purity thorium with calcium for 3 weeks at 1000°C according to a method reported by Peterson.3 The high C-Th contained 400 ppm C, the high N-Th contained 400 ppm N, the high 0-Th contained 220 ppm 0, and the low 0-Th contained 25 ppm O. The high O-Th was brine-quenched from 1500°C to retain most of the oxygen in solution at room temperature. These concentration levels were all below the solubility limits in 0 thorium at 1400°C. A resistance-heated high-vacuum furnace was used to heat the couples. The samples were mounted horizontally on a tantalum support which had small grooves near each end. Spacer rods of thorium, 0.4 cm in diam, were placed in these grooves to prevent contact between the sample and the tantalum support. This arrangement should have prevented contamination of the sample by contact with the support. In further effort to reduce contamination, the oxygen diffusion couples were sealed inside evacuated outgassed tantalum cylinders lined with thorium foil. Thorium rings around each end of the samples acted as spacers in this case. Pressure during diffusion runs was about 10-6 torr after an initial outgassing stage. Temperature measurements were made by sighting on black body holes in the sample support adjacent to the samples with a Leeds and Northrup disappearing-filament optical pyrometer. Temperatures were constant during a diffusion anneal to ±5C. The observed temperatures were corrected for sight glass absorption after each diffusion run. The pyrometer was checked against a calibrated electronic optical pyrometer and a calibrated tungsten strip lamp with the electronic pyrometer being taken as the standard. All temperature readings agreed to within ±3C over the temperature range 1450" to 1690°C. Time corrections due to diffusion during heating and cooling were necessary because of the short diffusion times. The diffusion times ranged from 6 min for the oxygen sample run at 1690°C to 90 min for the carbon sample run at 1500°C. A series of temperature vs time plots were made for heating and cooling of the samples to the various diffusion temperatures. This data was then used in a method according to shewmon6 to determine the time corrections. The corrections amounted to

Jan 1, 1970

By F. W. Luerssen, J. F. Elliott

F LUSHING the early slag from a stationary open Fhearth having a high percentage of hot metal in its charge is necessary in order to remove silica from the system. The flush slag is strongly oxidizing and is somewhat acidic. It has, however, considerable capacity to extract phosphorus from the bath and it also removes considerable manganese. It seems probable that factors which control the distribution of phosphorus and manganese between slag and metal in the refining period also should be dominant in the flush and postflush periods. Several studies, as summarized elsewhere,1,2 support the viewpoint that conditions closely approaching equilibrium for these elements are rather readily established during the refining period. Over the years these studies have repeatedly demonstrated that 1—high slag v01ume, 2—low bath and slag temperature, 3—basic slag, and 4—strongly oxidizing slag favor rapid elimination of phosphorus from the bath to the slag. They also show that the following conditions favor retention of manganese in the bath: 1—low slag volume, 2—high bath and slag temperature, 3— basic slag, and 4—minimum oxidizing power of slag. When it is considered that the flush slag often carries as high as 75 pct of the manganese charged and only 25 to 60 pct of the phosphorus charged, it is evident that in removing silica much manganese is sacrificed but phosphorus removal is far from conplete. Because of overriding circumstances, this is accepted in most operations and actually it is considered to be inevitable. This may account for the fact that little attention has been paid to conditions affecting the elimination of phosphorus and manganese in the flush slag. A recent study of the behavior of various charge oxides has developed considerable information on the flush and postflush periods. Because the data are felt to be of general interest, they have been brought together and Presented in this paper. The object is to show the various factors in the flush and postflush periods which influence elimination of phosphorus and manganese. Physical Conditions During and After Flushing Physical conditions existing during the flush vary from plant to plant, from shop to shop, from furnace to furnace, and even from heat to heat. They are strongly influenced by the physical and chemical character of the charge oxide which is ordinarily necessary to provide sufficient oxidizing power early in the heat. Invariably the period is characterized by a vigorous reaction between the principal re-actants: the hot metal being added and the charge oxide. During the flush, it is probable that the slag acts to some extent as an oxidizer; but, because of the critical influence of the behavior of the charge oxid'e on flushing action, it seems apparent that the oxide itself is the dominant oxidizer. Fig. 1 shows the course of two heats which were selected as being typical of the group studied. Heat A was charged with 55 pet hot metal, based on the total metallics charged, and heat B had 57 pct hot metal. As indicated in Table I and Fig. 1, the melt-down slag, which is not usually voluminous and which is principally FeO, expands greatly in volume and will show rather high levels of SiO2, MnO, and P2O5 very soon after the beginning of the hot metal addition. Simultaneously, large volumes of CO are liberated which cause violent mixing of slag and metal. It is of interest to note that the time required to bring carbon down to a low level is very much longer than that required for the removal of silicon, manganese, or phosphorus. At the end of flush, carbon in the bath is still approximately 2 pct. When strongly reducing hot metal is brought into contact with strongly oxidizing conditions within the furnace! it is probable that the rate of mass transfer to the slag (and atmosphere) of silicon, manganese, phosphorus, and carbon initially depends principally on the rates at which the two participating phases are brought into contact That is, it depends on the nature of the various reactions. Later in the flush period, when the scrap is virtually all dissolved and the action of the bath has settled down to a steady and somewhat gentle boil, it is likely that other factors, such as the transfer of oxygen across the slag-metal interface, become dominant. The temperature of the slag-metal system is far from uniform. Heat is being driven by the flame down through the slag. Bubbling and surging of the metal also frequently brings portions of the bath in contact with the flame. At areas of contact between the ore and liquid metal, or slag and liquid metal, the oxidizing reactions generate much heat. On the other hand, scrap is being melted which tends to absorb large quantities of heat. Because the liquid bath is high in carbon, the steel scrap is brought into solution rapidly. This can proceed at a rather low temperature; and until much of the scrap has been taken into solution, the bath temperature would not be expected to increase appreciably. Consideration of these factors leads to the conclusion that during the flush period the slag should be rather hot and the bath relatively cold. Both observation and temperature measurements bear this out. Experimental Data The extended program of charge oxide evaluation permitted study of the widely varying conditions existing during the flushing period. Slag and metal analyses and bath temperatures reported herein (Tables I and 11) were obtained toward the latter portion of the work. Four different types of charge oxide, sinter, two types of hydraulic cement-bonded soft ores, and a pyrobonded agglomerate were used in the study. Although the heats reported were from only one 205 ton furnace, they show variations in flush slag analyses all the way from 25 pct FeO, which is typical with the use of a hard natural charge ore, to 45 pct FeO which resulted when a very poorly agglomerated fine ore was used. The physical behavior of the flushes showed a correspondingly wide variation from well controlled reactions to violent surges following periods of inac-

Jan 1, 1956

By Michael J. Messel

THE critical shortage of asbestos fiber in the world today brings to the foreground the question of locating and developing new deposits. The object of this paper is to discuss some of the more important factors which should be considered in the examination and valuation of a new asbestos enterprise. Some of the more important uses of asbestos fiber are for textiles, heat insulators, building materials, filters and a series of other uses. The properties of this mineral, such as fibrous structure, color, strength, silkiness and flexibility, coupled with resistance to fire, certain chemical action and decay make its application unique for certain industrial uses which consume over 500,000 tons annually. These same unique properties which make this mineral so valuable also make a deposit one of the most difficult to appraise accurately, because of the many undeterminable and varying factors which must be considered before a deposit can properly be termed commercial. The majority of the asbestos fiber today, having the above mentioned properties, is sold by grades which are based on fiber length. Present day fiber prices vary over a wide range from $800 to $225 for crude fibers and $300 to $20.00 per ton for milled grades. For valuation purposes a careful study should be made of existing fiber prices and markets. EXAMINATION OF DEPOSITS In carrying out prospecting and examination of a deposit, considerable caution is required to get the necessary information in the form that will have the most value for the final determination. There are two main classes of asbestos fibers, chrysotile and the amphiboles, the chrysotile being, by far, the most important both in abundance and uses. This paper will stress mainly chrysotile deposits, however, the amphiboles have many important uses, especially amosite and crocidalite. Their valuation presents special problems as other factors may be involved, especially as they are not graded according to any well defined and adopted standard but usually according to the use for which they are being supplied. Most chrysotile deposits occur in two main types of rock, (I) mainly in basic igneous, such as dunite and peridotite, (2) to a lesser extent in sedimentary rocks, such as dolomite and limestone. All of these require a certain degree of metamorphism to be favorable to asbestos formation. Approximately 90 pct of the asbestos deposits are derived from serpentinization of dunite or peridotite, whereby the magnesiumsilicate olivine was altered to hydrous magnesium-silicate serpentine. Under certain favorable geological conditions, this serpentine takes a fibrous form having a definite crystal structure, probably due to molecular rearrangement, and is known as chrysotile. The fiber veins are usually ir-

Jan 1, 1947

THE task of the smith who works in iron is very laborious, indeed far more so than that of the coppersmith just described. For he also handles heavy weights continually, and stands constantly erect be- fore the fire of the forge, since the hardness of the iron cannot be softened except by means of heating and boiling it well. In this place he continually moves his body, now thrusting the iron into the heart of the fire with large thick tongs, now removing it to look at it and to put sand, tuff, or other earth over it, now putting on fresh charcoal, now moistening and slowing down the fire, and now cleaning it. Finally, while the iron is hot

Jan 1, 1942

By C. C. McDermond, Others, B. N. Zavoico

Production of crude oil in Venezuela for the year 1937 was 186,653,-916 bbl., as compared with 155,228,982 bbl. produced in 1936, an increase of almost 31,500,000 bbl. The oil-field strike, which started on Dec. 14, 1936, lasted until Jan. 25, 1937, when a total of 10,000,000 bbl. of production was estimated to have been lost (5,750,000 bbl. in 1936 and the remainder in 1937). Of the total of 186,653,916 bbl. produced in 1937, the Lagunillas field contributed 45.6 per cent, a drop of approximately 10 per cent under 1936 figures; Tia Juana, 14.3 per cent; Quiriquire field, 14.0 per cent; La Rosa area, 13.3 per cent and the Mene Grande field, 7.6 per cent, these being the five leading contributors of the year's production. Detailed production figures by fields and by companies are shown on Table 1. Of the total production of Venezuela the following four major companies accounted for the greater proportion: Standard of Venezuela and Lago Petroleum Corporation together, 48.3 per cent; Shell, 37.4 per cent and Venezuela Gulf, 14.0 per cent. At the end of the year, 2491 wells were producing, of which number 1291 wells were pumpers, or about 52 per cent. Production The accompanying statistics of production record of Venezuela oil fields from its inception to Dec. 31, 1937, shown on Table 2, indicates that the cumulative production reached 1,503,283,228 bbl. In order of importance, Lagunillas leads all the fields, having accounted for about 50 per cent of Venezuelan production, followed by La Rosa area, which produced about 21 per cent; Mene Grande, which produced about 13 per cent, and Quiriquire, which produced 6.5 per cent. Table 3 shows the age of each field. Mene Grande is the oldest, having produced for 24 years; Tarra is next, 21 1/2 years old, and El Mene third, 171/2 years. The gravity of the crude from the various fields, also shown on Table 3, remained unchanged, the only addition being the new Tia Juana field, which averages 15.6' A.P.I. Table 4 shows the method of production by fields as of Jan. 1, 1938; at the end of the year 2491 wells were producing, compared with 2005 wells producing at the beginning of 1937, or an increase of 486 wells. The completions for the year reached 512. Of the 2491 wells producing crude oil, 1291 wells, or approximately 52 per cent, were pumping, 925 (approximately 37 per cent) were flowing naturally and 275 (11 per cent) were on

Jan 1, 1938

By J. B. Austin

IN developing a consistent picture of the thermal expansion of the commercial chromium steels, which cover a range of carbon contents, it is desirable to know the expansion in the limiting case of the binary, carbon-free, iron-chromium alloys. We have, therefore, determined the thermal expansion of a series of five special alloys, ranging in chromium content from 3 to 10.5 per cent, with not more than 0.03 per cent carbon, over a temperature range extending beyond the transformation region; this low carbon content enables us to draw reasonably reliable conclusions as to the behavior of the carbon-free system. Moreover, the measure-ments serve to determine the beginning and the end of the alpha-gamma transformation; and they emphasize once more the fact that a transforma-tion temperature determined by any method in which the specimen is cooled at an appreciable rate is apt to be seriously in error, particularly if the metal contains a transformation-retarding element such as chro-mium or managanese. The lag, or undercooling, observed at the ? - a transformation is explained in terms of the influence of temperature on transformation velocity; the rather unusual shape of the ? loop is attributed to a change with temperature and with composition of the distribution of chromium between the alpha-iron and gamma-iron solid solutions. The exact composition of the alloys which were obtained through the courtesy of Dr. W. Rohn, of the Heraeus Vakuumschmelze A-G., is given in Table 1. Determinations of the linear thermal expansion and of transformation temperature were carried out in the vacuum dila-tometer previously described,1 using a rate of heating and of cooling of 3.0° to 3.5° per minute unless otherwise stated. Magnetic susceptibility, which was measured in studying the rate of transformation, was determined with a magnetic balance, which also has been described.2

Jan 1, 1935

By J. B. Austin, R. H. H. Pierce

IN developing a consistent picture of the thermal expansion of the commercial chromium steels, which cover a range of, carbon contents, it is desirable to know the expansion in the limiting case of the binary, carbon-free, iron-chromium alloys. We have, therefore, determined the thermal expansion of a series of five special alloys, ranging in chromium content from 3 to 10.5 per cent, with not more than 0.03 per cent carbon, over a temperature range extending beyond the transformation region; this low carbon content enables us to draw reasonably reliable conclusions as to the behavior of the carbon-free system. Moreover, the measurements serve to determine the beginning and the end of the alpha-gamma transformation; and they emphasize once more the fact that a transformation temperature determined by any method in which the specimen is .cooled at an appreciable rate is apt to be seriously in error, particularly if the metal contains a transformation-retarding element such as chromium or managanese. The lag, or undercooling, observed at the ?-a transformation is explained in terms of the influence of temperature on transformation velocity; the rather unusual shape of the ? loop is attributed to a change with temperature and with composition of the distribution of chromium between the alpha-iron and gamma-iron solid solutions. The exact composition of the alloys which were obtained through the courtesy of Dr. W. Rohn, of the Heraeus Vakuumschmelze A-G., is given in Table 1. Determinations of the linear thermal expansion and of transformation temperature were carried out in the vacuum dilatometer previously described,1 using a rate of heating and of cooling of 3.0° to 3.5° per minute unless otherwise stated. Magnetic susceptibility, which was measured in studying the rate of transformation, was determined with a magnetic balance, which also has. been described.2

Jan 1, 1935

By H. F. JR. Miller

(Butte Meeting, August, 1913.) THE major cause of the deterioration of the open-hearth furnace as its length of service increases, is the melting down, or rather the slagging, of the checker-brick, together with the deposition of dirt in the form of iron oxide, etc., which helps to close the openings, as well as to slag the brick by chemical action. Any construction that will do away with the necessity of having the waste gases come down through the checkers will eliminate the main reason for their deterioration. There are some other well-defined reasons which are subordinate to the main one given above. Some of the defects of the present type of regenerator chambers are as follows: 1. The checkers cannot be cleaned while the furnace is in operation, nor can they be cleaned at the end of the run without taking out all of the checker-brick. This causes high costs for labor and brick. The labor cost is high because all checker-brick have to be handled twice. The brick cost is high because many of the bricks are spalled in the double handling, rendering them useless because a spalled brick will not stand up. 2. The top courses of brick become coated with iron oxide, etc., melt clown, and large amounts of dirt are deposited throughout the checkers, especially at the bottom. The draft of the furnace is decreased by the closing of the top and bottom openings, especially the top ones, and the entire working of the furnace is affected. If an effort is made to clean the checkers the dirt and brick falling down into the holes still further diminish the draft. 3. The distribution of the air or waste gases through the checkers is in many cases uneven, resulting in a lower temperature of pre-heated air and therefore a slower working furnace. Also, the passage of air and waste gases is so crooked that sometimes the chimney is not powerful enough to overcome the friction.

Jan 6, 1913

By William S. McAleer

Two major trends in the coal industry today focus attention on the need for heat-drying equipment of a simpler, more flexible and less expensive type than has been considered standard equipment for drying coal. These trends are: I. The tremendous growth in the use of mechanical equipment to load coal both in underground mining and strip mining, which necessitates efficient mechanical cleaning of the fine as well as the coarse coal and thus means a growing tonnage of washed fine coal? with its attendant moisture problems. 2. The growing consumer demand for the smaller sizes for use as domestic stoker coal, with increasingly rigid specifications covering size, ash, and moisture analyses. ACCEPTED PRACTICE In the past, when, for example, 4 in. too coal has been washed, there was little trouble in producing a washed product 4 to o with a satisfactory resultant moisture. The 4 to 3/8-in. could be taken from dewatering screens at a surface moisture ranging from 2.5 to 3.5 per cent, depending upon the size consist. The 3/8-in. to o coal was generally dewatered satisfactorily with centrifugal driers, to final surface moistures from 5.5 to 8 per cent, again depending upon size consist. The centrifugal type of drier has definitely proved itself to be the most economical type of machine to handle coal approximately 3/8 in. to o as recovered by dewatering screens or drainage elevators with 15 to 25 per cent surface moisture and turn out a product with moistures as stated above. Sometimes such moistures (5.5 to 8.0 per cent) in the product are satisfactory. If not, an ultimate moisture, lower than 3 per cent, is seldom required and the centrifugal drier removes 70 to 85 per cent of the total moisture to be removed. In certain districts there has been a growing tendency to circumvent the use of centrifugals or other types of driers, by dewatering over screens of the wedge wire type and wasting all the finer sizes. Sometimes all the minus 28-mesh has been wasted and often the size wasted has been as large as 1/8-in. By wasting these finer sizes, a lower moisture can be obtained in the finished product, but taking into account the cost of the tonnage so lost, plus the added cost of ultimately disposing of this wasted tonnage, often the cost will be greater than the cost of heat-drying in a modern plant, which makes possible the recovery of all the tonnage. Moreover, with the moisture standards for domestic stoker equipment even these wasteful approaches to its solution do not solve the problem and there remains only the alternative of heat-drying. HEAT-DRYING Until about four years ago, heat-drying of coal at the preparation plants was confined chiefly to drying the fine sizes (approximately 3/8 in. to 0). Occasional

Jan 1, 1941

By Herbert Hoover

THE desire of the engineers over the last few years, growing out of their contact with public affairs, that this Institute should take a wider vision than the narrower field of technology and should apply its skill to the development of civic problems which must lay in their foundation on engineering, has led to this discussion today. Some of us in San Francisco, in discussing this question of the relation of the engineers to civic problems, raised the question as to whether or not in this national emergency it was not the duty of the Mining Engineers to bring, forward their combined skill and knowledge and experience to bear upon the problems of the coal industry. This industry, considered as a whole, is one of the worst functioning industries in the United States. It is equipped with capital, with machinery, plants and labor to a peak load at least 20 per cent. above the average necessity. This peak load, therefore, involves the use of probably 100,000 men diverted from other productive industries; it involves an intermittency of employment through its whole personnel that results not only in a long train of human woe, but results also in a higher cost of coal -to the general public. The problem of whether the industry can, by any device, be cured or even partially cured of its intermittency, is solely an engineering problem. It is therefore an apropos problem for this Institute. Your President and myself and others thought that we could best develop this discussion by calling upon men of large experience in the particular branches of the soft coal industry, to bring the facts in front of this general committee, with a view to an exhaustive discussion and perhaps subsequently the appointment of a committee to formulate those facts and such remedies as may be developed into a report that would be of constructive value.

Jan 3, 1920

F. G. CLAPP, New York, N. Y. (written discussion *).-Whatever processes of appraisal have been found most correct and feasible in one field or group of fields will generally prove most adaptable in others. So far as the California fields are concerned, Mr. Requa's paper appears to outline the most up-to-date processes of appraisal. It remains, then, to discuss and adapt these and to make such revisions in methods and processes of calculation as will give us results elsewhere. The trouble about most attempts to place a value on oil lands, whether in this country or elsewhere, has been that many of the so-called "experts" called upon to express an opinion either have not possessed the requisite engineering and geological knowledge to make an accurate appraisal of the lands, or that they were not furnished with sufficient information for the purpose in hand. The Independent. 011. Producers' Agency of California, for whom Mr. Requa's original report was prepared, had many advantages in this respect not generally available to engineers making reports, as all existing information seems to have been at the experts' disposal within the limits of a large number of properties, practically commensurate with the extent of the fields in question. Hence the report could be and was more accurate than any similar report for a single company is likely to be in other fields. Very few companies are so exempt from competition that all the data on neighboring leases of other companies will be freely turned over to them. In many companies, certain available data are concealed from the engineer who makes the reports, particularly if the properties are supposed to be worth less than their apparent value. In the case of other companies, having the best of intentions, the data are insufficient to help the engineer greatly in his appraisal, simply because the oil business has been so, unsystematic in most fields that only the largest and wisest companies have kept accurate figures regarding runs and gravity of oil from individual wells and from different depths. In many wells, which ran wild for clays or weeks in the older fields, there was a waste which is not recordable with exactness. These and many other difficulties confront even the most experienced expert in actual practice outside of the California fields. We may justly say, therefore, that an engineer in other fields of the United States and in the European, South American and Asiatic fields, must not only begin where the Independent Oil Producers' Agency

Jan 4, 1918

By Persifor Frazer

(Read at the Amenia Meeting, October, 1877.) IT has been the aim of the writer, by measuring his base line on the territory of theoretical chemistry, to attempt to fix by triangulation certain points within the domain of mineralogy. As the barest first experiment in this direction, a few of the hydrated oxides of iron have been selected, their theoretical construction reduced to percentage of the constituents into which the ordinary analytical methods would resolve them, and the results compared with actual analyses compiled from the most reliable sources; the accidental errors being as much as possible eliminated. This method seems to be a simple one and one easily pursued, but, as will shortly appear, it is beset with grave difficulties, all of which the writer does not pretend to have satisfactorily surmounted. In the first place arises the important question, what are we to understand by the hydrated oxides of iron ? In all books of chemistry and lexicons of minerals, the proposition, long ago taught by the earlier chemists, that water might exist in two forms of combination, viz., as water of crystallization or as water of constitution, is tacitly assumed. There is nothing in the principles of the new chemistry which is opposed to this ; for (to carry the mind's eye into .the process of construction of the least units into which a definite chemical compound is capable of being divided without losing its characteristic properties), however unlikely it may seem, it is, nevertheless, possible that a given molecule of iron may, under certain conditions of heat, pressure, etc., attract to itself as many molecules of the water in which it is natant as from the relative size, shape, attractive force, etc. of either, it is capable of taking up, and this complex system of associated molecules might oscillate as a physical unit so long as the conditions on which its existence was dependent remained unchanged. Moreover, it is highly probable that the first effect upon such a molecule produced by physical or chemical forces would be to separate it into two or more simple ones of different kinds, while a further application of these forces might rend asunder the bonds of the simpler compounds themselves.

Jan 1, 1878

By Persifor Frazer

It has been the aim of the writer, by measuring his base line on the territory of theoretical chemistry, to attempt to fix by triangula tion certain points within the domain of mineralogy. As the barest first experiment in this direction, a few of the hydrated oxides of iron have been selected, their theoretical construe tion reduced to percentage of the constituents into which the ordinary analytical methods would resolve them, and the results compared with actual analyses compiled from the most reliable sources; the accidental errors being as much as possible eliminated. This method seems to be a simple one and one easily pursued, but, as will shortly appear, it is beset with grave difficulties, all of which the writer does not pretend to have satisfactorily surmounted. In the first place arises the important question, what are we to understand by the hydrated oxides of iron ? In all books of chemistry and lexicons of minerals, the proposition, long ago taught by the earlier chemists, that water might exist in two forms of combination, viz., as water of crystallization or as water of constitution, is tacitly assumed. There is nothing in the principles of the new chemistry which is opposed to this; for (to carry the mind's eye into the process of con struction of the least units into which a definite chemical compound is capable of being divided without losing its characteristic proper ties), however unlikely it may seem, it is, nevertheless, possible that a given molecule of iron may, under certain conditions of heat, pressure, etc., attract to itself as many molecules of the water in which it is natant as: from the relative size, shape, attractive force, etc. of either, it is capable of taking up, and this complex system of associated molecules might oscillate as a physical unit so long as the conditions on which its existence was dependent remained unchanged. Moreover, it is highly probable that the first effect upon such a mole cule produced by physical or chemical forces would be to separate it into two or more simple ones of different kinds, while a further ap plication of these forces might rend asunder the bonds of the simpler compounds themselves.

Jan 1, 1879

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By Clark L. Corey, Bogdan Lisowsky

Electrical resistivity, X-ray line positions, degree of order, and microstructures have been investigated for Ni-A1 alloys near the Ni3Al composition. The results indicate that Ni3Al undergoes disordering between 1250oC and the mp; also supersaturated y, produced in y + y' alloys by gas quenching, is extensively ordered prior to y' (Ni3Al) phase separation. The latter reaction, if not both, must follow the cooperative phenomena model. Shifts in line position as a function of quench-indulced super satulration are shown. Lattice pavarneters of equilibriunz and nonequilibrium phases are given. THE objective of this investigation was to determine the mechanism and kinetics of the reactions which occur in Ni3A1 and hypostoichiometric Ni3A1 alloys. The results are of particular significance relative to pre-precipitation phenomena. Early work on Ni-A1 binary compositions near the Ni3A1 composition (13.6 wt pct Al) has been adequately reviewed by Hanssen,1 whose phase diagram is presented in Fig. 1. williams2 verified the suggestion made by Taylor and Floyd3 and others4 that y', Ni3A1, may precipitate coherently on (100) planes of the y phase (see Fig. 1 for phase nomenclature); he further suggested a two-step precipitation mechanism consisting initially of probably short-range ordering followed by actual precipitation of y'. The precipitation stage in low-aluminum hypo-eutectic compositions has been studied by a number of investigators;*"7 short-range order or "zone" formation have been suggested as explanations for various diffuse X-ray scattering effects. The ordering reaction in Ni3A1 alloys is characterized by a) a very rapid rate of ordering in nonstoi-chiometric compositions, b) absence of a disordered phase region for the stoichiometric compound, y', or Ni3A1, c) precipitation phenomena as a dominant aspect in hypoeutectic alloys, and d) an increase in elec-trical resistivity on ordering.' The latter two factors were found by Newkirk to characterize ordering in Co-Pt, for which an extensive and detailed analysis was made.' An electrical-resistivity increase on ordering has also been reported for cuAu3.10 PROCEDURE Ni-A1 alloys in the form of 1300-g chill-cast ingots were prepared by vacuum melting electrolytic nickel and high-purity (99.99 pct) aluminum. Very small heats prepared from high-purity carbonyl nickel, supplied through the courtesy of Dr. Goff of the Naval Research Laboratory, were used for comparison with the larger ingots and no differences were noted. The cast material was homogenized in purified argon for a minimum of 72 hr at 1200°C and water-quenched from 1350°C. Compositions studied are given in Table I. The 10 pct A1 alloy was both hot- and cold-rolled. X-ray superlattice line intensities and peak positions were obtained from -270 mesh filings, using CuK, radiation with a LiF crystal monochromat adjusted to receive both 01 and a2. One-degree slits and a 1/8 deg per min scan rate were used to record line traces. A standard tungsten powder, obtained through the courtesy of G.E. Research Laboratory, was used to calibrate line positions.

Jan 1, 1968

By S. J. Rothman, L. T. Lloyd

S. J. Rothman and L. T. Lloyd (Argonne National Laboratory)— Hagel's paperz0 discusses the question of the mechanism for self-diffusion in bcc transition metals. Recent work21"23 has led us to agree with him in reabandoning the ring mechanism in favor of a defect mechanism, most likely vacancies. On the other hand, we think that Hagel's attempt to group together all self-diffusion in bcc transition metals is wrong. We prefer the scheme of Peart, Graham, and omlin," who separate them into two groups. One group contains the anomalously behaved metals P titanium,', y uranium, and perhaps zirconim.' The other group contains a iron," this alloy was held at 1800°C for 2 hr before quenching, its structure was all a. B. C. Giessen, I. Rump, and N. J. Grant (Authors' reply)—We very much appreciate the discussion by Deardorff and Kato regarding the a to /3 transformation temperature of hafnium. In the W-Hf program, as well as in a current study of the system Cr-Hf, standard precautions were exercised against contamination, including vacua of less than 10"5 mm Hg and a weight control check of all specimens to insure an impurity rise of less than 100 ppm. Following receipt of the above discussion, a revision was made in the annealing process. Arc-cast specimens were etched with a 10 pct HF-90 pct HNO solution until 1 mm of surface, including a possible oxide film, was removed. Annealing was done in a hafnium container which provided a long diffusion path for gaseous contaminants. Finally, the heat treating time was shortened. Structural changes were noted to occur quite slowly. A 99.5 at. pct Hf alloy showed 70 pct /3 after 30 min at 1700°C and was 100 pct /3 after 10 min at 1715°C. After 24 hr at 1740C, the alloy was found to be 10 pct/3. This change is due to contamination; it was estimated that it corresponds to an increase of 60°C in the transformation temperature over a 24 hr period. The corresponding change in 30 rnin would be slight. Using the same hafnium as in the above publication, and three new alloys at 98, 99, and 99.5 at. pct Hf, the transformation temperature was indicated to be 1715" 15°C. Since this hafnium contained 4.4 at. pct Zr, a correction of 40 5C, based on an assumed approximately linear transformation temperature curve, must be made for pure hafnium. This yields a value of 1755 20°C in good agreement with Deardorff and Kato's value. Because the slope of the boundary is small, this permits a good extrapolation, and we regard the W-Hf alloys as well suited to check the Hf transformation temperature. niobirn,'' and molybdenum,22 whose activation energies correlate with the melting temperature and whose Do values follow Zener's predictions.28 We have no quarrel with Hagel's placing chromium into the second group; we disagree with his interpreting our data to make uranium fit into that group. Hagel considers that the measurements of self-diffusion in uranium below about 950°C represent combined volume and grain boundary diffusion. This contention is based on the curvature of the penetration plot for our 891°C run,4 which also has a nearly straight line plot of log c vs x. Hagel has extrapolated these characteristics to our 803.5C run and fitted his Arrhenius plot for self-diffusion in y uranium to our four highest temperature points only. We think this is wrong for the following reasons.

Jan 1, 1963

By Joseph E. Pogue

THE period of new oil discoveries in Illinois began in February 1937, when The Pure Oil Co. found the Clay City field the forerunner of a number of limestone pools. The importance of the area was emphasized greatly in December of the same year with the discovery of excellent sand production by The Carter Oil Co. at Louden and in June, 1938, with the discovery by The Texas Co. of the Salem field producing from two sands and one lime- stone horizon. By September, 1939, new discoveries in Illinois were estimated to have added, under prevailing production practices, some 500,000,000 barrels to the crude oil reserves of the United States and to have produced to that date some 63,000,000 barrels with daily production passing the 300,000-barrel mark by Sept. 1.

Jan 1, 1939