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By Harold R. Bradford

EXPANSION initiated during and after the war has placed industrial plants in new areas and increased reduction and manufacturing facilities in communities already established. With added expansion interest has grown in possible area contamination from waste products. Evolved flue waste contains many chemical contaminants that may or may not cause concern; however, atmospheric pollution has always been a problem to industrial communities. For some time effects attributed to small quantities of compounds of fluorine in various waste gases have been studied by industrial, medical, agricultural, and associated interests.1'2 Aside from an article by Churchill, Rowley, and Martin in 1948," little has been published on the subject of fluorine in coal except by foreign investigators. The first indication of fluorine compounds in coal was noted in England in 1934 by R. Lessing,4,5 who found that the presence of fluorine in Midland and West County coals was definitely established by etching of glass and by severe corrosion of porcelain fillings in a gas works scrubber. Etching of glass in a direct contact annealing kiln initiated research, and in 1944 four papers were published by H. E. Crossley,6-9 giving results of investigations of fluorine in coal of England by the Fuel Research Board, Department of Scientific and Industrial Research. These investigations studied methods of determining fluorine, the quantities present in various coal deposits, the geographical distribution of fluorine in British coals, occurrence of fluorine in minerals associated with coal, amounts of fluorine compared to other constituents of coal, the nature of fluorine compounds, and industrial significance of fluorine in coal. It was shown that British coals contain from 5 to 200 ppm of fluorine, which is probably present as fluorapatite [Ca10F2(PO4)6], often written as [3Ca3P2O8.CaF2]. The fluorapatite is intimately associated with shale in some coals and can often be separated from these coals along with the shales. H. E. Crossley8 also reported no correlation between the amounts of chlorine, sulfur, or ash and the amount of fluorine in different coals. He found, however, a relationship between the content of fluorine and phosporus in many British coals. Thus it should be possible to anticipate likely fluorine-rich coals from existing data giving phosphorus content. Behavior of the fluorine compounds of coal was compared with that of 12 fluoride-phosphate minerals in sink-float separations and solvent ex-

Jan 1, 1958

By H. N. Eavenson

Prior to 1907 nearly all coke was made in beehive ovens, and most of the gas produced was made in the old-style gas retorts, and while there were a few coke plants in southern West Virginia, southwest Virginia and Kentucky operating on high-volatile coals the proportion of the total product made by them was small and usually was used locally. The greater part of the coke made, and the coal gas produced, came from the Pittsburgh seam of western Pennsylvania and northern West Virginia, which was then regarded as the standard coking and gas coal of the country, and the best coal available anywhere for these purposes. With the advent of the byproduct oven and the building of coke plants at the furnaces, the restriction of the use of one grade of coal for making coke was removed and the use of mixtures of low-volatile and high-volatile coals began. The change in the locations of the coke plants removed the necessity of using Connellsville coal and also made sources of gas available to the public utilities other than of their own manufacture. Most of the first oven plants were built at points distant from the Connellsville region and this afforded an opportunity for the use of coals from the southern Appalachian fields, which were then at approximately equal distances from the ovens. Since that time development has been made on a number of seams of coal of great purity in southern West Virginia, southwestern Virginia and eastern Kentucky, which have been largely used for gas, cokemaking and metallurgical purposes where low amounts of ash, sulfur and phosphorus are determining factors. These coals are much lower in the objectionable elements than most of the coal shipped from the Pittsburgh seam, or than any northern coal, and when blended with low-volntile cod produce coke in byproduct ovens that is not excelled for any purpose by any coal mined in this country, and is equaled very seldom. Coal from several of these scams is shipped in great quantities without beneficlation and is lower in ash and sulfur than any but the best washed product from the Pittsburgh seam in the north. The writer has made a study of these coals to ascertain their relative qualities and the areas and reserves of coal available in each of them. No attention has been paid to the coals of Alabama, which do not compete with any of these coals, and no coal of equivalent quality is found in

Jan 1, 1934

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By C. G. Dunn, F. Lionetti

W. G. BURGERS*—It seems almost certain that this investigation shows the way which finally, when more analogous data have been obtained, must lead to the understanding of many features of preferential growth-directions of crystals and of the occurrence of recrystallization textures. In this connection I should like to mention that Mr. Tiedema in my laboratory succeeded in developing an analogous method for preparing crystals in aluminum plates with a chosen crystal-lographic plane and direction parallel to the surface of the plate (to be published in Cryst. Ada). If such crystals were grown in high purity aluminum and test-pieces containing a few crystals such as the authors describe were prepared for this metal, it might be possible that due to the absence of growth obstructing particles, even in this low-melting point metal boundary displacements approaching equilibrium positions might be realized. With regard to the apparently marked drop in surface energy for orientation differences approaching zero degree, and orientation differences approaching those existing between twins, it seems of interest to remark that in aluminum a crystal growing at the expense of fine grained material cannot (or can only very reluctantly) absorb grains in either ap- proximately (within 5—10°) parallel or spinel twin orientation (May, Tiedema and Burgers, Nature (1948) 162, 740 and Cryst. Ada in press). Consequently with aluminum the method of preparing a crystal with a definite orientation does not succeed when the new crystal has to absorb its own texture; for example it is not possible to grow in a polycrystalline wire with a [lll]-texture a crystal with a [11 Indirection parallel to the wire axis (Tiedema: Cryst. Ada, in press). Finally I should like to mention the well-known fact (Burgers: Proc. Acad. Amsterdam (1947) 50, 723) that prolonged annealing of recrystallized nickel-iron sheet with cube-texture never succeeds in transforming this into one single crystal of the same orientation; if, by "secondary re-crystallization," large crystals are formed

Jan 1, 1950

THE Copperton mill in reality was a sort of proving ground. It was. designed to serve three purposes: (1) to verify the accuracy of the mine sampling by actually treating substantial tonnages of ore, (2) to demonstrate on a reasonably large scale the percentage of the copper in the ore that could be recovered, and (3) to permit the testing of various kinds of machines and devices for crushing and concentrating the ore, so as to guide the engineers in designing the proposed 6000-ton milling plant at Garfield. As a matter of fact, it contained a lot of second-hand equipment sent by MacNeill and Penrose from the works of the United States Reduction &Refining Co. in Colorado; and it was by no means a model installation. Probably it would have been even less efficient, except for the skillful work of George O. Bradley and-Frank-G, Janney, both of whom had worked with Jackling at Mercur. Bradley was a mechanical engineer employed to design the plant. Later he directed the design of the concentrator at Garfield and remained as consulting mechanical engineer to the company until 1915. Janney, who afterwards became manager of mills, a position that he retained until his death in 1916, was a skilled mechanic at the Golden Gate mill at Mercur when Jackling built the plant in 1897. His flair was making machinery do what it was intended to do. He was not an ore-dressing engineer in a technical sense; but Jackling him- self was a specialist in this respect as well as in designing and construction and Janney's mechanical aptitude made him a particularly valuable man in the Utah organization. John McDonald, another of Jackling's Mercur associates, was the first mine superintendent. With practically all of the available funds earmarked for construction of the Copperton

Jan 1, 1933

By W. L. Dennen, V. H. Wilson

This paper is a description of the opera-tion and results of a Humphreys Spiral Silt Cleaning Plant at the Powderly Colliery 01 The Hudson Coal Co. during the first nine months of operation and follows a preliminary description given at the .Institute cite Institute in May, 1947, in a paper titled "Preparation of Anthracite Silt for Boiler Fuel in a Humphreys Spiral Test Plant" by H. H. Otto, V. H. Wilson and W. L. Dennen. This plant is considered a full size op-erating test plant and, like all new plants, numerous minor changes in the methods of operation have been made from time to time to secure the results desired. Views of the silt preparation plant and of the screening house are given in Fig I and 2. This plant consists of 48 spirals in 8 batteries of 6 spirals each, 36 of which were to be operated as primary spirals and the remaining 12 as secondary spirals. A brief description of the plant and its operation follows. The only material cleaned at the plant during 1947 was that carried in the underflow from the Thickener which han-dles the Breaker waste water. This under-flow, amounting to approximately 2000 gpm of water and containing 12.6 pct of solids, is pumped to vibrating screens where the plus 3/16-in. material is removed. (Fig 3). This oversize material drops into a pocket from which it is trucked to the run-of-mine tipple for re-preparation.

Jan 1, 1949

By Roy A. Lindgren

SINCE the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced', at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces'. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a supe¬rior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1937

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By J. A. Herbst, A. L. Mular

Digital simulation is defined and simulation techniques are re- viewed. Typical methodology involves the selection of models, the adjustment of raw data, the selection of a fitting strategy, the assessment of model accuracy in a statistical sense, and the development of an executive simulation structure. Simulations serve as aids for process engineers in evaluating the feasibility of a proposed flowsheet and the effect of a modification to an existing flowsheet. In addition, simulation plays an important role in off-line optimization and in the evaluation of alternative circuit control strategies. Several examples are presented to illustrate these uses for simulation including applications in crushing circuits, grinding circuits, and flotation circuits. It is the opinion of the authors that, within the next decade, mineral processing plants will be studied routinely via digital simulation during the preliminary design stage. Simulation will constitute an important component of the design decision making process.

Jan 1, 1978

By C. W. Haworth, M. G. Hall

THE diffusion of copper in silver has been studied by Sawatzky and Jaumot1 and Cahoon and Youdelis.2 Sawatzky and Jaumot measured tracer diffusion in single crystal specimens but the 12.9 h half-life of CU64 limited the time of the diffusion anneal to about 50 hr, and in consequence the minimum temperature of the investigation was 716°C. Cahoon and Youdelis employed polycrystalline diffusion couples, and measured the interdiffusion coefficient over the range 0 to 2 at. pct Cu. These experiments were performed at temperatures down to 630°C and a discontinuity in the Arrhenius plot was observed at -700°C. The high D-values at lower temperatures were attributed to the effect of grain boundary diffusion. The present experiments were undertaken to investigate this anomaly and study the low temperature region of the diffusion of copper in silver. The method employed single crystal samples and a plated source of copper. Silver single crystals 2½ by 4 in. sq were grown from zone-refined silver bar (>99.99 pct Ag) by the Bridgeman technique, and $ in. thick slices were cut by spark machining. The specimens were electro-polished, and a 2 µm layer of copper was electroplated on to the planar surface at one end of each specimen using a potentiostatic voltage source. The following solution was used for plating: CuSO4 . 5H2O 125 gm H2SO4 (S.G. 1.8) 53 ml H2O 1000 ml The diffusion couples were sealed in capsules, in an argon atmosphere, and were annealed at either 701, 597, or 498°C. The temperature measurements were made to an accuracy of *l°C After the anneal, the penetration of copper into the silver was determined using an electron probe micro-analyzer. 100 sec scaler measurements of the intensity of Cu Ka! X-radiation were performed at 2 to 5 µm intervals along a line normal to the source, with a beam potential of 25 kv. Allowances were made for the background radiation, and the dead-time of the counting system in the normal way, and the intensity ratios were corrected to weight concentration by the method of Duncumb & de-Casa.3 For the analysis of the diffusion profiles, it was first observed that the copper layer did not completely dissolve in the host crystal for the specimens annealed at 498 and 591 whereas for the specimen annealed at 701°C, a single phase solid solution was formed. For the 498" and 597°C specimens, the concentration of copper in the silver at the interface was therefore constant throughout the anneal and the analysis for a

Jan 1, 1970

By Frank T. Sisco

The discovery of phosphorous is usually credited to the German alchemist Brand, in 1669, and the element was rediscovered the next year by Boyle in England. IT was more than 100 years later, however, before its presence was detected in high-carbon iron produced in early blast furnaces. In 1781 the German chemist Meyer published the results of his investigation on the ?white earth? that he had found in cast iron made from bog ores. This white earth was metallic in appearance, it was extremely brittle, it was readily fusible, and it was not attracted by magnet. Meyer noted that cast iron containing this white earth was more fusible than other cast iron, and he was sure that he had discovered a new metal ? for which he proposed the name Wassereisen, or the Latin term Hydrosiderum. Two years later the distinguished Swedish Chemist Bergmann made the same discovery, finding a ?white calx? in cast iron, which he also mistakenly considered to be a new metal, and for which he proposed the Siderum.

Jan 1, 1944

By L. B. Slichter

After statement of the principles of similitude which apply to electromagnetic modeling, charts showing the inductive response of conducting spheres as dependent upon frequency, conductivity, and size are exhibited in this paper. The shape of the curve which relates intensity of response to frequency is significant in indicating the advisability of low frequencies in the exploration for conducting bodies, when consistent with the securing of a large percentage of the ideally possible response. Comparisons of theoretical response and that observed with models are shown, and relationships with the subject of applied electromagnetic prospecting are indicated. Maxwell Field Equations The Maxwell field equations summarize the physical laws that govern electrical field phenomena; they are the basis for the solution of electromagnetic problems. These concise equations, with adequately formulated boundary conditions, specify the complete electrical condition of continuous media, and the development of their solution amounts merely to a more convenient re-expression of phenomena already completely described. Thus, the immediate content of the field equations themselves is sufficient and sometimes convenient for the treating of certain questions (such as those relating to electromagnetic models) which are independent of the special factors of geometry, or the nature of an impressed field. The four Maxwell field equations are written below, in c.g.s. gaussian units: curl E = -B/c [21 div eE = 4pp [31 div B = 0 [41

Jan 1, 1932

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By John J. McKetta. Jr., Louis B. Lesem, George H. Fancher

The proration of oil produced in the field frequently is based partially or entirely upon the gas-oil ratio of wells. The measurement of the gas-oil ratio is one of the more important field tests in regulatory and pro-ration work, and the test always should be conducted according to standardized methods and procedure. Obviously, the gas-oil ratio and the volume of gas produced by a well depend upon many factors but should be independent of the method of measurement and of the devices used to measure gas and oil. Consequently, the volume of gas accompanying a barrel of oil produced by a well may be measured by any reliable and accurate device or instrument. Frequently either a critical flow prover or an orifice well tester is used for this purpose, and for a particular well the same rate of flow of gas should be obtained regardless of whether a critical flow prover or an orifice well tester is employed in the test. In Texas, when using either instrument, either Capacity Table 1 or 5' is employed in making the necessary computations. If the tables are used, a discrepancy always is found whenever the two instruments are compared by extrapolation to the same conditions of flow. Clearly, Tables 1 and 5 must be at fault in some respects. The orifice well tester and the Bureau of Mines type of critical flow prover are essentially the same instrument; both devices utilize a square-edged orifice 1/8 in. in di-ameter as the primary element, and both freely discharge gas to the atmosphere. Tables for the orifice well tester' have been published in the ranges of 0 to 15 in, of water and 0 to 40 in. of mercury (Hg) differential in pressure. Coefficients for the critical flow prover have been published for differentials in pressure greater than 75 psia. An extrapolation of either differs from the other set of data as much as 18 per cent at some points. No immediately obvious reasons for the discrepancy was found, and data available from the literature were insufficient to effect reconciliation. Consequently, a series of experiments was performed to check the available data and to determine discharge coefficients for the two devices in an overlapping range of differential pressure. The correlating equation used in preparation of tables such as Tables 1 and 5' is the so-called hydraulic equation, Q = C1 vh .....(1) The tables cover orifice sizes from 1/8 through 1 1/4 in. A second set of tables, for use with greater differentials in pressure, apply only to the 3/4, 1, and 1 1/4-in. orifice plates over a pressure range of 0 to 40 in. of Hg. The correlating equation used in preparation of the tables is Q = C2 vH(29.32 + 0.3H)/G . (2) Each of these equations is valid only for the range to which it has been applied, and neither equation is valid for extrapolation. Theoretical equations for flow through an orifice are based upon assumptions of fractionless flow and an emergent jet the size of the orifice. A multiplier, C,, called the discharge coefficient, is inserted into the theoretical expression to compensate for both frictional losses and the contraction of the jet experienced in the plane of the orifice. Buckingham3 shows that C, should vary with the ratio of upstream to downstream pressure for flow of a compressible fluid at any average linear velocity through the orifice less than the velocity of sound. Work published by the National Advisory Committee for Aeronautics4 indicates that the variation continues into the so-called critical flow region until the vena contracta coincides with the plane of the orifice. The NACA work, however, does not indicate a leveling off of the coefficient. The work of the Bureau of Mines5 for the critical flow prover was based on differential pressures greater than 75 psi and indicates that the discharge coefficient, Cd, is constant in this region at a value of about 0.86.

Jan 1, 1958

By A. H. Larson, T. P. McNulty

RECENTLY, an investigation of the absorption of sulfur dioxide gas in molten binary copper alloys was conducted. A Sieverts-type apparatus, consisting of a mercury-filled gas dispensing buret and a mercury manometer, was used initially for determining the volume of gas absorbed as a function of pressure. The equilibration behavior of the alloys studied indicated that the mercury in the gas measuring system was absorbing sulfur dioxide. Owing to the widespread use of mercury as a displacement medium in absorption studies, an investigation was made to determine the nature and magnitude of the mercury - sulfur dioxide absorption effect. The gas measuring system was modified by substituting a Worden Quartz Products Type PDHV fused-quartz-spiral pressure gage for the mercury-filled dispenser and manometer. The dispensed gas volume at known temperature and atmospheric pressure was measured by evacuating a Pyrex vessel of known volume and by admitting sulfur dioxide into the vessel until the attached quartz pressure gage registered atmospheric pressure. Atmospheric pressure was measured concurrently with a separate mercury barometer. The volume of the empty sample chamber and its attendant apparatus was determined by measuring the equilibrium pressure accompanying the addition of a measured volume of sulfur dioxide into the initially evacuated system. The volume of the mercury sample was calculated from the density of mercury at the temperature of the study (25°C). Measured volumes of sulfur dioxide were then dispensed into the system and the equilibrium pressure accompanying each gas addition was determined. From the difference between the system volume and the mercury volume, the number of moles of gaseous sulfur dioxide remaining in the system at each pressure was calculated. The difference between the number of moles of gas dispensed into the system, denoted Enso2: and the number of moles of gas remaining in the system after absorption equilibrium had been attained, denoted nso2(g), was equal to the number of moles of absorbed gas, denoted nSO2. The number of moles of absorbed gas was then converted to absorbed volume, denoted VSo2, in cu cm at stp conditions of (PC and 760 mm Hg. Table I contains calculated values of Snso2, nSo2(g), and VSo2 for different sulfur dioxide pressures. In the original system, denoted Run I, volume limitations of the gas dispensing system prevented absorption studies at equilibrium pressures near atmospheric pressure, so a different gas dispensing system, denoted Run 11, was used for determining the last pressure reading in Table I. The data in Table I are expressed in terms of the absorption of sulfur dioxide in 49.68 cu cm of mercury. In Fig. 1, these data are expressed in terms of the absorption of sulfur dioxide in 100 cu cm of mercury. Since the absorption data plotted in Fig. 1 show a linear relationship, the volume of sulfur dioxide absorbed in mercury is a function of the first power of pressure. The absorption reaction is So2(gas) = SO2 (in Hg) The first-power pressure dependence, coupled with the fact that the sulfur dioxide could be removed from the mercury by applying vacuum, indicated reversible

Jan 1, 1967

[A AALSETH Earl P (M 51) Consult Geol Engr 2019 Eldorado Dr, Billings, Mont ABADIE Henry G (M 43) Asst to. Supt of Oper Long Beach Oil Dev Co 925 Harbor Plaza, Long Beach 2, Calif. ABBET Waldo (A 56) Asst Diet Oper Supt Sun Oil Co P 0 Box 66, Stowelt, Tex ABBOTT Clifton T (A 60) Apartado 677, Maracaibo, Venezuela ABBOTT Fred E Jr (M 59) Abqaiq Diet Mgr Arabian American Oil Co Dhahran, Saudi Arabia ABBOTT J L (M 56) Partner Pritchard & Abbott 1010 Ft Worth Natl Bk Bldg, Fort Worth 2, Tex ABBOTT Richard H (J 51) Partner Abbott & Howard 422 W Hermosa, San Antonio 12, Tex ABBOTT William G (M 50) Div Mgr Rice Engrg &. Operating Inc Box 1142, Hobbs, N. M. ABDERHALDEN Ronald R (J 59) Prod Engr Continental Oil Co Box 100, Carml, 111]

Jan 1, 1961

By H. LeChatelier, B. Bogitch

Page Introduction........................... 134 Methods of Investigation....................... 135 The Tridymite Network...................... 137 Independent Variables....................... 146 Manufacturing Operations..................... 153 Introduction Silica brick are indispensable in the manufacture of steel because they alone are able to withstand the high temperature of regenerative furnaces. All attempts to replace silica brick by other refractory materials for this purpose have failed, but the reason for this failure has remained obscure; we shall give an explanation later in this paper. Before the war, silica brick employed in France came principally from abroad, for which reason, since the beginning of hostilities, certain French steel works have been seriously handicapped. Our attention was first directed to the question by M. Bied, Engineer of the Teil Works. With him, we began certain investigations, at first using our laboratory and the furnaces of neighboring steel works. The larger part of our experiments, however, have been made in the laboratory of the Faculty of Sciences at the Sorbonne. For the heating of our samples, we are deeply obliged to MM. Charpy, Yeatmann and Guerineau. In undertaking these studies, our first aim has been to render assistance to French industry, by indicating, as precisely as possible, the necessary conditions for the manufacture of high-grade brick; but at the same time me have

Jan 1, 1919

By H. I-Lieh Huang, O. D. Sherby, J. E. Dorn

RECENT investigations1-4 have suggested that the total plastic strain, C, for high temperature creep under a given stress can be correlated by means of a temperature-compensated time, te- where t is the duration of test, e is the base of natural logarithms, aH is the activation energy for creep, R is the gas constant, and T is the absolute temperature. A typical set of data on which this deduction was based is given in Fig. la. Inasmuch as the e-in t curves for the various temperatures are identical except for their displacement along the In t axis where f and are appropriate functions. If the increase in creep rate with an increase in temperature is exclusively ascribable to a single process involv- ing thermal activation, (T) should equal RT and therefore it = constant [2] where ?= te Assuming the validity of this relationship, ? = ?2 at the same strain, or where the subscripts refer to two alternate test conditions.

Jan 1, 1957

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962