Search Documents

By Leason Adams

THE thermocouple as a device for the measurement of temperature is rivaled only by the platinum-resistance thermometer. Both instruments are capable of the highest precision, but the thermocouple, on account of its cheapness, ease of construction, and small cross-section, is finding a continually widening field of usefulness for industrial control as well as for laboratory measurements. Formerly, the thermocouple was subject to two disadvantages: errors due to lack of homogeneity of the metal and the labor involved in the interpolation between fixed points on the temperature scale. Former publications from the Geo-physical Laboratory have described the methods' for the selection and testing of thermocouple wire and have presented standard calibration curves2 for platinum-platinrhodiun and copper-constantan couples, so that the most important objections to the thermocouple as a precision thermometer have been removed. The calibration tables published in 1914 covered the range 0-1755° for the platinum-platinrhodium couple and 0-350° for copper-constantan. It has seemed desirable to extend the table for copper-constantan to -200 and also to include a table for the Hoskins thermocouple. Accordingly, in this paper, the new tables are presented, together with a brief explanation of their use; and, finally, certain diagrams and a paragraph on "cold-junction corrections" are given. Standard Calibration Tables.-In Fig. 1, which illustrates how the electromotive force (e.m.f.) of each of the three couples varies with the temperature, the temperatures of one junction are plotted as abscissas and the corresponding thermo-e.m.f.'s as ordinates. The second junction of the couple is supposed to be at 0°; the curves, therefore, pass through

Jan 9, 1919

By William E. Hubbard

During the last decade the known reserves of petroleum in the United States have increased from about five billion to over thirteen billion barrels. From the standpoint of public welfare the existence of these known reserves presents an undeniably favorable picture, but viewed from the position of many a harassed operator the blessing has not always been considered an unmixed one. Along with this increase in excess reserves, curtailment of production has come into being as a matter of necessity and the principle of proration as a matter of equity. As a practical matter it has been considered necessary to curtail the production of old wells as well as that of new wells in a pool. The right of new pools to produce has been recognized, and the allowable for them has come partly from increased market demand and largely from the allowables already enjoyed by the developed pools. The natural result—a downward trend in daily per-well allowables—has been especially felt by Texas operators. This trend may be illustrated by Table 1, which comprises the five active areas in Texas, and from which may be noted the following: 1. The average daily allowable per well has decreased about 53 per cent in three years. 2. Of the 184,000-bbl. increase in total allowable for the five areas, 29,000 bbl. came from the increase in state demand and 165,000 from the combined allowables of the remaining pools in the state.

Jan 1, 1937

By W. Mostowitsh

I. Introductory LEAD sulphate occurs as anglesite, and is formed in every roasting of lead sulphides or sulpho-salts containing lead. In smelting in the blast furnace an ore containing natural or artificial lead sulphate, a large part of the sulphur present goes to the formation of the intermediary product matte which requires further treatment for the recovery of the values it contains. It is therefore of importance to study the behavior of lead sulphate at elevated temperatures, both without and with reducing agents, especially as the information available gives data which are more or less conflicting. II. Decomposition of Lead Sulphate by Heat The dissociation of PbSO4 into PbO and S03 or S02 and 0 has been discussed by many metallurgists. The following data are considered to be representative. Doeltz and Graumann1 found that PbSO4 was not affected by heat at 800° C.; that dissociation began at 900° C., and was rapid at 1,000° when the salt lost in 1 ½ hr. 14.3 per cent. of its weight, the dry salt containing 26.43 per cent. SO3. Hofman and Wanjukow2 summarize their work upon the dissociation of metallic sulphates with the statement that the decomposition of PbSO4 begins at 195° C., but progresses very slowly, with the formation of the basic salt 6PbO.5S03 at 705°; that this salt undergoes a transformation at 847°, begins to be decomposed at 888°, to sinter at 896°, and to fuse at 910°; rapid dissociation begins at 952°, and is accompanied by volatilization of PbO; retardations at 958° and 962° indicate an acceleration of decomposition which, however, is not complete. Proske3 found that PbSO4 gave off at 900° C. in 30 min. only 0.63 per cent. of its SO3, and that the loss increased with

Jan 5, 1916

By W. Mostowitsch

Lead sulphate occurs as anglesite, and is formed in every roasting of lead sulphides or sulpho-salts containing lead. In smelting in the blast furnace an ore containing natural or artificial lead sulphate, a large part of the sulphur present goes to the formation of the intermediary product matte which requires further treatment for the recovery of the values it contains. It is therefore of importance to study the behavior of lead sulphate at elevated temperatures, both without and with reducing agents, especially as the information available gives data which are more or less conflicting. 11. Decomposition of PbS04 by Heat The dissociation of PbSO4 into PbO and SO3 or SO2 and 0 has been discussed by many metallurgists. The following data are considered to be representative. Doeltz and Graumannl found that PbS04 was not affected-by heat at 800" C.; that dissociation began at 900" C., and was rapid at 1,000° when the salt lost in 1 1/2 hr. 14.3 per cent. of its weight, the dry salt containing 26.43 per cent. SO3. Hofman and Wanjukow2 summarize their work upon the dissociation of metallic sulphates with the statement that the decomposition of PbS04 begins at 195' C., but progresses very slowly, with the formation of the basic salt 6PbO.5SO3 at 705"; that this salt undergoes a transformation at 847") begins to be decomposed at 888") to sinter at 896", and to fuse at 910"; rapid dissociation begins at 952") and is accompanied by volatilization of PbO; retardations at 958" and 962" indicate an acceleration of decomposition which, however, is not complete. Proske3 found that PbSO4 gave off at 900" C. in 30 min. only 0.63 per cent. of its 803, and that the loss increased with

Jan 1, 1917

[RECEIPTS Magazine, Advertising $ 32,823.60 Sale of Magazines 3,933.29 Total Magazine $ 36,756.89 Dues, Arrears 5,866.97 Dues Current 100,223.80 Dues of New Members 6,143.29 Dues in advance 1,586.32 Initiation fees 6,820.00 Sale of Transactions 5,464.99 Sale of Binding 5,618.90 Sale of Pyrometry Volume 336.30 Sale of Indexes and Emmons 106.10 Sale of Pamphlets 575.32 Miscellaneous Receipts 105.60 Interest on Bank Balances 1,217.67 Interest on Life Membership Investment 512.18 Interest on James Douglas Library Fund 5,678.67 Total Receipts $177,013.00] [ ]

Jan 1, 1925

By John D. Kalasky

The success in providing adequate ventilation to the active faces of a coal mine for all methods of mining depends upon good face control and the air distribution and control system. A good system provides overcasts, air locks, regulators and bleeders so that an adequate flow of air will be confined to the working places with least opportunity for interruption, and that a flow of air is maintained, however small, across the worked out area to the bleeder and away from men and equipment at all times. In gaseous mines, it is just as important to satisfy effective bleeding as it is to satisfy the air volume requirements in the operating splits. The two requirements go hand in hand. Although not complicated, ventilation and methane drainage in longwall mining in a gaseous mine require careful forethought and adequate facilities to make them safe.

Jan 8, 1966

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By John E. Conley

The slate industry of the United States has shown a marked decline in value of products made annually since the peak year 1925, although there has been moderate improvement over the lean years 1932 to 1934. In 1940, the value of all slate products sold was approximately 5¾ million dollars for a total output of 473,450 short tons. The quantity sold was a little less and the value a great deal lower than the annual averages for the past two decades. Enormous quantities of waste materials result from the quarrying, splitting and milling of slate. Obviously, utilization of such waste material is desirable, not only from the viewpoint of economical operation but also for the purpose of conserving natural resources. One possible use is to produce expanded or puffed lightweight aggregate for use in concretes. Such concretes are strong enough for specific uses, and the advantage of lightness could be obtained in such structures as the walls and roofs of buildings, suspension-bridge roadways and various other applications where weight is a factor. Conceivably, these uses could consume an appreciable annual tonnage. Use of Waste Slates for Making Aggregates The lightweight-aggregate industry has been discussed elsewhere4,5 and need not be covered in detail in this paper. The materials commonly utilized are naturally occurring aggregates such as volcanic cinder, tuff and pumice; by-product materials, such as ordinary cinders and air-cooled slags; and the specially manufactured products, including Haydite, Pottsco, Gravelite, Cel-seal, Superock and Waylite. Slates, however, have not been given the consideration they merit, especially in the United States. In the British Isles, some work has been done3 on certain Welsh slates by the Building Research Station to stimulate the use of these wastes. Requirements for Raw Materials As pointed out by Hughes,4 the lightweight-aggregate industry is segregated in regions adjacent to large cities in order to localize the market and avoid the necessity of long freight haulage. Waste slate from the deposits of eastern Pennsylvania, northern Maryland, and Virginia would meet the basic requirement of ally low-priced structural raw material. One apparent advantage is attained when slate waste, normally discarded, is utilized in the manufacture of a by-product. Mining or quarrying costs usually have been assessed against the main product. Some additional grinding might be desirable, but this operation would be relatively cheap, as most slates grind easily. It is believed that virtually all slates, when properly heated, will expand to some degree. However, types that will expand from 3 to 7 times their original volume are preferred. Fig, I illustratcs the expansion of a Pennsylvania slate. The cube originally

Jan 1, 1942

By M. H. Harris

A solution has been obtained to the problem of calculating flow into a cased and perforated well. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. Computer experimentation indicated that the results are within 3 per cent of the exact solution. Computed results are presented as an apparent skin effect, on a series of dimensionless working curves. Productivity ratios can be rapidly calculated from these data for the wide range of wellbore and reservoir properties actually encountered in field practice. Any reasonable vertical unisotropy ratio can be included in the computation. Productivities can be calculated for wells perforated in a regular pattern, a single horizontal plane or a vertical line on one side of the casing. Solutions for asymmetrical perforation patterns can he easily obtained from the working curves. Solutions for flow into sells completed with a horizontal notch are also provided. Results show that productivity can be increased by extending perforation penetration. This is especially true for shallow penetrations. The highest productivity is obtained when perforations are arranged in horizontal planes, as opposed to a vertical line on one side of the casing. Four or five perforations in one plane will approach the maximum productivity. The effect of perforation hole diameter is small, and is rioticeable only in shallow penetrations. INTRODUCTION The perforating method of well completion has been successfully and widely used in most producing areas. In the past, the desired perforation results were achieved by simply shooting numerous large holes in the casing. A perforating scheme for an area, or particular well, was established by evaluating two types of experimental data: the well flow index and the productivity ratio.' 3 The well flow index test is a means of determining the relative flow capacity of perforations in a linear system. This test also gives information on the perforation size, shape and hole damage which can be expected under well-bore conditions. However, relative flow data from this test cannot be accurately tarnsformed into the radial wellbore system. Thus, no true indication of the productive capacity of a perforated well can be obtained from the well flow index test. A well productivity ratio is derived from electrolytic models built to simulate perforated wells. Available productivity ratio data 2,3 are limited in that all important variables are not extensively evaluated. For example, data are limited to well radii of 3 and 6 in., and to maximum perforation penetration of 1 ft. Practically no information is available on the pattern of flow into a perforation. The effect of various perforation patterns on well productivity has not yet been determined and the effect of perforation diameter has not been thoroughly studied. Also, it will be shown that this type of electrolytic model data is probably in error by as much as 10 per cent or more. Modern completion techniques such as limited-entry perforating, single-plane fracturing, steam and hot air injection and chemical consolidation of incompetent formations all rely on injection and/or production from a limited type of completion. These completions may consist of several high-capacity perforations or a horizontal notch which is equivalent to an infinite number of perforations in one plane. Proper design of these new completion techniques requires, in part, accurate estimates of a well's productive capacity. Data on perforated and notched well productivity have been determined in this investigation. Results are presented as a function of the pertinent variables. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. DESCRIPTION OF PROBLEM PRACTICAL APPLICATION The computed results can be applied to wells which meet several general specifications. An external drainage radius of the well must be known or assumed, but the well need not be drilled on a regular pattern. The well must be cased and cemented through the entire producing interval. And, the casing must be perforated with one or more horizontal planes of perforations. The perforation pattern itself must conform to three geometrical requirements. 1. The perforations in a plane must divide the plane into equal angular segments (Fig. 1). Four perforations per plane would be 90" apart. 2. Perforations in a plane must be directly above or beneath perforations in adjacent planes. For two shots per plane, perforations would lie in the BB' plane (Fig. 1). 3. Horizontal planes must have equal vertical spacing and be separated from the top and bottom of the formation by one half the spacing interval. Single planes of perforations should be in the middle of the formation. This is shown in Fig. 2 where h is the formation thickness in a single plane conlpletion or the spacnig interval in a multiple plane completion. The spacing interval at the top and bottom of the formation may vary somewhat without causing an appreciable error in the productivity calculation if the formation is reasonably thick and there are many horizontal planes of perforations. A special provision has been made to calculate the productivity ratios of wells with uneven spacing intervals, or for the case where a single plane of perfora-

Jan 1, 1967

RECEIPTS [Magazine Advertising $ 62,564.83 Magazine Sales 3,591.44 Totalm 66,156.27 Dues, Arrears7,032.88 Dues. Current96,839.74 Dues, New Members6,525.00 Dues, in advance 1,907.02 Initiation Fees7,584.00. Sale of Transactions3,909.03 Sale of Binding7,845.05 Sale of Special Editions 338.20 Sale of Year Book76.20 Sale of Pamphlets1,189.06 Sale of Authors' Reprints867.54 Miscellaneous Receipts62.93 Interest on Bank Balances1,712.89 Interest on General Reserve Fund337.50 Interest on Life Membership Fund557.84 Interest on James Douglas Library Fund....5,491.89 Total Receipts$208,433.04] [ ]

Jan 1, 1925

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By H. H. Reamer, B. H. Sage

The formation volume and the relative volume of the liquid Phase of mixtures of Condensate and gas from five different parts of a field in the Louisiana area have been established experimentally. These studies included gas-condensate ratios as high as 25.000 cu ft/bbl at pressures up to 5,000 psi. The gravities of the tank condensates were between 53.9° and 63.9° API. The compositions of the condensate and gas samples inves-ligated are presented in tabular form. The formation volume. the relative volume of the liquid phase. and the specific volume of the mixtures are available. A rough correlation of the formation volume as a function of pressure. temperature, and gas-condensate ratio has been presented. This correlation i-considered applicable only to the range of conditions covered in this investigation for systems of similar nature and com-position. INTRODUCTION Often a knowledge of the influence of temperature. Pres sure, and relative quantities of condensate and gas upon the volumetric behavior of fluid*. from a given field has been employed in estimating the Conditions existing in the reservoir. The early work of Beecher and Parkhurst' and the more rrcent Studies of the Dominguez' and San Joaqnin Valley Field;: are examples of experimental studies of this character. Correlation of the volumetric behavior of naturally occurring hydrocarbon mixtures has Proved To be feasible' . at low gas-conden-sate ratios-; for fluids*. from a single geographic area. Progres 5 is being made in the Prediction of the volumetric behavior of distillate systems at high gas-condensate ratios and pressure.. However. the estimation of the retrograde". ' dew-point pressure still remains uncertain and probably can best be established by experiment. For this reason it appears of interest to make available experimental information about the volumetric behavior of mixtures of condensate and gas from five different part.; of a single field. This material shows a rough similarity to data for mixtures of condensate and gas from San Joaqnin ' Valley Fields. In the present paper. 110 attempt has been made to coordinate the available information on tbe volumetric behavior of fluids from condensate fields. It appears hopeful that progress can be realized by the utilization of recently developed equa-tions of state.!' However. the primary problem in any such correlation is the proper identification of the components and constituents of naturally occuring systems. Additional experimental information may be required to permit the determination of the values of the constants of the equation of state for References given at end of paper. Manuscriptt received in the office of the Petroleum Branch June 11. 1951. *For present purposes low gas- condensate ratios will he considered as those below 3,000 cu ft/bbl, and the region of high gas-condensate ratio will be limited to compositions containing more than 5,000 cu ft of pas per bbl of condensate. Mixtures Containing between 3,000 and 5.000 CII ft OF gas per bbl will be considered of intermediate gas-condensate ratio.

Jan 1, 1952

By H. L. Riley, B. W. Gandrud

AS far as the present writers know, this system of flotation has not been used elsewhere in this country, but in the last couple of years it has been introduced, with minor variations, at one plant in England and one in Wales.' The system has been described and discussed in a number of publications.2-5 The following is quoted from an abstract of the latest of these,5 a paper presented at an International Conference on Industrial Combustion in 1952. On the basis of experience to date with the commercial plants, it is believed that the kerosene-flotation process incorporates all the necessary elements to make it greatly superior to anything else now available for treating of fines in wet processes of coal preparation. Additional study and investigation are still needed, however, to determine if certain phases of the process can be improved to such an extent as to make it generally satisfactory and acceptable to the industry. Further improvements will be needed with respect to the capacities of the flotation cells and the reagent consumption. The situation referred to above explains why an investigation is being made of the possibilities of achieving better cell capacities. Results obtained from this investigation, which is still in progress, are believed significant with regard to both cell capacity in general and the relation of cell design to cell capacity in particular. Commercial equipment now being used in a laboratory-type investigation should have performance characteristics similar to those of the larger machines. Equipment and Procedures: All flotation tests have been made in a standard Denver sub-A 24x24-in. unit cell of 12-cu ft volume. Cell modifications to make it more suitable for the tests were an adjustable front-wall section for varying cell depth and a perforated scraper-drag assembly for removal of the float product. There is also an apron dry-coal feeder, a gravity-feed water supply, reagent feeders, and a centrifugal pump that feeds the mixture of coal, water, and reagents into the flotation cell. A wattmeter connected into the drive-motor circuit records the power requirements of the impeller throughout each run. Dry coal, water, and reagents are all fed through a pan-type intake to the feed pump. A Sturtevant blower was set up to furnish air for supercharging. A centrifugal pump with a garbage-can intake provides for disposal of refuse flow to an outside settling tank. Figs. 1 and 2 show the flotation cell; Fig. 2 also illustrates the blower for supercharging. For purposes of this investigation, the percentage by weight of the feed coal recovered in the float product under a standard set of conditions has been considered as the criterion of cell capacity. The authors realize that such a criterion may be somewhat unorthodox, as the term cell capacity is usually understood to refer to feed input and ordinarily takes into account the ash analyses of the float product and refuse. However, the word capacity is flexible enough so that Webster gives one definition as maximum output, a definition which seems to justify, at least partly, acceptance of the above criterion. It has been the authors' experience in the Birmingham district that the ash-reduction efficiency of the coal-flotation process is generally satisfactory and that the only real problem is to increase the rate of float recovery so that the feed rate to any given bank of cells can be increased without undue loss of coal in the refuse. Originally it was planned to operate the flotation cell to simulate continuous operation during sampling periods. It was assumed that operating for reasonable time with feed coal, water, and reagents turned on would stabilize conditions so that the weight of float coal discharged during a fixed time interval would be an accurate measure of the rate at which the coal was being floated. It developed, however, that this supposition was erroneous. The float coal, caught for fixed time intervals and weighed, gave widely varying results in duplicate runs. Efforts to correct this trouble failed, and it was decided to try to operate on a batch-test basis, whereby all the float coal produced during a run on a known weight of feed coal would be caught in tubs, dewatered, and weighed. This method gives consistent and reproducible results, with total float product weight rarely varying by more than 3 or 4 pct on duplicate runs. The standard test procedure is as follows: A 132-lb sample of dry feed coal is weighed and placed in the feed hopper. The feeder is adjusted for a rate of 800 lb per hr. Feed water and reagents are turned on, and the feed and refuse pumps are started. One minute later the impeller is started. Six minutes are allowed for the cell to fill up with the water-reagent mixture. The feed of dry coal is started at the end of this 6-min period. One minute later the float-coal removal drag is started. The float coal is caught in one tub for the first 6 min after the flow of feed coal starts. Tubs are then changed, and the float coal is caught in a second tub until the feed coal runs out, when the tubs are again interchanged to catch the float coal for the remainder of the run in the first tub. The cell is kept running for 3 min with the water and reagents on after the feed stops to allow residual float coal to be removed. At the end of a test the wet float coal in both tubs is weighed and the total weight recorded. The product in the second tub is used for moisture determination and screen-size analyses. When the

Jan 1, 1956

By N. H. Parker, J. G. Papailias, G. Gutzeit

In its many forms, the turbine has greater latitude of application than any other mixing device. It is readily adaptable to all tank shapes, from the shallow pan to the tall and narrow stovepipe. Although turbine mixers can be adapted to most tank conformations, experience has shown that there is a preferred shape for optimum efficiency in each service. In the accompanying drawings this relationship is illustrated by the shallower tank for slurry suspension. The taller tank is preferable for continuous staged systems, or maximum retention of the gas phase in absorption. No single turbine covers the entire range of these applications with maximum efficiency. The back-sloped blade offers maximum power economy. The straight blade develops a higher discharge velocity for the dispersion type of service requiring localized shear. The same high shear environment is provided by the back-sloped impeller with stator ring assembly, which permits the most positive discharge control, Fig. 1. Positive stream control is critical in solids suspensions.

Mar 1, 1956

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By M. Smutz, C. J. Baroch, E. H. Olson

IN 1949 an orebody containing some 10 billion lb of recoverable rare earth metals was discovered in the Mountain Pass district of San Bernardino County, California.' The following year Molybdenum Corp. of America purchased a number of claims at the deposit and a mill on the property which had been constructed to process the district's gold ores. Average composition of ore from the San Bernardino deposit is less than 0.1 pct Tho2, 25 to 35 pct calcite, 10 pct rare earth oxides, 15 to 20 pct silica, and 30 to 40 pct barite.' Rare earth content of the ore analyzes 50.7 pct CeO2, 4.2 pct Pr6O11, 11.7 pct Nd2O3;, 1.3 pct Sm2O3,, and 34.3 pct La2O3 and others.' By floating the barite and depressing the bastna-site, Molybdenum Corp. of America produced a concentrate that contained 60 to 70 pct rare earth oxides. More than 25 pct of the rare earths, however, was lost in flotation. It seemed likely that a more economical method could be found. At the present time most of the rare earths in the concentrates are converted to rare earth chlorides, which are either fed to ion exchange columns for separation of the individual rare earths or reduced to misch metal. Current investigation shows that solvent extraction may achieve this separation more economically than ion exchange. The study reported here was undertaken to develop an economical method of preparing a pure rare earth nitrate mixture from California bastnasite ore. Results indicated that more than 98 pct of the rare earths could be recovered. Several possibilities were considered for processing bastnasite ore, but only the method outlined in Fig. 1 was investigated. This involved leaching the calcined ore with nitric acid. The nitric acid process is discussed under the following headings: 1) calcination of the ore, 2) leaching of calcine, 3) filtration studies, 4) solvent extraction, and 5) nitric acid recovery. Calcination: Since California bastnasite ore contains 25 to 35 pct calcite and about 10 pct bastnasite, calcination was needed to reduce the violence of reaction with nitric acid. Weight losses of 26 to 30 pct were obtained by calcining the ore at 900°C for I hr or at 800°C for 4 hr. Longer periods resulted in no further weight loss. Leaching the Calcine: When the bastnasite calcine was leached with 30 pct nitric acid for 8 to 10 days, rare earth recoveries of only 45 to 50 pct were

Jan 1, 1960

By G. G. Hancock, H. H. Johnson

Hydrogen gas at atmospheric pressure is shown to cause substantial embrittlement in a martettsitic high-stretzgth steel. Subcritical crack growth is observed at very lom stresses and with high growth rates. It is suggested that an adsorbed layer of hydrogen atoms at the crack-tip surface provides the damaging hydrogen. Oxygen in small quantity, as little as O.7 pct by volume, is shown to eliminate subcritical crack growth in gas environments caused by hydrogen or water vapor. However, dissolved oxygen in water has little or no influence upon crack-growth rates. Oxygen-stopped cracks may be restarted by water, or by hydvogen or water vapor if oxygen is removed from the environment. These observations are interpreted in terms of preferential adsorption of oxygen at the crack tip and the formation of an oxide barrier. RECENT investigations1-3 have demonstrated that environmental factors are frequently responsible for delayed failure in martensitic high-strength steels. The environment causes crack initiation from preexisting cracklike flaws at unexpectedly low stresses, often far below the uniaxial yield strength. The crack then propagates at a rate controlled by the environment and the crack-tip stress-field intensity; during this period crack propagation will cease if either the stress or the aggressive environment is removed, and this may be considered a definition of subcritical crack growth. Fracture occurs when the crack has grown to a critical length, such that the fracture toughness of the steel is exceeded. Several liquids are known to cause delayed failure, but water and water vapor are the most severely damaging of the environments investigated to date.'-3 It has been suggested that hydrogen produced during corrosion reactions may be the actual embrittling agent2 The severe embrittlement caused by water vapor inevitably raises the question as to whether other gas environments are damaging. Previous work4'5 has demonstrated that high-pressure hydrogen (2250 psi or greater) is an effective embrittling medium, as measured by such criteria as reduction in area, notch tensile strength, and time to failure. Moreover, the embrittlement was eliminated by the addition of small quantities of air or oxygen to the high-pressure hydrogen, but it was not influenced by additions of nitrogen or argon.4 In the present study attention is focused upon gas environments at atmospheric pressure, in particular hydrogen and oxygen. The influence of these constituents upon the initiation and growth of a crack from a pre-existing cracklike flaw in a high-strength steel was determined directly by the electric-potential method of monitoring crack growth. MATERIALS AND PROCEDURE The H-11 steel was supplied by the U.S. Naval Research Laboratory as 3 by 12 by 0.065 in. sheet specimens with 1-in. transverse center slots. The slot tips were finished by Elox machining to a radius of 0.001 in. or less. The yield strength was 230,000 psi; chemical composition and heat-treatment schedule are given in Table I. The experimental apparatus, precracking procedure, and incremental loading sequence have been described previously.3 In the only significant change, precracking was sometimes carried out by a hydrogen embrittlement and baking technique. All experiments were conducted at room temperature; the hydrogen gas environment was purified by a commercial palladium purifier. Crack initiation and propagation were followed by the electric-potential method,'-3 using a calibration that has been recently dicussed. Stress-field intensities at the crack tip were computed by the conventional Irwin frmula; the plasticity correction was negligible and therefore not included. EXPERIMENTAL RESULTS A striking brittleness associated with molecular hydrogen at atmospheric pressure is demonstrated by the data in Table I1 and Fig. 1, which indicate that subcritical cracks in hydrogen initiate at lower stress-field intensities and propagate more rapidly than in fully humid argon. Ki and Kf are the crack-tip stress-field intensities at initiation and termination of subcritical crack growth, respectively. Termination, of course, corresponds to fracture. In both hydrogen and humid argon Ki is less than Kf

Jan 1, 1967

By Mark Sheppard

DURING the winter of 1937, the writer visited a West Virginia stone quarry at which the overburden is stripped hydraulically. The quarry is in a bed of limestone, about 200 ft. thick, which outcrops on a hillside above a small river; the quarry face is 175 ft. high. The top of the stone is cut in all directions by erosion channels, which are filled with a tough, red clay. Some of the larger channels are 30 ft. deep and 8 ft. wide. The thickness of the clay overburden ranges from a few inches to 10 ft., the average being estimated as less than 3 feet. The topography of the district is rugged, and the hillside above the quarry face is not suited to the use of the usual mechanical methods of moving dirt. Until hydraulicking was started 10 years ago, the over- burden was dug by hand labor, dumped to the quarry floor and transported to the dump in quarry cars. Cleaning deep channels was a slow and expensive process. When hydraulicking was started, the top of the quarry face was over 200 ft. above the level of the river. The pipe line was carried in a semi- circle around the top of the quarry about 200 ft. from the face and about 50 ft. above it. As there is no adequate supply of water above the quarry, the water must be pumped from the river. As quarrying progressed the pipe line was moved until the discharge points are now over 300 ft. above the river. Water is pumped from the river by a four-stage centrifugal pump having a 5-in. intake and a 4-in. discharge. It is direct-connected to a 200-hp., 2300-volt, 1760-r.p.m. induction motor. At 1760 r.p.m. the rated capacity of the pump is 750 gal. per minute under a head of 600 ft. The pump is installed in a house of frame construction on the river bank, about 10 ft. above normal water level, which also houses the pump for the mill-water supply. Above the pumps are hoisting bays into which the motors are raised whenever the river reaches flood stage. An 8-in. suction line, equipped with a strainer and a foot valve, takes the water from a concrete sump at the edge of the river. The pipe line from the pump consists of 1750 ft. of 8-in. spiral steel flanged pipe and 800 ft. of 4-in. spiral steel flanged pipe. The connection from the pump

Jan 1, 1938

By K. A. Natarajan, I. Iwasaki

Platinum electrodes are not inert as often thought to be. The reactivity of platinum electrodes can explain their erratic behavior in many electrochemical measurements of metallurgical interest, e.g, in flotation systems, streaming potential measurements, contact-angle measurements, and in leaching systems. The anomalous behavior of platinum electrodes in redox potential measurements in aqueous systems was studied through Eh and pH measure ments in water-oxygen, iron-water-oxygen, and manganese-water-oxygen systems. Stability relations between Fe++ and Fe (OH), and between Fe (OH), and Fe (OH), were studied to judge the correspondence between experimental and theoretical equilibrium lines. The practicality of redox potential measurements in estimating ferric-ferrous ratios in aqueous systems was investigated along with their suitability as indicators in leaching operations, e.g., the removal of iron by aeration from manganese leach solutions. Platinum electrodes have often been used in the measurement of dissolved oxygen concentrations and of redox potentials (Eh) in a variety of fields, e.g., analytical chemistry,' corrosion," geology and mineralogy,,'' biology,"' sewage treatment,' * hydrometallurgy,"I" and flotation."la The effectiveness of Eh-pH diagrams, first reported by Pourbaix' in 1949, has contributed much towards the theoretical understanding of numerous problems encountered in the metallurgical industry. Not many references are available in the literature, however, wherein attempts have been made to confirm Eh-pH diagrams from experimental measurements. One reason might be that, in spite of the apparent simplicity of the electrochemical technique, the direct measurement of Eh involves complex practical problems.' Factors such as the purity of the solution, the type of electrodes used, the history of the indicator electrode, and the type of atmosphere (namely, oxidizing, reducing, or inert) do have effects on the measured Eh values. The influence of mixed potentials cannot be underestimated. The poisoning of platinum electrodes by organic and inorganic impurities present in the solution may lead to erratic results. Platinum, commonly thought to be an inert electrode material, is not really so, as attested by a number of previous investigators who advised caution concerning the anomalous behavior of platinum electrodes in various electrochemical measurements.'" In the present article, a few pertinent experiments related to Eh-pH measurements in systems of interest in the metallurgical and water pollution fields are described in an attempt to correlate such information with what is already known, especially in the electrochemical literature. Iron-water and manganese-water systems were selected with a view of studying the correspondence between experimentally observed and theoretically established equilibrium lines. The work included an investigation of the behavior of platinum electrodes with respect to pretreatment and adsorption characteristics, the measurement of dissolved oxygen concentrations and their relation to Eh, the determination of the electrode potential of the ferric-ferrous couple at different pH, and the measurement of oxidation potentials in iron-manganese leaching systems. Experimental Procedure A rotating platinum electrode was used in many of the measurements to study the effect of rotation on measured Eh values. The electrode made by the Pine Instrument Co. consisted of a stainless steel rod with a platinum disk soldered to the end. It was covered with a Teflon insulation along the sides, so that only the circular tip of the electrode was exposed to the solution. Prior to its use, the platinum surface was brightened on a metallurgical polishing wheel with alumina as an abrasive, unless specified otherwise. The electrode was rotated with a Sargent cone-drive motor at 350 rpm. The contact of the electrode with the external circuit was made by filling a notch at the top of the stainless steel shaft with mercury and by dipping a copper wire into the mercury pool. The performance of the rotating platinum electrode was compared with the performances of a Beckman platinum button electrode and a platinum wire electrode. All the potentials were measured with respect to a saturated calomel electrode. A saturated KC1-agar bridge was used to minimize the liquid junction potential. A Beckman Zeromatic pH meter together with a Beck-man electrode switch was used to measure both the Eh and pH. A double-walled, all-Pyrex jar with a capacity of about 1 liter and themostated by circulating water of constant temperature was used for a reaction cell. Four equally spaced ports in the cover provided access for a glass electrode, a salt bridge connecting the saturated calomel electrode, a dispersion tube for bubbling gases into the cell solution, inlet and outlet tubes for passing the desired gases over the solution, and a graduated burette for introducing reagents from outside. The rotating platinum electrode was inserted through an opening in the top-center of the cover, and a positive gas pressure was maintained inside the cell to prevent air from entering into the cell compartment. A magnetic stirrer was used to mix the solution inside. For the determination of dissolved oxygen in the test solutions, the polarographic techniquex was used.

Jan 1, 1971