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THE composition and quality of finished steel depend upon selection and proportioning of the raw materials of the charge as well as on control of furnace practice. This chapter deals only with those raw materials of the basic open-hearth process which are important in determining the composition of the steel or slag. They are the metallic charge, oxygen-bearing materials, fluxes, and alloying and deoxidizing additions. Refractories, which may also affect the slag composition, are discussed in the previous chapter. Wide variations are possible in the type and composition of charged materials, but in all cases certain fundamental relationships among the elements of the charge must be maintained. Since the process consists essentially of refinement by oxidation of undesired elements, a balance must be established between the sources of oxygen and the elements in the charge that are subject to oxidation (see Chapters II and VII). For example, if it is desired to use a high ratio of blast-furnace hot metal to scrap, it is necessary to add an oxygen-bearing material such as ore or mill scale to eliminate the excess carbon and silicon that are present in the hot metal. An example of the opposite extreme would be the use of a metallic charge composed entirely of steel scrap. With this type of charge, it is common practice to substitute burnt lime for limestone as a flux and to charge some carbonaceous material such as coke to avoid an excess of oxygen in relation to the elements of the charge that are subject to oxidation. Elements such as copper and nickel, which are not subject to oxidation or other reactions resulting in their elimination, may be introduced into the charge only to the extent to which they are permissible in the finished steel. An example of adjustment of the charge for elements of this type would be found in the use of steel scrap high in copper. In this case, metallic components of the charge other than the scrap should below in copper, or a sufficiently high ratio of pig iron to scrap should be charged to dilute the copper from the scrap, so that the average copper content of the melt will be below the required maximum.

Jan 1, 1944

By Norman F. Schulz

The technical excellence of separation achieved in a mineral concentration process, or any other process where two constituents of any kind are physically separated from each other, is expressed uniquely and quantitatively by the separation efficiency (E,): E. = (R - R,), where R is the percentage of the valuable constituent and R, the percentage of the waste appearing in the concentrate. The separation efficiency meets all the usual requirements of a true efficiency and is independent of the nature of the process used. It can be visualized as the percentage of the feed material that, in effect, actually undergoes complete separation while the rest of the feed is distributed randomly and unchanged into the two separation products. The problem of quantitatively assessing the results of a mineral concentration process recurs whenever one tries to decide which of two similar test results is more desirable. Although economic factors may greatly influence the eventual choice of process, they usually have very little to do with the technical excellence of a separation and are, therefore, not a consideration at this point. Concentrate grade and recovery, used simultaneously are the most widely accepted measures of performance, and if both the grade and the recovery are greater for one case than for another, the choice is simple. However, when the results of closely competitive operations are compared, it often occurs that one set of test results shows a higher grade and a lower recovery than another and the choice is no longer obvious. Laboratory investigations of a mineral concentration process applied to a given feed material can often be designed to yield successive paired values of concentrate grade and recovery over the practical range of the course of a separation process.' These results may be plotted as some combination of the cumulative values of grade, weight recovery, or unit recovery in the concentrate. The resulting correlations for two slightly different sets of conditions can then be compared qualitatively, or even quantitatively in particular cases.2 Such comparisons are not applicable, however, to individual concentration test results. The reduction of a separation test result to a single efficiency figure, preferably as a percentage of ideality, would afford the simplest and most precise means for comparing the results of competitive tests. The effective proportion of feed material that undergoes complete separation in any real concentration process, hereafter referred to as "separation efficiency," is such a figure. It is essily calculated from the usual feed and product data and can even be evaluated, in many cases, from data in publications describing various concentration processes. Mineral Concentration Processes and Their Evaluation Mineral Concentration Processes: The overall concentration process may be subdivided into a liberation process which severs the bonds between unlike mineral species, and a separation process, which sorts the resulting liberated particles into two products—a concentrate rich in mineral A and a tailing lean in mineral A. A perfect mineral concentration process is represented by the idealized scheme shown in Fig. 1 in which liberation and separation are not differentiated. The feed mixture consists of two mineral types which are completely liberated early in the process and then sorted by type. All the mineral particles of type A which respond uniquely to the selection forces acting in the ideal separator, report to the concentrate, while all the mineral particles of type non-A report to the tail-

Jan 1, 1971

By Pradeep K. Rohatgi, Clyde M. Adams

An analysis of heal conduction in the freezing of a solution has been performed. The case considered is the semi-infinite mass of solution, bounded by a con-stant-temperature plane with one-dimensional heat flow, Numerical cooling rate and freezing rate distributions hare been calcutated for the particular case of unidirectional freezing of aqueous solutions against. a cold copper chill. The solution at each level parallel to the chill surface is subjected to a spectra of frcezing rates; the freezing rate is inilially lour., passes through a maximum, and then decreases until solidification is camplete. Arange and maximum freeeing rates are inversely proportional to the square of distance from the chill surface. The temperature of the chill surface in contact with the solution remains constant during solidification. Experimentally, it is observed that deudrite sparing increases linearly with distance from the chill surface; in the light of heat -flow analysis this means that the dendrile spacing is imersely proportional to the square root of the maximum freezing rate. SOLIDIFICATION of liquids is accompanied by rejection of latent heat at the solid-liquid interface. The over-all rate of liquid to solid transformation is governed by the rate of heat extraction. Analysis of the heat transfer in the liquid during freezing is important since it determines the freezing rate and resulting structure. A considerable amount of work has been done on metallic systems since solidification is frequently a major step in processing metals. Unidirectional freezing from heat sinks has been treated by several investigators.1-4 Much of the work has been limited to the simpler case of substances such as pure metals which freeze isothermally at a unique transformation temperature. In this case the thickness of the solid zone y, next to a chill surface. is a parabolic function of the time. 8. where a and b are constants. Eq. |1| is a close approximation giving the progress of solidification for the case in which there is a small but finite thermal contact resistance at the interface between the freezing liquid and the chill.' It has been used with some success in connection with large steel ingots4 when the therma1 contact resistance is negligibly small (as is the case when water is brought into contact with the metal chill). The constant, b. becomes zero and Eq. [l] is then exact. even when the thermal properties of the chill and the freezing liquid depend on temperature. Analysis of unidirectional solidification of solutions is more complicated since the latent heat is evolved over a range of temperatures. Next to the all-solid zone in contact with the chill surface there is a solid plus liquid zone in which solidification takes place. Although the equations presented are considered quite general the numerical and experimental results are for freezing of aqueous solutions from a copper chill. I) EXPERIMENTAL PROCEDURE Solutions of potassium chloride, sodium chloride. and lithium chloride have been used. These solutions form a eutectic: a typical phase diagram is shown in Fig. 1. A solution at its liquid us temperature is poured into a tygon tube mounted on a relatively large copper chill. The chill is immersed in a freezing mixture of dry ice and acetone at -70°C. A thermocouple connected to a high-speed recorder was mounted near the top of the chill to measure the fluctuation in the temperature of chill surface in contact with the solution. In this system the progress of solidification can be visually observed through the tygon tube. After the specimens freeze to a desired height they are removed from the copper chill and stripped from the tygon tube. Longitudinal and transverse sections are cut from the specimen for micrographic examination. Specimens in the form of a thin slice are mounted on a transparent glass slide by freezing small drops of water around the periphery. They are then polished on a series of emery papers; the final finishing is done on a soft tissue paper. A Leitz Biological microscope was used for structural observations; photography was

Jan 1, 1968

By C. M. Nickerson

In times of overproduction such as the operators have been struggling against for the past several years it is the practice of the oil industry to shut in certain wells in order to reduce the flood of oil. The purpose of this paper is to present certain variations in production of oil wells when the offset wells are shut in. The scope of the study has been confined to California fields, and more especially to those of the San Joaquin Valley. The accepted definition of a shut-in well is a well where production has been suspended by closing in the casinghead arid tubing or by cessation of pumping. The immediate effect of such a procedure, of course, is to reduce the oil production from the lease, which is the result desired. However, it appears that certain types of wells vary widely in production of oil, gas and gasoline after adjacent wells have been shut in, which variation has a very material effect on the ultimate recovery of oil from the property. The increase or decrease in the oil production itself may not be of sufficient volume to occasion comment, but wide fluctuations in the gas and gasoline recovery under the changed conditions arc of the utmost importance in the future recovery of oil. The scope of this paper includes: (I) the effect on producing oil wells of shutting in offset wells, the wells being studied in three groups arranged according to their relative stages of depletion; (2) probable source of excess gas and the effect on the ultimate recovery of oil; (3) suggested procedure when wells are shut in; (4) methods that could be employed to prevent undue migration of gas from the shut-in area; and (5) the need for future studies of the situation. Three Classes of Producing Oil Wells For the purposes of this paper producing wells in California have been arranged in three groups according to the age of the well, or to the relative stage of depletion of the producing zones. The first group consists of those wells with a high fluid level, or in other words those wells whose fluid levels are a considerable distance above the top of the perforations. This type of well is in the flush period of its life and ordinarily produces

Jan 1, 1929

By Clarence E. Sims, Donald W. Williams, George A. Moore

INTRODUCTION DURING the past several years the steel casting industry has made studies of heavy castings in which the test bar has been taken from heavy sections rather than from attached or separately cast coupons. It has been noted that the ductility properties of these heavy sections are often lower than those normally expected. Such lowered ductility is usually accompanied by a spotty test bar fracture and the ductility values often can be greatly improved if a low-temperature aging treatment is given to the casting. A loss of ductility of this type is considered "abnormal," since it is not accompanied by an increase of tensile strength or hardness, and "temporary" when the ductility can be restored by aging. The cure of such an abnormal condition represents a real improvement in the quality of the steel. Some hundreds of previous investigations, largely qualitative in nature, have established beyond reasonable doubt that hydrogen is normally present in newly manufactured steel and that this gas, in small amounts, can cause a temporary abnormal loss of ductility. The commonly observed association of high gas content and low ductility has given strong evidence for the presumption that hydrogen, possibly assisted by other gases, is the primary cause of the low ductility observed. Accordingly, the Steel Founders' Society of America has, since Nov. 1, 1944, sponsored investigations at Battelle Memorial Institute whose primary objective is to obtain quantitative information on the relation of the amount of hydrogen and nitrogen in steel, together with associated methods of steelmaking and treatment, to low-ductility effects and porosity. In order that these investigations might proceed on a quantitative basis, hydrogen analyses of a precision considerably higher than any previously reported in the literature were necessary. The method chosen was selected entirely on the basis that it had the highest probability of freedom from uncontrollable errors and will be described in detail in another publication.1 Briefly, the method used consisted of the hot extraction of solid pieces of steel weighing from 45 to 50 g in a highly evacuated quartz tube maintained at 1050°C (1925°F) for a period 0f approximately 40 hr. The greatest precautions were taken to eliminate blanks and insure a sound gas-collection system. Vacuum and temperature conditions were maintained automatically. Mercury-filled risers were used for the introduction of samples in order that the system could be degassed thoroughly in

Jan 1, 1948

By J. H. McCormick

This plant, near Marysville, Mont., was planned to treat the ore from the Piegan and Gloster mines, the latter being one of the early and famous producers of the Marysville district. When the mill was closed in 1888, treatment consisted of stamp milling, followed by pans and settlers for pan amalgamation. The extraction was evidently poor, because, a few years later, thousands of tons of tailings were re-treated by the ranchers in the valley below the mill, by the then new cyanide process, and gave a handsome profit. In 1914, the present owners, after laboratory tests and an experimental mill run, decided upon the following treatment: crushing to 40 mesh in cyanide solution, concentration, amalgamation, classification, and cyani-dation of sands by leaching, and of slime by agitation and decantation in charges. The ore averaged about $7 per ton, gold and silver, the ratio of weight being 1 oz. gold to 7.56 oz. silver. The ratio of gold and silver in tailings was 1 oz. Au to 36.6 oz. Ag; the quartz was sharp and sandy, however finely ground, and rather difficult to slime. The mechanical equipment was a No. 5 Symons gyratory crusher; three 10-ft. Lane slow-speed Chilean mills; one Wilfley roughing and one finishing table; one submerged-type Akins classifier; five 26 by 10-ft. fir leaching tanks; one 24 by 7-ft. Dorr thickener; four 14 by 16-ft. Dorr agitators; four 6-compartment double-row zinc-boxes having compartments 18 in. wide, 18 in. deep, and 34 in. long; Johnson zinc lathe; acid and vacuum filter tanks for treating precipitate; roasting furnace; and Case tilting No. 275 crucible furnace for melting precipitate. The mill is driven by electric power supplied by the Montana Power Co. at the following rates, per kw.-hr.: 200 to 300 hp., 0.68 c.; 300 to 500 hp., 0.61 c.; 500 to 750 hp., 0.55 c.; plus $1 per month per installed motor horsepower. The plant as above described was operated from May, 1915, to the end of the year, when an additional Dorr thickener and a 12 by 12-ft. Portland revolving filter were added, increasing the nominal capacity of 100 tons per 24 hr., but not the percentage of extraction. The combined treatment, at a cost of $1.48 per ton, saved 90 per cent. of the gold arid

Jan 1, 1919

By J. B. Cohen, S. L. Sass

The nucleation process for y', Ni3Ti, is shou'n to change from heterogeneous to uniform as the undercooling within the phase boundary increases. As unifornz nucleation beconres copious, (100) alignment is observed in the early stages of aging; howecer. whether or not the alignment is due to spinodal decomposition could not be determined. The presence oi a large-scale reversible segregation of titanium and not the intermediate precipitate y' may be the cause of the initial strengthening in this alloy system and the discrete regions detected magnetically by Ben-Israel and Fine. Evidence is presented for the role of dislocations in the formation at long aging tines oJ the equilibrium precipitate . ThE nickel-rich portion of the Ni-Ti phase diagram consists of a terminal fcc solid solution of titanium in nickel called y.' For temperatures below 1290°C if the solubility limit is exceeded and the temperature is high enough, the excess titanium will combine with nickel to form q, Ni3Ti, a four-layer hcp ordered structure with stacking sequence ABAC."~ Since a change in structure is involved, formation of q is slow and a metastable precipitate referred to as y' forms. This metastable precipitate is an ordered cubic phase in the unconstrained state having a structure similar to Cu3Au (LIZ) with the composition Ni,Ti."'5 From X-ray studies,8, 7 the following sequence is indicated for the precipitation reaction at low temperatures: 1) The appearance of satellites around low-index diffraction spots and splitting of high-index spots, indicating the formation of a slightly tetragonal phase in an imperfectly periodic arrangement. The tetragonal phase is y' or the depleted matrix, depending on the volume fractions of matrix and precipitate (and hence, the alloy composition); tetragonality apparently arises from coherency strains. 2) The appearance of diffraction spots from the equilibrium second phase, q. Ben-Israel and Fine'" used magnetic methods to measure the changes in matrix composition during aging, and to estimate the precipitate composition in a Ni-10.1 at. pct Ti alloy. They observed that the alloy, solution-treated at 1270°C and quenched, contained heterogeneities with discrete compositions which gradually vanished upon aging. It was suggested that y' may initially form as a defect structure with several possible compositions deficient in titanium as compared to Ni3Ti; the composition Ni3Ti develops with prolonged aging. The initial composition was Ni6Ti which would require a very large deviation in stoichiometry for y'. It was noted that at 700°C the precipitation reaction was 80 pct complete after 2 hr and that the volume fraction of second phase was 0.2 after 1 hr. Mihalisin and Decker' suggested that the equilibrium precipitate, besides being nucleated at grain boundaries, could also form at stacking faults. ~errick" examined the formation of in Ni-Cr-Ti, and suggested that a collapsed vacancy cluster within y' acted as a nucleus for intragranular q at high temperatures, 820" and 900°C. After long aging times at lower temperatures, 650" and 750°C, diffraction patterns taken from regions containing ribbons of stacking faults showed spots associated with q. Aging greatly enhances the mechanical properties of these alloys, even at high temperatures, and the metastable precipitate y' is thought to be responsible.' At 600°C the hardness of a Ni-10.1 at. pct Ti alloy increases rapidly during the first 20 hr of aging and continues to increase slowly thereafter.'" At 700°C the hardness reaches a maximum at 1 to 2 hr and then decreases.l1 In this paper the kinetics of formation of y' and the mechanism of transformation to in a Ni-Ti alloy are described. Evidence is presented that suggests that large-scale regions of titanium segregation are present initially and these may have an important influence on the initial strengthening of the alloy: these regions may be the heterogeneities detected by Ben-Israel and Fine. I) EXPERIMENTAL TECHNIQUES The Ni-10.3 at. pct Ti-0.6 at. pct A1 alloy was prepared by vacuum melting. Its chemical analysis is given in Table I. A 0.007-in.-thick strip was sandwiched between foils of the alloy and placed in an open Vycor tube with titanium chips (to get oxygen) and solution-treated for ; hr at 1150°C in a Globar Furnace under a flowing argon atmosphere. Following a quench into an ice-brine mixture at -5" to -2"C, a sample to be aged at temperatures up to and including 700°C was sealed in an evacuated Vycor capsule before being put into a fused salt bath. Aging above 700°C was carried out on bare samples in a salt bath. When removed from this bath and quenched into an ice-water mixture, the sample was normally coated with a thin layer of oxide easily removed with emery

Jan 1, 1970

THE following statement is contained in an article entitled "Mortgaging the Future." by Walter C. Teagle, president of the Standard Oil Co. of New Jer-sey, appearing in the current issue of the Lamp, the official organ of the Standard Oil Co.: "During the last eight months the domestic daily production. of crude oil has risen 300,000 bbl.. which means that no less a volume than 2,500,000 bbl. now are coming to market each day. . . . Every twenty-four hours 250,000 bbl. more than the consumer required are being added to our surplus oil storage. The temporary advantage of cheap petroleum products and the availability of fuel .oil, for a widespread use as a substitute for coal are not being weighed against the time when scarcity may follow on the heels of plenty and the public of tomor-row may have to pay for today's excesses. The over-production of crude and its consequences constitute a problem of national import which far outweighs the temporary advantages either to a part of the industry or to sections of the public.

Jan 8, 1927

By E. Klar, A. B. Michael

Differences in the electrical conductivities of copper powder sintered under reducing, selectively oxidizing, and neutral atmospheres are related to impurities in solution or as precipitated oxides. The precipitation of impurities as oxides during sintering in nitrogen is proposed for maximizing the conductivity of sintered copper. Conductivity equations for two-phase systems are summarized. Selected equations are applied to porous sintered copper and composite structures. A recent review of the influence of impurities on the electrical conductivity of copper by Gregory et al.1 emphasized that an impurity in solid solution has a much more pronounced effect on reducing the electrical conductivity than when present partly or wholly as a second phase. When impurities in solid solution can be precipitated as oxides, the copper is purified with respect to these elements and the conductivity is increased. Cast and wrought copper, therefore, frequently contain an intentional residual oxygen concentration to oxidize and precipitate impurities less noble than copper. Copper powders generally also contain impurities which can contribute to a reduction in the electrical conductivity of the sintered material. The most deleterious impurities commonly found in commercial copper powders which markedly decrease the electrical conductivity when in solid solution but which can be precipitated as oxides include iron, tin, antimony, arsenic, cobalt, and nickel. In addition to impurities, porosity in sintered copper also contributes to a reduction in the electrical conductivity. The work reported herein discusses the influence of impurities, sintering atmospheres, and porosity on the electrical conductivity of sintered copper. These are important factors for controlling the electrical conductivity of materials such as sintered copper electrical contacts. Several publications on the electrical conductivity of sintered copper and composite materials with random pores or obstacles have incorrectly considered the conductivity to be proportional to the volume fraction of conducting material. However, analyses and equations have been proposed, the earliest of which is perhaps Lord Raleigh's of 1892,' which more accurately describe the conductivity of two-phase systems. These equations which in many cases allow one to closely estimate the electrical conductivity of porous sintered materials and two-phase composites will be reviewed and related to the measured electrical conductivity of sintered copper, copper-graphite. and Ag-W composites. INFLUENCE OF IMPURITIES AND OXIDIZING, REDUCING, AND NEUTRAL ATMOSPHERES Zone-Melted and Leveled Copper. The electrical conductivities of an electrolytic copper and a lower-purity compacting grade of copper powder after consecutive treatments in reducing or selectively oxidizing atmospheres are compared in Fig. 1. The powder and drillings from the electrolytic copper ingot were melted and solidified in a graphite crucible under hydrogen. The vertical zone leveling technique of multiple passes in opposite directions was used to obtain a uniform distribution of impurities. The electrical conductivity was measured on machined specimens 3 by 0.10 in. diam of the zone-leveled material and after the same specimens were consecutively treated as follows: 1) heating in hydrogen at 1600°F for 3 hr; 2) heating in air in a sealed tube so that 0.04 pct 0 was introduced; heating was started at 1000°F for 1 hr and continued at 1800°F for 8 hr; the stepwise diffusion treatment was used to avoid loss of copper due to evaporation of copper oxide at higher temperatures; and 3) final heating in hydrogen at 1600°F for 3 hr. A L&N Kelvin Bridge, type 4306, and a test fixture with knife edges 2 in. apart were used to measure the room-temperature conductivity with an estimated accuracy of ±0.5 pct. In all cases the conductivity of the electrolytic copper was approximately 100 pct of IACS. The conductivity of the impure copper was 80 pct of IACS both in the cast state and after heating in hydrogen. However, after the heating in air, the conductivity of the impure material was 100 pct IACS. After again heating in hydrogen, the electrical conductivity decreased to 60 pct of IACS. This decrease is attributed both to the dissolution of impurities and observed intergranular cracks due to the phenomenon of hydrogen embrittle-ment in copper. These data show that the electrical conductivity of commercial copper as represented by a compacting type powder can be increased significantly by the precipitation of impurities as oxides through heat treatment in an oxidizing atmosphere. Sintered Copper Powder. A commercial compacting type of copper powder pressed to various densities was sintered either in nitrogen, dissociated ammonia, or dissociated ammonia followed by a selectively oxidizing atmosphere of air in sealed Vycor tubes so that 0.06 pct O was added to the material. The electrical conductivity was measured perpendicular to the pressing direction on as-sintered specimens of approximately 3 by 0.25 by 0.15 in. The fully dense material was obtained by zone melting and leveling

Jan 1, 1969

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan' presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner's contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-' demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann' and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,' who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By J. A. Clum, R. W. Heins, T. D. Tiemann

The use of Na-montmorillonite clay hinders (Western Bentonite) in the pelletizing of iron ore concentrates is well established as is the idea that alternative binders must be found. 1-6 This note summarizes work done7 in evaluating a Wisconsin montmorillonite clay binder. The clay occurs in irregualr beds overlying the Prairie du Chien Dolomite and the St. Peters Sandstone near Hersey, St. Croix County. The raw Wisconsin clay contained 65% quartz and 35% clay minerals. The Na20to CaO ratio was 0.234. Suspension viscosity tests of the raw clay gave results only slightly better than water alone, even after treatment with activator materials. Sedimentation treatment reduced the quartz in the decantate to 5% after 240 min (four hours). Twenty minutes of sedimentation produced a decantate with 27.5% quartz which was found as effective as the 5% quartz decantate in pelletizing behavior. The 20 min decantate was used in subsequent tests. The decantate was filtered and dried at 110°(230°F). The minus 200 mesh portion of this was added directly to the magnetite concentrate. Pellets were made in a laboratory sized disc pelletizer from pastes consisting of ore concentrate, balling water (9%) and binder (clay, or clay + resins, or resins). The pastes were premixed in a Waring blender. The binders were: (1) 1% of a commercially used Western Bentonite; (2) 1 % or 3% of the Wisconsin clay (raw, or 20 min decantate); (3) 20 min decantate washed with activator solutions, (to exchange Na for Ca in the clay); (4) decantate with activator added in the balling water; (5) decantate with organic resins; (6) organic resins. Measurements of the 0.46 m (18 in.) Green Drop Number, the Dry Strength and the Fired Strength (fired at 1260°C (2300°F) for 30 min) were made. The dry and fired compressive strengths were determined on an Instron testing machine using a C-load cell and a F-load cell, respectively. The cross-head speed was 0.004 m/sec (0.1 in./min) for both. The results of each measurement were averaged for 15 pellets. A summary of those results is presented in [Table 1]. More detailed results and procedures are presented in another report.7 In addition to the effects on pellet strength due to various binders the effect of varying magnetite concentrate characteristics is noted in [Table l]. There, a few comparative data are shown for Cornwall, PA Magnetite, which has a generally liner particle size than the Black River Falls magnetite which was used for most of the tests.

Jan 1, 1979

By Wm. E. Milligan

LEAD stocks at the beginning of 1943 were comfortable when compared with those of other base metals such as copper, zinc and tin. This situation was early recognized by W.P.B. and other Governmental agencies and every effort was made to encourage the substitution of lead for these latter metals in all essential uses. Despite this apparently healthy condition, lead was not denied participation in the various measures inaugurated by the Government to relieve metal shortages. Thus in the Mexican trade agreement, effective Jan. 20, the tariff on two important classes of lead importss was halved. Similarly, in the setting up of B quota premiums, a B base was allotted to lead, with all pro¬duction above this figure receiving an additional payment of 2.75c. per lb., or a total payment of 11.75c. per lb. At about the same time it was announced that all quota transactions would be based upon the lead content as shown by the smelter settlement sheets. This basis was 86 percent of the lead content for all ores shipped to custom milling plants and 95 per cent for ores and concentrates shipped to custom smelting plants. The importance of this action can be appreciated when in the Coeur d'Alene it was estimated as equivalent to a 5 per cent increase compared to the previous base.

Jan 1, 1944

By Henry Fay

THE CHAIRMAN (ALBERT SAUVEUR, Cambridge, Mass.).-In forcing us to face and to discuss the important question of erosion of steel guns, Prof. Fay is performing a public service. His investigation has been fruitful and his results illuminating and suggestive. It is not in a spirit of adverse criticism, therefore, that I venture a few remarks suggested by his paper, but rather to add my mite to the discussion in the hope that it may not be entirely without value. Prof. Fay considers it conclusively demonstrated that the hard layers forming in the inside of guns of large calibers after they have been fired a number of times consist of martensite. Still, he admits that he never was able to detect in the hard layers the structural characteristics of martensite. This leads him to conceive the existence of amorphous martensite. We may well hesitate before accepting this theory on the strength of the evidence offered. Martensite, as we know it, is essentially a crystalline condition assumed by a close association of iron and carbon, possibly if not probably of the nature of a solid solution. Lacking this crystalline character we are hardly justified in calling it martensite on the ground, merely, of its being very hard.

Jan 4, 1917

By C. H. Jacoby

Since salt, sodium chloride, is an essential mineral to animals and humans alike, the delineation of the salt deposits of the world has been continuous from prehistoric times. As man explores deeper into the crust of the earth, particularly in search of petroleum, numerous new deposits of salt have been recorded. This paper deals with the factors that equate the current economic value of a salt deposit. The value of a salt deposit is not only determined by the chemical purity of the sodium chloride, but also the method of extraction to be used, the use of the product, and/or the use of the deposit. Salt is basically an inexpensive industrial commodity where large tonnages must be available to conduct a successful mining operation. Therefore, not only must the deposit contain these large tonnages, but also it must be accessible and transported as low cost freight to a large market. The geological environmental conditions surrounding the deposit must be such that it will be conducive to low cost mining operations. These conditions include not only the depth, size, shape, and internal structure of the deposit, but also the characteristics and extent of the overlying ground water.

Jan 1, 1973

By Robert Glass Cleland

THE MEMBERS of the Phelps-Dodge, Phelps-James co- partnership differed widely from one another in certain aspects of temperament and personality; but in one thing Anson Phelps, William Dodge, and Daniel James were fundamentally alike. They were all bred in the English Puritan tradition. Their creed, moreover, was the stern, militant, uncompromising creed of John Calvin and John Knox. The present generation, harshly intolerant of such a creed, has little understanding of the authority it exercised on the thinking and conduct of its adherents or of the contributions that those same adherents made to human welfare and social progress. The men who accepted its authority "were characterized by a blend of strong individualism and an equally strong sense of social duty, and they submitted their own souls to the same searching scrutiny that they applied to their business ledgers." To all three of the immediate founders of Phelps Dodge, their religion was the most real and important thing in life. It was with them day and night, in joy and sorrow, in loss and prosperity, in their most trivial personal affairs, in business transactions of the greatest moment. It was with

Jan 1, 1952

By W. R. Opie, O. W. Mole

By confining the electrolytic reduction of TiCl4 to the interior of a porous basket-cathode the electrolyte between the anode and the cathode can be kept free of reduced chlorides of titanium eliminating undesirable reactions of reduced titanium chlorides with brickwork or oxygen in the cell atmosphere. Semiwalls are not needed. Operating conditions are given and discussed. Titanium yields based on TiCl4 introduced are 93 pct. Cell voltage and amperage characteristics are adaptable to multiple cathode-series cell urmngements. EXPERIMENTS conducted in the National Lead Co., Titanium Division, Research Laboratories showed that titanium metal could be deposited in an electrolytic cell in which titanium tetrachloride was introduced through a tubular cathode.' The reduced chlorides as formed were confined to the vicinity of the cathode. They were reduced to form a cocoon-shaped growth of sponge titanium metal at the end of the cathodic tube below the surface of a sodium chloride-strontium chloride electrolyte. No diaphragm was needed.' Although high-purity, coarse crystalline metal was produced in the cocoon growth, the yields of metal removed from the cell, based on the amount of titanium introduced as TiCl4, were usually only 40 to 60 pct. The growth of the cocoon deposits was away from the cathodic tube for introduction of TiC14 toward the anode following the flu lines. The reduced chlorides of titanium diffused through the deposit and were reduced to titanium electrolytically within the deposit or on the outer surfaces. Deposition within the pores of the cocoon was detrimental to further deposition because it plugged the passages used by the reduced chlorides to diffuse away from the point of titanium introduction. As plugging due to deposition in the pores proceeded, the reduced chlorides in the center of the cocoon would force their way out by forming a channel and would escape from the vicinity of the cathode without being reduced to metal. Some work had been done previously1, 2 which indicated that if the end of the cathodic tube for introducing TiC14 was surrounded by a screen connected to the tube so that it too was cathodic, growth could be made to occur within the screen. Direction of growth was observed to be from the screen toward the point of TiCl4 introduction. Through a series of design modifications a cathode evolved which consisted of an introduction tube surrounded by a perforated metal basket as shown in Fig. 1. Modifications of this design are described in Refs. 3, 4, and 5. This basic cathode designa" was incorporated in electrolytic cells containing graphite anodes and constructed of high-silica brick refractory for containing the electrolyte (see Fig. 2). The inner crucible was surrounded by insulating brick and the entire unit contained in a welded steel shell. Suitable cooling chambers with inert gas atmospheres were devised so that the cathode could be removed from the cell without exposing the deposit to air while hot. Various alkali and alkaline earth chlorides were used as electrolytes.

Jan 1, 1961

By R. Simon, L. Yarborough

This paper presents a correlation for predicting the critical pressures of gas-solvent-reservoir oil systems of the type encountered in gas and solvent injection processes. Experimental data from 14 systems were used to develop the correlation which expresses critical pressure as a function of composition, C7+ mol weight, and C7+ characterization factor. Critical pressures predicted by the correlation for the 14 gas-solvent-reservoir oil systems have an average deviation of 2.8 per cent of the experimental values. The correlation war used to study a wide variety of other hydrocarbon mixtures reported in the literature whose critical conditions are in the range of interest in oil recovery work (100 to 280F and 2,000 to 6,000 psia). Critical pressures predicted by the correlation had an average deviation, expressed as per cent of experimental value, of 5 per cent for 20 miscellaneous mixtures from the literature, and 6.4 per cent for I7 methane-butane-decane mixtures reported by Sage and Lucey. INTRODUCTION Predicting critical points of hydrocarbon mixtures is an important part of phase behavior calculations. If the critical point can be predicted for a specific mixture, the separation between the bubble-point and dew-point regions will be defined, and physical properties of the mixture can be calculated by using the principle of corresponding states. Numerous correlations for predicting critical points of hydrocarbon mixtures have been published. Six of these correlationsl-8 were for light hydrocarbons, and two correlations7,8 ere for high boiling-point petroleum distillates. Organick9 And Eilerts" presented correlations which combined the published data from both light and heavy mixtures, and these correlations became the only available methods for predicting critical pressures for wide boiling range mixtures. In the course of the authors' work on secondary recovery by gas and solvent injection, experimental data were obtained for 14 mixtures of dry gas, ethane-propane-butane solvents, and various reservoir oils. The critical pressures and critical temperatures of these gas-solvent-reservoir oil systems were in the range of 1,900 to 4,800 psia and 180 to 265F. The critical pressures predicted for the 14 mixtures by the correlations of Organick and Eilerts had an average deviation from the measured values of about 13 per cent. The authors felt that it was necessary to develop a better correlation for engineering calculations and the resultant correlation, which is presented on Figs. 1 and 2, predicts the critical pressures of the 14 mixtures with an average deviation of 2.8 per cent. The validity of the correlation was tested by applying the correlation to other hydrocarbon mixtures reported in the literature. This subject is discussed later in the paper. The authors feel that there is also a need for an improved critical temperature correlation for gas-solvent-reservoir oil systems. However, developing a critical temperature correlation is a significant study in itself and is not included in this paper. EXPERIMENTAL DATA The compositions and critical points obtained by the authors for 14 gas-solvent-reservoir oil mixtures are shown on Table 1. The methane concentrations in these mixtures varied from 20 to 63 mol per cent. The intermediate hydrocarbon group, consisting of ethane, propane, and butane, varied from 20 to 64 mol per cent, and the concentration of the C,, fraction from 10 to 20 mol per cent. The physical properties of the C,, fraction covered the range from light, paraffinic, nonasphaltic (Mixtures 5, 6, 7, 8, 9 and 10) to heavy, aromatic, and asphaltic (Mixtures 13 and 14).

By Ralph Monaghan, Arthur Youmans

General principles of scintillation counter-type instruments for radioactivity logging are discussed and the various possible causes for instability are examined. It is shown how instrumentation problems are solved. Means are discussed for minimizing drift and instability due to "fatigue" of the photomultiplier tube and neutron activation of the crystals. INTRODUCTION Neutron and gamma-ray logs made with logging instruments employing scintillation counters are now routinely available from most of the logging service companies. The superior characteristics of scintillation counters by comparison with older types of detectors promises to bring about important improvements in quantitative interpretation of radioactivity logs. Moreover, new types of logs can be made with scintillation counters which are not possible with other detectors. But in spite of the obvious superiority of these counters with respect to efficiency, speed, and versatility, they suffer from a number of inherent difficulties and weak- nesses. Unless these inherent diffi-culties are fully recognized and satisfactorily overcome by sound engineering of the associated instrumentation, scintillation counter logs are particularly likely to exhibit drift and instability of sensitivity. This defect in logs when they are intended for quantitative interpretation is intolerable and more than outweighs any advantages over the older type of instrumentation when the latter is operating correctly. SCINTILLATION COUNTER OPERATION In general all radioactivity logging instruments consist of a detector sensitive to gamma radiation or to neutron radiation coming from the strata. This radioactivity is either due to naturally decaying radioactive elements in the rock, radioactivity induced in the rock by a neutron source in the instrument, or scattering by the rock of neutrons or gamma rays coming from a source in the instrument. In the scintillation counter the gamma radiation or neutron radiation reacts with the scintillation phosphor to produce light pulses. These light pulses are then converted to amplified electrical pulses by the multiplier phototube. Basically the problem of making a good scintillation counter logging instrument is to make the radiation sensitivity of the system as nearly constant as possible. The size of each scintillation counter pulse is dependent on the energy of the individual quantum of radiation being detected. In normal radiation logging, gamma rays of all energies, up to some maximum value, reach the detector. If a suitable scintillator is used, such as a sodium iodide crystal, each gamma ray produces a number of photons proportional to the energy absorbed by the crystal from the impinging radiation. The light flashes are detected by means of a photo-multiplier tube which contains not only a photo-sensitive cathode from which photoelectrons are collected, but also an amplifier, called an electron multiplier, built inside the photomultiplier tube; the electron multiplier usually has about 10 stages, having an over-all gain of perhaps 500,000. In an ordinary gamma-ray log one wishes to detect all gamma rays down to the lowest possible energy; therefore, one wishes only to reject the "noise" pulses which are invariably present due to thermal emission of electrons from the photo-cathode of the photomultiplier. In other radioactivity logs it may be desired to measure the radiation within a particular energy band, or above

Jan 1, 1958

By John A. Church

IN May, 1878, I had the honor of presenting to the Institute, at the Chattanooga meeting, some observations upon the heat of the Comstock Lode, and since then the subject has attracted some attention and criticism, in the course of which, I have observed errors of apprehension which I beg leave to correct now. Mr. John Arthur Phillips discussed it before the Geological Society, his paper being printed in the Quarterly Journal for August, 1879.* His criticism is based upon that part of my paper in which I quote a number of analyses of the mine waters, to illustrate the fact that the heat does not come from the oxidation of pyrite. I pointed out that these waters contain only an insignificant proportion of sulphuric acid, and not enough to account for even one per cent. Of * A Contribution to the History of Mineral Veins. By J. Arthur Phillips, Esq., F.G.S. Quarterly Journal of the Geological Society for August, 1879.

Jan 1, 1880

By Ruder, W. E.

CONSIDERABLE interest has been shown lately in various types of furnaces for the production of high, temperatures, both for laboratory purposes and for small industrial uses. Dr. J. A. Harker1 described certain modifications of the Arsem graphite resistance helix for high-temperature work at the National Physical Laboratory. Dr. Northrup ,also has developed two interesting forms of high-temperature furnaces. In 1911, Messrs. Winne and Dantsizen2 described two forms, of resistance furnaces using ductile molybdenum or tungsten as resistors. Since the discovery, by this laboratory, of methods for producing these metals in ductile form, their use as resistance elements in the research laboratory of the General Electric Co. has grown to such an extent that they are now almost indispensable. These furnaces are used here for alloy research, annealing, heat-treating, and practically all f the thermal processes requiring temperatures above 900° C. Various types of furnaces have been developed to meet the general needs of laboratory work, and it is the purpose of this paper briefly to describe some of these furnaces. A tubular furnace wound with a metallic resistor is the simplest type to construct, and almost every laboratory has made such furnaces. The only essential difference between a furnace wound with platinum or base metal and one wound with tungsten or molybdenum is that the coils of the latter must be heated in a neutral or reducing atmosphere. It has long been our custom here to build our resistance furnaces with a metallic casing from which the tube could be easily removed for rewinding. The heat-insulating material-usually calcined magnesia, alumina, silica, or silex, depending upon the nature of the resistor-is used in powdered form so that it can he readily removed and replaced. In order to adapt this method to tungsten or molybdenum windings, it

Jan 2, 1918