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By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf's remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By Subhas G. Malghan

Feldspathic deposits occur widely throughout the United States, but North Carolina, California, Connecticut, and South Carolina accounted for over 80% of the total domestic feldspar output for the year 1973.1 Pegmatites and granites constitute the major feldspar reserves of the United States, 2 and in addition, feldspar is produced as a byproduct by firms whose major products are spodumene and mica. 3 Feldspar flotation is practiced in the United States, Mexico, Finland, Norway, West Germany, Japan, and the USSR. According to the US Bureau of Mines estimates, the production of feldspar in the United States and rest of the world were 704,000 and 2,514,000 t, respectively. Feldspar is principally used as a flux in making glass, pottery, porcelain, enamel, tile, and other ceramic products. In recent years, the domestic feldspar industry is faced with a number of problems. As a result of increased cost of energy and the introduction in 1972 of new legislative programs relating to air, water, and noise pollution, land-use restrictions, and mined-land rehabilitation, the production costs have increased. Apart from the increased cost of operation, an operational problem exists with the feldspar producers in North Carolina, especially those in the Spruce Pine area. This problem is concerned with the use of hydrofluoric acid in the feldspar flotation. Feldspar producers in Spruce Pine, NC, have been discharging process waste water into the North Toe River. The mill waste water contains active fluoride ions. Fluoride in excessive concentrations is undesirable in waters used for drinking. It is stated that water containing 0.9-1.0 ppm fluoride will seldom cause mottled enamel on children's teeth; and for adults, concentrations less than 3-4 are not likely to cause endemic cumulative fluorosis and skeletal effect. Although the literature on this subject is rather confusing and inconclusive, the inference that concentrations over 4 ppm may affect bone structure is clear. According to the recent Federal Register,4 maximum fluoride level of 1.4 ppm at 79°-98°F is considered to be adequate and safe for the protection of health of the consumers. The EPA and state environmental agencies have accelerated their drive to reduce water pollution on a faster schedule. By 1977, the EPA specifications for maximum contaminant level of fluoride ions in the discharge waters of feldspar milling operatins is expected to be reduced to 2.0 ppm. The other problems of using hydrofluoric acid are the following: toxicity, hazards of handling and storage, and high cost as compared to other inorganic acids (almost 16 times the cost of sulfuric acid). In order to reduce fluoride levels in mill discharge waters, mining companies have taken the following steps: I) Recirculating a part of their mill water. Even though recirculation of mill water seems to be a novel method of reducing fluoride contamination of the discharge water, there are certain operational and handling problems. 2) Conducting research on the treatment of fluorides in mill waste water. The technology of treatment of fluoride ions has received considerable interest in the recent years. A recent research report5 estimates that the cost of fluoride ion removal to meet the present specifications in the feldspar industry is approximately $0.25/t of ore processed, and about $0.50/t of feldspar produced. At the request of the feldspar producing industries in North Carolina, the North Carolina State University (NCSU) Minerals Research Laboratory has taken up a research program directed towards overcoming the fluoride ion pollution problem. After a close study of the operational, technical, and economic aspects of feldspar flotation, it was decided to attempt to replace the conventional hydrofluoric acid process. Conventional Feldspar Flotatin Using Hydrofluoric Acid Since the inception of the feldspar flotation process using hydrofluoric acid by O'Meara2,6 the process has achieved a great commercial success. In the conventional flotation separation of feldspar-quartz, hydrofluoric acid is used to suppress quartz and activate feldspar, and a long chain amine salt (acetate or chloride) is used as a collector. The bulk of amine collectors used in current feldspar operations are applied as the water-soluble acetates of the free-base amines. These products are pastes or waxy solids which are available in a range of acetic acid neutralization levels generally 50 to 100% neutralized. In spite of the problems mentioned in connection with the use of hydrofluoric acid, this process is extremely stable with respect to changes in the process variables. With the exception of a few operations, alaskite and pegmatite are the major sources of feldspar.7 In the flotation treatment of a pegmatite that contains iron-bearing minerals (heavy minerals), mica, feldspar, and silica, a logical order of removal presents itself considering the following:8 1) Mica is readily floated by an amine collector in a pulp pH 3.5. Some iron-bearing minerals will usually respond to amine collector in acid circuit with the mica concentrate. 2) Since iron minerals tend to occur invariably in the feldspar concentrate, it is desirable to remove most of these prior to feldspar flotation. A fatty acid or a petroleum sulfonate collector used in this flotation step in acid circuit will float iron-bearing minerals. 3) Using hydrofluoric acid to maintain pH of 2.5, an amine collector employed in a final step will float feldspar away from silica, usually leaving the latter in the tailing as a high-grade silica concentrate. The problems connected with the flotation separation of feldspar-quartz arise due to the similarities in their chemical structure. Therefore, any reagent system that is likely to succeed in feldspar-quartz separation should have adsorption affinity towards one of the minerals and depression effect towards the other mineral.

Jan 1, 1979

By E. Miller, K. L. Komarek, M. Ettenberg

The activity of aluminum in solid Co-A1 alloys has been measured by an isopiestic technique between 850° and 1200°C from 45 to 80 at. pct Al. The activity shows a Precipitous decrease around the stoichzornetric composition of CoAl. Free energies of mixing have been calculated over a limited composition range. Considering an antistructure-vacancy defect mechanism, the degree of intrinsic disorder, a , in CoAl was related to the alunminum activity. Excellent agreement between the calculated and experimental activity curves was obtained for a = 1.25 x 10-4. ThERMODYNAMIC properties of solid aluminum-transition metal alloy are being studied in an investigation of disordering in ordered compounds. In a continuing series of investigations, activities of solid Fe-1,' Ni-A1, kd r-A13 alloys have been measured. From the results for Fe-A1 and Ni-A1, the degree of intrinsic disorder for the equiatomic compounds was calculated2 using equations derived by Wagner and chottk. From the results for Cr-A1 the degree of intrinsic disorder was calculated from equations derived by Orr.' In this paper, the results of the study of Co-A1 alloys are described. Published activity data in the Co-A1 system has been limited to liquid alloys at 1600°C.° A heat capacity study7 of stoichiometric CoAl indicated that a second-order phase transformation occurs at 790° C, attributed to an order-disorder reaction. Oelsen and Middel,' employing the calorimetric mixing of pure liquid metals, obtained heats of formation for compositions from 6 to 90 at. pct Co. Heats of formation for 50 and 78 at. pct Co alloys have also been measured by acid solution calrimetr. The Co-A1 phase diagram, as compiled by Hansen and Anderko,lo is in good agreement with more recent X-ray evidence. The method for measuring activities of aluminum in this study is essentially that employed in the studies of the Fe-1,' i-Al, and r-A13 systems. This isopiestic method entails placing cobalt specimens, in a temperature gradient, in a sealed alumina system containing a pure liquid aluminum source of fixed vapor pressure. The specimens are equilibrated, cooled to room temperature, and their final compositions determined. From the measured temperature of the specimens and the known vapor pressure of pure aluminum the activities of aluminum in the alloy can be calculated. EXPERIMENTAL PROCEDURE The cobalt was 3-mil-thick sheet of 99.9 pct purity (herritt Gordon Mines Ltd., anada). The major impurities were 0.1 pct Ni, 0.014 pct C, 0.018 pct Fe, 0.004 pct S, and 0.005 pct Cu. The aluminum metal had a purity of 99.99 pct (Aluminum Corp. of America) and all alumina parts were 99.7 pct A1,O3 (Triangle RR Grade, Morganite Refractories, Inc.) with major impurities 0.05 pct SiOz, 0.1 pct Fe203, 0.2 pct NazO, and 0.05 pCt K20. Runs 1 to 3 were made with annular cobalt specimens (12 mm ID by 21 mm OD) punched from the sheet. The specimens were deburred and degreased in carbon tetrachloride and in acetone. The samples, each weighing about 150 mg, were then positioned along an alumina rod, a in. OD by 14 in. long, separated by alumina spacers, i in. ID by | in. OD by & in. long. The lower end of the rod was placed in a hole drilled in the center of an 80-g aluminum cylinder. This assembly was put into an alumina crucible, 1+ in. ID by 13 in. OD by 3+ in. high, and the position of each sample was measured to within 50.5 mm relative to the bottom of the crucible. An alumina tube, 28.5 mm ID by 35.5 mm OD by 14 in. long, closed at the top, was slipped over the whole assembly, so that it fitted snugly into the bottom crucible. The entire reaction assembly was tied with molybdenum wire and lowered into a mullite tube, closed at the bottom. A quartz thermocouple tube, closed at one end, containing a t/Pt-10 pct Rh thermocouple, calibrated according to the specifications of the National Bureau of standards,'' was placed along the reaction assembly inside the mullite tube. The temperature of each specimen could be determined by gradually raising the thermocouple and measuring the temperature gradient along the reaction assembly. The combined error in temperature measurement and sample position resulted in a total error of Q°C in the recorded temperature of each sample. The mullite tube was sealed at the top by a water-cooled brass head, connected to a conventional glass vacuum system. The aluminum reservoir is heated to its melting point sealing the alumina system containing the samples. During this process the pressure is maintained below 0.01 li Hg. During subsequent heating to establish the proper temperature gradient and throughout the entire run the pressure is maintained below 2 1 Hg by means of a two-stage mechanical pump. Equilibration runs lasted from 4 to 6 weeks and were terminated by air cooling. The temperature of the liquid aluminum reservoir was brought below its melting point in less than 20 min. For runs 4 and 5, alloy buttons with 49 and 69 at. pct A1 were prepared from the initial high-purity metals by arc melting under purified argon. The alloy buttons were comminuted to powder with an alumina mortar and pestle until the powder passed through a 400-mesh screen, particle size 0.0014 in. Portions of this powder weighing between 50 and 200 mg were placed in small alumina trays, 25 by 15 by 5 mm, which were then

Jan 1, 1969

By E. T. Turkdogan

The activity of sulfur was determined as a function of composition of ferrous sulfide by equilibrating with hydrogen sulfide-hydrogen gas mixtures at 670° , 800°, and 900". The present results supplement the available data over the composition range from 36.6 to 39.5 pct S. The X-ray lattice spacing measurements made are in accord with the available data and indicate that the limiting composition FeSl.008 may be taken for the iron-iron sulfide equilibrium. The growth rate of ferrous sulfide on iron was measured by reacting iron strips or blocks in hydrogen sulfide-hydrogen gas mixtures. Owing to the slow approach to equilibrium between the gas phase and the surface of the sulfide layer, The sulfidation experiments were carried out for several days. It is shown that the growth rate ullimately proceeds in accordance wilh the parabolic rate law. From the parabolic rate constants and the thermodynamic data on iron sulfide the self-difiusivity and chemical diffusivity of iron in ferrous bisulfide are evalualed. The self-diffusivity of iron thus derived zs found to increase with increasing sulfur content. THE ferrous sulfide known as "pyrrhotite" is a non-stoichiometric phase having a wide composition range from about 50 to about 58 or 60 at. pct, depending on the sulfur activity. RosenQvistl studied the thermodynamics of this phase over wide ranges of temperature and composition. Hauffe and Rahmel' and Meussner and ~irchenall~ studied the parabolic rate of sulfidation of iron in sulfur vapor. By using markers, these investigators showed that the iron cations were the predominant diffusing species in iron sulfide. This is confirmed decisively by the self-diffusivity measurements of condit4 who showed that the self-diffusivity of sulfur in ferrous sulfide is several orders of magnitude lower than the self-diffusivity of iron. Although much has been learned from these studies about the Fe-S system, further research on this subject was considered desirable for better understanding of the physical chemistry of iron sulfide. This work was confined to the study of the kinetics of sulfidation of iron in hydrogen sulfide-hydrogen gas mixtures. The results of this study are given in two consecutive parts. Part I, the present paper, is on the parabolic rate of sulfidation of iron and the diffusivity of iron in ferrous sulfide. The second paper, Part 11, is on the kinetics of the surface reaction between hydrogen sulfide and ferrous sulfide. EXPERIMENTAL Three types of experiments were carried out: i) equilibration of ferrous sulfide with gas of known E. T. TURKDOGAN, member AIME, is Manager,Chemical Metallurgy Division, Edgar C. Bain Laboratory for Fundamental Research, U. S. Steel Corp., Research Center, Monroeville, Pa. Manuscript submitted March 6. 1968. ISD sulfur potential; ii) X-ray studies of ferrous sulfide; and iii) measurements of the parabolic rate of sulfidation of iron. Equilibrium Studies. About 1 g of iron powder or foil. contained in a small recrystallized alumina crucible ind suspended from a calibrated silica spring, was reacted with a hydrogen sulfide-hydrogen mixture of known ratio until no further change in weight was observed. %hen the gas composition was changed and the new state of equilibrium was established after several hours of reaction time. The composition of the sulfide was obtained from the initial weight of the sample and the weight after equilibration. X-Ray Studies. The lattice parameters of some of the equilibrated samples were determined using the General Electric XRD-5 diffractometer with a cobalt tube (no filter) set at 40 kv apd 10 ma; the CoK, radiation was taken as 1.79020A. Observed 220 and 311 diffraction peaks of silicon served as an internal comparison standard to correct for possible misalignment of the goniometer. The lattice parameters of the sulfide phase were calculated from the corrected Bragg angles of the 110 and 102 peaks. Rate Studies. In the initial experiments attempts were made to measure the parabolic rate of sulfidation by measuring the gain in weight of a thin iron strip, -0.05 cm thick, suspended from a silica spring in the reacting atmosphere. The preliminary experiments showed that this technique was not reliable for the measurement of the parabolic growth rate of the iron sulfide layer. In the subsequent experiments the data on growth rate were obtained by measuring, on a microscope stage, change in the thickness of the sample after reaction for a specified time in a hydrogen sulfide-hydrogen mixture of known sulfur activity. For each reaction time a new sample was used. Precision-machined iron blocks, 0.5 by 2 by 5 cu cm, were de-greased and annealed in hydrogen for several hours prior to the sulfidation rate measurements. The experiments were carried out at 670°, 800°, and 900°C in gas mixtures having the ratios, and 1.0 for periods of times from a few hours up to 8 days. Apparatus and Materials. A vertical globar tube furnace with a 3-in.-long uniform temperature zone was used. The glass tube fittings were fused on the zircon reaction tube, 1.5 in. diam. The temperature was measured with a Pt-10 pct Rh/Pt thermocouple placed in the hot zone of the furnace inside the reaction tube (an alumina thermocouple sheath was used). A separate thermocouple was used for the temperature controller which maintained the furnace temperature constant within about 2°C. Anhydrous liquid hydrogen sulfide and oxygen-free dry hydrogen from gas tanks were used in preparing the gas mixtures by the constant head capillary flow-meters. In all cases volume flow rate was 1000 cu cm per min at stp, corresponding to a linear velocity of about 6 cm per sec at 800°C; under these conditions

Jan 1, 1969

By W. F. Stowasser

downdraft traveling grate process to agglomerate pelletized iron ore concentrates has been successfully demonstrated in a pilot plant at Carrollville, Wis. Work there followed several years of development in the Allis-Chalmers Mfg. Co. laboratories, and the pilot plant phase was carried out in cooperation with Arthur G. McKee & Co., consultants and engineers to the iron and steel industry. End result of the process is conversion of iron ore concentrates into a form which can easily be transported and smelted in the blast furnace. Process Description The first of two process steps incorporates the art of balling and prepares the concentrates for burning. The second step consists of burning the green balls on the grate machine to the hardness required for shipping and handling purposes and for reduction in blast furnaces, see Fig. 1. Facilities are provided at the pilot plant to receive carload quantities of concentrate. The concentrates are loaded into a 50-ton bin direct from railroad cars. Because of the variable moisture content of the concentrates after shipment in an open railroad car it is necessary to repulp and refilter the concentrates to maintain a uniform and proper moisture content for the balling operation. Concentrates are conveyed to slurry tanks, and the slurry, at 50 to 60 pct solids, is pumped to a 4x4-ft drum filter. The filter provides feed of uniform moisture to the plant. Magnetite concentrates are normally filtered to produce a cake containing about 10 pct moisture, a necessary requirement for the following balling operation. The filtered concentrate is conveyed to a rotary bin table feeder which acts as a surge bin for the filter cake and delivers a steady flow of concentrates to the balling drum. It is often desirable to make additions to the concentrates as they are fed to the balling drum. These additives, such as bentonite, increase the strength of the finished green pellet and improve ballability of the concentrate. A vibrating feeder supplies additive to the feed belt, and the additive is mixed with the concentrate in the balling drum. The balling drum, shown in Fig. 3, is 8x3-ft diam. An oscillating cutting bar maintains the lining in the drum by trimming off the buildup of excess concentrate as it forms. The drum is operated in closed circuit with a lx4-ft rod-deck vibrating screen. Undersize pellets or seed pellets from the screen are returned to the balling drum until they grow to the desired size. Size of pellets is controlled by the opening in the screen deck. The formation of pellets in the balling drum is affected by many variables. Some of these are: the size distribution of the feed, the particle shape of the concentrate, the feed rate to the drum, the moisture in the concentrate, the speed of rotation of the drum, the slope of the drum, and the type of trimming obtained with the cutting bar. In this process, attempts are made to control the pellet size within the limits of % to 5/8 in. diam. The screened oversize pellets are conveyed under a coal feeder where sufficient powdered coal is added to the belt to produce desired results in the burning process. The top size of the coal successfully used has been 20 mesh, and anthracite was used in the test program. Fig. 4 illustrates the vibrating screen and the coal feeder. The pellets and free coal are conveyed together to the 5x3-ft diam- reroll drum that rolls the coal onto the surface of the pellets. This drum is also equipped with a cutting bar. The prepared pellets, containing bentonite, water, and surface coal, are elevated to the traveling grate, which consists of a continuous strand of 37 pallets. Each pallet, with a grate bar area 2 ft wide by 1 1/2 ft long, has 14-in. high side plates, Fig. 5. Feeding and distribution of the green balls to the grate is handled by a short conveyor which oscillates back and forth across the 2-ft width of the grate. An adjustable vertical plate located several inches in front of the head pulley of the oscillating conveyor controls the height of the bed and levels the moving bed of pellets. This method of feeding prevents segregation of various size pellets as well as fines and produces a uniform, permeable bed. The pallet train moves under the furnace and across four windboxes, located beneath the pallet frames, see Fig. 2. As the green pellets are deposited on the grate, partial drying of the pellets begins over a 2-ft long updraft windbox. The low temperature air reduces the moisture in the pellets in the lower level of the bed and this operation is essential to prevent sagging of the bed during later stages of the Process. The air used for this drying is recuperated from cooling the pellets on the grate, and supplemental heat, required for starting the Process, is obtained from an auxiliary burner. The pellets are then moved by the grate into the furnace and over an 8-ft windbox, designated as the downdraft waste windbox. Products of combustion are exhausted from this windbox to atmosphere. The furnace, shown in Fig. 6, is constructed with three chambers to provide downdraft drying, preheating, and ignition, respectively, to the pellet bed as it passes through. Overall length of the furnace is 5.57 ft; however, the exterior wall ends may be moved to reduce the length and also adjusted to Obtain the bed height desired, The drying, preheating, and ignition sections of the furnace are supplied with medium temperature

Jan 1, 1956

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 M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By Lynn C. Jacobsen

Among the unforeseen consequences of the 1973 Arab oil embargo has been a considerable array of new or increased taxes on the so-called energy minerals. These taxes will be the subject of this report. Both Federal and State taxes have been enacted, but I will be concerned mostly with state severance taxes and particularly those on uranium. Severance taxes are considered to include all taxes having the distinctive feature of being applied on a natural resource at the stage of extraction. The tax may be based on units of production or on value, and if on values it may be on gross value or on gross value less either arbitrary or cost-related deductions. The tax has a number of aliases - resource excise tax, conservation tax, privilege tax, mining excise tax, ad valorem production tax, and more - and this makes comparison of tax burdens among states difficult. The windfall profit tax on oil is an example of a severance tax at the Federal level. Severance taxes are an established feature of state tax systems, but they continue to be a controversial issue, and proposals to raise or modify existing severance taxes are regularly submitted to the legislatures of the Western energy producing states. No concensus exists as to what is a reason- able and proper level of severance taxation or to the form it should take. The taxes which have been adopted by the various states reflect the interaction of a variety of interests and the specific circum- stances in each state. What follows is a summary of theoretical, practical, and emotional viewpoints and arguments that surface in any statehouse in which a severance tax bill has been introduced. The New Mexico experience will be heavily relied upon. THE ECONOMISTS Marginal effects. A severance tax which is based on a gross percentage of revenue or on units of production is a constant addition to variable costs, and to the mine operator has the same effect as any other increase in operating costs. The direction of these effects is straightforward: the tax will cause the property to have a lowered present value, to be mined at a lower rate than without the tax, raise the minimum grade that will be mined, lead to lower total recovery, make marginal properties sub-marginal and discriminate in favor of richer, more profitable operations (Lockner, 1965; Steele, 1967). In the short run, production facilities are fixed and imposition of a severance tax will have little effect on production levels. In the longer term, capital is mobile and investment and exploration expenditures will shift from minerals and jurisdictions with high taxes to those with low taxes. Over a considerable range of taxation the effect will be to change the relative position of the taxing state, but an overly optimistic evaluation of the capacity of mineral producers to absorb a tax can bring an industry to a halt. It is generally acknowledged that imposition of high severance taxes on taconite in Minnesota stopped development completely, and that only the adoption of a constitutional amendment limiting the amount of taxes that could be imposed in the future brought the firms back and encouraged them to make the huge investments required (Weaton, 1969). A tax which is a percentage of the net operating income (gross revenue less cash operating costs) does not influence the cut-off grade for recovery nor change the time preference for extraction, and hence, is free of the negative features of the tax applied to gross revenues or units of production. In theory it is a more efficient tax but relative administrative complexity and inherent difficulty in predicting revenue have discouraged its use. The Wyoming severance tax on uranium, which uses grade of ore as well as price in establishing taxable value, is the most cost related, and hence, the most neutral and efficient of the various state severance taxes on uranium. Economic rent. Despite the discrimination and the anti-conservation aspect inherent in most severance taxes, economists generally endorse their use because they are seen as a vehicle to appropriate rents - that is, returns greater than the long-run competitive supply price. Conspicuous examples of supposed economic rents are the returns to oil producers because of the OPEC cartel, the returns of the uranium producers under AEC buying contracts in the 19501s, and the high prices obtained by the uranium producers for contracts entered into in the 1976-1979 period. Mining of coal in the Western states is believed by some to generate huge economic rents because of the OPEC caused increase in price of a competitive fuel (McLure, 1978, p. 261), and possibly because of clean air regulations favoring the burning of low-sulfur coal. In theory, such surplus returns could be taxed completely away without affecting supply. In practice, the situation is more complex (Steele, 1967, pp. 234-236); economic rent of mineral production is an elusive quantity involving as it does replacement costs, and technical and market risk, and it, like beauty or pornography, probably exists mostly in the eye of the beholder. Rent may also be perceived to be present in the upper portion of a cyclic market which also has a downside. Where rent exists, it is almost certain to be short-lived - cartels self- destruct, government subsidies end, competitive adjustments occur - but the taxes imposed to capture it tend to be immortal. There is little doubt that the perception of un- usual and undeserved (obscene) profits in the mid- and late 1970's was a major factor in the adoption of energy mineral taxes strikingly higher than had been previously considered. At the New Mexico legislature of 1977 supporters of a moderate tax were repeatedly confronted with some variant of the statement, "You can't expect me to believe that a

Jan 1, 1982

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By M. Semchyshen, A. P. Coldren, W. G. Scholz

A survey of the Fe-Mo-B system was made to determine the extent to which boron might affect the microstructure and strength properties of iron-rich Fe-Mo alloys. Seventeen vacuum-induc tion melted ingots were prepared with approximate mo-lybednum contents 01 2, 4, 9, and 19 wt pct and approximate boron contents of 5, 14,50, and 630 ppm by weight. Phases extracted from annealed specimens and identified by X-ray diffraction analysis included E Fe3MO2, Mo2FeB2, and an oxide hazling a diffraction pattern practically identical to that of MnFez04. Three types of alloy strengthening were observed: a) Fe-2 pct Mo-B alloys were hardenable by a bainitic-type transformtion of austenite to ferrile; b) Fe-4 pct Mo-B alloys were hardened by the solid-solution mechanism; and C) Fe-9 pct Mo-B and Fe-19 pct Mo-B alloys were hardened by precipitation of the E Fe3Moz phase. Boron was observed to have a very strong hardening effect in the Fe-2 pct Mo alloys and a mild strengthening effect on the 1200°F properties of the Fe-4 pct Mo alloys. In the Fe-9 pct Mo alloys there was no consistent effect of boron on strength at either room temperature or 1200° F. The Fe-19 pct Mo alloys were so brittle that meaningful tensile or creep-rupture data could not he obtained. No dispersion hardening from borides was recognized in any of the alloys. THE high-temperature properties of iron-rich Fe-Mo alloys were studied by Reiter and Hibbard.' They found that the strength of the alloys increased markedly as the molybdenum content was raised from 0 to 15.9 pct by weight. The authors explained the various degrees of strengthening in terms of a) solid-solution strengthening, b) strengthening from a martensitic-type transformation, and C) precipitation strengthening. The objective of the present investigation was to conduct a survey of the iron-rich portion of the Fe-Mo-B system to determine whether the beneficial effects of molybdenum on the strength of iron can be enhanced by the presence of boron. It was thought that perhaps fine dispersions of molybdenum- rich borides would be found which could improve the high-temperature strength of ferritic alloys beyond the strengths attainable by molybdenum additions alone. Also, it was considered worthwhile to study the effects of boron in alloys which are essentially free of carbon. Most, if not all, of our present knowledge about boron in high-temperature alloys pertains to alloys containing carbon and carbides. EXPERIMENTAL PROCEDURES Alloy Preparation. Seventeen 8-lb ingots were prepared from electrolytic Plastiron, unalloyed molybdenum chips, and boron powder by a vacuum-induction melting procedure employing hydrogen as the main deoxidizer. The alloys were melted in alumina crucibles using 35-lb melts, with each melt being split four ways to achieve varying boron contents within four Fe-Mo base compositions. The results of chemical analyses conducted on chips machined from the chilled ends of the ingots are presented in Table I. The boron analyses were performed by a spectrographic method utilizing primary standards prepared from boric acid. They indicated that in ingots to which no boron was

Jan 1, 1964

By C. H. Li, R. J. Stokes

This paper compares the fracture behavior of tungsten rods in three conditions: recrystallized. recovered, and wrought. Notched specimens suhjected to a 50 in.-lb impact load showed ductile-brittle transitions at 700, 4.90°, and 440°C, respectinely. The recrystallized material had an equiaxed pain structure and jracbred by simple cleavage from a grain boundary source at all temperatures up to 700°C. The wrought and recovered material had an elongated fibrous structure and at low temperatures fractured by cleavage originating from the notch. As the transition temperature was approached cleavage was preceeded by more and more intergvanular splitting which deflected the crack front into planes parallel to the tensile axis. The enhanced toughness of wrought and recovered tungsten was attributed both to its inability to initiate cleavage because no pain boundaries were suitably oriented perpendicular to the tensile stress and to its inability to maintain cleavage because of intergranular splitting ahead of the crack. It has been appreciated for a long time in a qualitative manner that the room-temperature brittleness of fully recrystallized tungsten may be alleviated by working the material at relatively low temperatures.' More recently this difference in mechanical behavior between wrought and recrystallized tungsten has been examined quantitatively by measurement of the tensile properties as a function of temperature. In these experiments brittleness has been expressed in terms of ductility or reduction in cross-sectional area upon tensile fracture or in terms of the bend radius before fracture under bending.' This work has shown the existence of a fairly sharp transition from brittle to ductile behavior with an increase in temperature. The ductile-brittle transition temperature for recrystallized material is approximately 200°C higher than for wrought material. An increase in strain rate, small additions of impurity,' or an increase in grain size4 shift the respective transition temperatures to higher values, but the difference between them remains approximately the same at 200°C. A number of explanations for this embrittlement by recrystallization have been given. It has been blamed either on the concentration of impurity at the grain boundaries, the increase in grain size, or the change in texture which occurs upon recrystallization. The present paper examines the effect of different heat treatments on the notch-impact behavior of commercial powder-metallurgy tungsten rods. The change in the ductile-brittle transition temperature for this method of loading and the fracture mode has been related to the different mi-crostructures produced by heat treatment. EXPERIMENTAL PROCEDURE Commercial swaged powder-metallurgy tungsten rods 1-3/8 in. in length and 1/8 in. in diameter were machined to introduce a sharp V notch 0.030 in. deep. To change the microstructure from that of the as-received wrought material some of the specimens were subjected to an anneal in nitrogen either at 1300° or 1400°C for 8 hr or at 1600° or 2000°C for 1/2 hr. The notched rods were then placed in a miniature Charpy-type impact machine and struck at their midpoint (opposite the notch) with a hammer designed to deliver 50 in.-lbs of energy. The strain rate at the base of the notch was estimated to be approximately 100 sec-1 at the instant of impact. The specimens were heated in situ to the desired impact temperature. The microstructures produced by the various anneals were studied by both X-ray diffraction and metallographic techniques. Fig. 1 reproduces the microstructures observed metallographically following a 10-sec electroetch in a 10 pct KOH solution. Fig. l(a) shows the elongated fibrous grain structure of the as-received material. Following the anneal at 1300" or 1400°C the grain structure was still elongated as shown in Fig. l(b) but the etch pits delineated dense polygonized dislocation arrays within many of the grains. Occasionally a relatively dislocation-free recrystallized grain was found growing into the matrix. The anneals at 1600° and 2000°C resulted in complete recrystallization and some grain growth. The grains produced at 1600°C were still slightly elongated as shown in Fig. l(c) whereas the anneal at 2000°C produced equiaxed grains. The changes in grain size produced the expected changes in the X-ray back-reflection patterns; there was no indication either in the as-received material or the annealed material of any preferred orientation. RESULTS a) Impact Behavior. Fig. 2 reproduces the ductile-brittle transition curves measured in the manner described in the previous section. It can be seen that under these testing conditions the as-received

Jan 1, 1964

By W. A. Backofen, D. Lee

Tlze condition of superplasticity or neck-resistanl flow that results front high strain-rate sensitivity has been observed in isothermal tension tests on several titanium alloys and one of zirconium hi general, il was associated with reasonably fine-grain micro-structures being stvained in the transformation range at rates below i - 10 -3 sec-&apos;. The metallographic mean-free path, L, was measured at room temperature after rapid cooling from the temperature of test-ing. The flow stress of Ti-GAL-4V at 950°C was proportional to La at different constanl <; the value of a decreased with increasing. E but at E< 1.5 x 10-4 sec-1 it varied only from 0.9 to 1.25. The findings were interpreted to mean that viscous boundary shear is the rate-controlling process of deformation at high levels of strain rate sensitivity in these materials. Elongation of over 1000 pet could be obtained, but a1 temperatures so high and rates so low that any practical application of the full effect would probably be difficult. As the transformation range was narrowed, by turning from Ti-6AL-4V to Ti-5Al-2.5sn to nomznally pure titanium, the allowable temperature varialion was correspondingly reduced. Superplasticily was not found in Armco iron, presumably because the transformation range was too narrow to allow the developtnenl of a reasonably stable microstructure for isolhermal lesting. THE work represented by this paper grew out of a recent study of texture hardening in a(hcp) titanium and zirconium-alloy sheet,&apos; of which part has now been published.2 It was found that, with heating, the tensile plastic-anisotropy index, R,* was decreased from well above 1 towards 1 as the temperature range for the a(hcp) -ß(bcc) phase change was entered. The clearest example of that trend is illustrated with previously unpublished data in Fig. 1. It might have been thought that such a development resulted simply from introduction of the cubic and therefore plastically less anisotropic phase. However, the accompanying change in the index of tensile strain-rate sensitivity, m = a log a/a log E, was rapidly upwards, to a high of 0.85 in some cases (also illustrated in Fig. 1). At the same time, the total tensile elongation rose to a maximum and the flow strength dropped away as R (and m) approached 1. Taken together, the observations cannot be understood as resulting from the presence of cubic phase, per se. It has been concluded instead that they reflect the largely noncrystallographic deformation which characterizes superplasticity. As demonstrated in other recent work? a necessary condition for super-plasticity is strain-rate sensitivity of flow stress sufficiently high that m is above a lower limit of -0.3. The origin of large m has been traced, in turn, to grain size so small that a substantial amount of viscous deformation is introduced by such processes as Nabarro-Herring diffusional flow4 and/or grain boundary shear.5,6 Because of problems in the processing of titanium and zirconium alloys—problems of high strength, limited ductility, and excessive springback, originating largely in slip resistance-it was natural to wonder if something useful might be done with superplasticity in those materials. Therefore experiments were made for more closely identifying and generally bounding the phenomenon with temperature and strain-rate limits, before attempting to decide about its exploitation. The results are being reported here. EXPERIMENTAL Materials. The two of primary interest were the titanium alloys of nominal composition (in wt pct) 5A1-2.5Sn and 6A1-4V. Others were a 4A1-1/4O2 titanium alloy, titanium of commercial purity (RC-70), Zircaloy-4. and Armco iron. All were received as annealed 3/16 in. thick sheet, except RC-70 which was & in. thick, and tested in that condition. Details of transformation temperature and grain size are given in Table I. The results of dilatometry for the measurement of transformation temperatures were unsatisfactory. Data were finally obtained by metallographic examination of each specimen after test, to determine from the amount of transformed 4 where the specimen had been heated in relation to the critical temperatures. Results were in reasonable agreement with information from the supplier. Strip tensile specimens were of full sheet thickness and taken along the rolling direction, except for those

Jan 1, 1968

By V. A. Phillips

Transmission-electron micrographs of electro-thinned samples of bulk-aged Cu-3.1 pet Co alloy show an aging sequence, supersaturated solid solution — coherent particles — quasi -coherent particles — noncoherent particles. Hardening is due to precipitation of coherent spherical fee coball-rich particles showing coherency strain fields, which are resolved at between 15 and 30A diameter. Loss of- full coherency did not occur until well into the overaged region, even with the assistance of deformation after aging. Different average particle diameters of 123, 92, and 149 ± 10Å were observed in samples aged to peak yield strength at 600°, 650°, and 700°C, respectively, indicating that there is no critical size for peak hardening. Noncoherent particles tended to develop (111) faces and became octahedral in shape. Dislocations tended to nucleate spherical coherent particles which eventually grew together forming large elongated particles. The surface energy of a noncoherent (low-angle) inter-phase boundary is estimated to he about 50 ergs per sq cm. A number of particle lining-up phenomena were observed. Overaging is principally attributed to increase in particle spacing, progressive loss of coherency, and increase in amount of discontinzdous precipitation. COPPER dissolves about 5.6 at. pet (5.2 wt pet) of cobalt at 1110oC1 and the solubility decreases to 0.75 at. petl (0.54 at. pet)2 at 650°C and to 0.1 at. pet or less at lower temperature.&apos; It has been known for many years3-5 that Cu-Co alloys are capable of age hardening. Since cobalt is fee above 417°C and its atom size is only about 2 pet smaller than that of copper, precipitation of coherent particles would be expected. The equilibrium phase precipitated at 700°C and below contains about 10 pet Cu in solution which tends to stabilize the fee structure, lowering the transformation temperature to 340oc.l The alloy is known to undergo discontinuous precipitation in addition to general precipitation; while the former can be seen with an optical microscope, the latter precipitates are not visible except in the grosly overaged condition.5, 6 Extensive use has therefore been made of the ferromagnetic properties of the precipitate in order to follow the course of aging, and it has proved possible to measure the average particle size, spacing, approximate shape, and volume fraction and to determine that the particles are coherent without ever seeing a particle (see for example Refs. 2, 7, and 8). The magnetic measurements of particle size are limited to diameters below about 120Å.7 The present study was undertaken using the techniques of transmission-electron microscopy in order to check the above conclusions, to extend the previous magnetic work to larger particle sizes, and to attempt a more detailed correlation of properties and structure. A portion of this work has already been published.9-11 The present paper is concerned with the metallographic features of precipitation in relation to aging curves. Bonar and Kelly12&apos;13 have published preliminary results of a similar study on single crystals of Cu-2 at. pet Co. EXPERIMENTAL Preparation of Alloy. A Cu-Co alloy, containing 3.12 wt pet (3.36 at. pet) Co by analysis, was prepared from 99.999 pet purity oxygen-free copper and electrolytic-grade cobalt. The alloy was melted and cast in vacuo in a high-frequency furnace using a graphite crucible and mold: Analysis showed chat 0.004 pet C was picked up during melting. The 1-1/2-lb ingot was homogenized in hydrogen for 24 hr at 1000°C. Slices were cold-rolled to 0.005 or 0.003 in. thickness, with an intermediate 650°C anneal in hydrogen at 0.080 in. thickness. Batches of six to ten strips were solution-treated in sealed-off quartz tubes in high vacuum in a vertical furnace and quenched by dropping into iced brine containing a device which snapped off the nose of the tube. Solution treatment consisted of 1 hr at 990°C or 2 hr at 965°C. The latter was employed for all mechanical-property studies, since a tendency was noted for the higher temperature to give porous material. Strips were usually aged individually in a horizontal vacuum furnace, inserting into the hot zone and withdrawing into a cold zone without breaking the vacuum. This method gave a rapid heating rate, permitting the use of short aging times. In some cases, particularly for the longer aging times at the higher temperatures, samples were sealed individually in quartz tubes in high

Jan 1, 1964

By Francis Cameron

Gloomy predictions that domestic mineral reserves are approaching exhaustion are unwarranted and may be harmful, this author contends. Specific mineral forecasting errors in the Paley Report are cited to support this contention, and steps that can be taken to insure a progressive mineral industry capable of keeping pace with the major raw material needs of the nation through advancing technology are suggested. Mining is both exciting and rewarding —although at times somewhat frustrating— and we all can have real pride in our industry, in its people, and in its accomplishments. It is, however, with concern that I have noted a deterioration in this Country in what might be called mining&apos;s stature and in the growth of a belief in many quarters that our mineral reserves are rapidly approaching exhaustion. In other words, there is a popular image that we are fast becoming a "have not" nation in many respects and that the domestic mining industry can no longer be considered, in the vernacular of Wall Street to offer much in the way of "growth potential." I do not subscribe to this hypothesis, nor do I be-li4ve that the record of the mining industry bears this out. However, let me add that we can, in time, talk ourselves into this frame of mind and we can hasten the day when this very well might come about by unnecessary and unwise legislation or regulation. My remarks today are basically designed to give my reasons for refuting this negative philosophy and to review our record. With your help, I know we can improve our image, and the public&apos;s recognition of our industry&apos;s peculiar problems. The progress of our civilization over the centuries has been fundamentally based upon proper use of raw materials, both agricultural and mineral, and upon energy, human or otherwise. As the standard of living has progressed century by century, the demands for mineral raw materials have increased in an irregular, but steadily rising progression. Fortunately, those minerals on which we depend most, i.e., iron, coal, petroleum, copper, aluminum, lead, and zinc have been neither too difficult to find nor to process into useful form. Iron, the most useful of all metals, is present in various amounts in most rock types and soils. Gold, seemingly the most generally desired (but certainly not the most useful of all metals), occurs in sea water in a far greater total tonnage than has been won from all of the world&apos;s known gold mines. If the latter is true, then why do we not see large installations treating sea water for the recovery of its gold content? The answer, of course, is that even the French, who seem, from their recent actions, to value gold above all else, have not devised a way of doing this at a profit. Theoretically, it is possible, but not with today&apos;s technology at a cost which would justify the effort. Man has exploited only those mineral concentrations which accidents of nature have placed within his so far limited means of finding and utilizing. What we geologists and engineers refer to as an orebody is nothing more than a concentration of minerals, exploitable with available knowledge, that will yield a value greater than the value attached to the energy and capital required to produce it. What is "ore" and what is not "ore" is, in the end, a matter of economics. The economic problem stems from the physical and chemical character of mineral deposits. The good Lord stacked the cards heavily in favor of rising costs by limiting the amount of the higher grade ores easily available. As the best and most accessible ores are depleted, it becomes necessary to work harder and with greater ingenuity to produce more from less accessible and lower grade resources. The quantity of mineral raw materials we can have in the future will be determined largely by what we can afford to pay for them in terms of human effort, capital outlay and production energies. We will always have the problem of cost with us and our only real means of keeping ahead of rising costs is by continually improving our technical abilities. We, in this country at least, no longer have open to us large and unexplored virgin wildernesses in which a pick-and-shovel prospector might uncover an untouched mineral bonanza. The rest of the world also has few conventional frontiers left in which the explorer-prospector is free to roam. We do, however, have enormous land areas unexplored, and untouched po-

Jan 1, 1969

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-&apos; cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

By J. L. Lehman, J. D. Sudbury, J. E. Landers, W. D. Greathouse

A full scale field experiment on cathodic protection of casing answers questions concerning (1) the proper criteria for determining current requirments, (2) the amount of protection provided by different currents, and (3) the transfer of current at the base of the surface pipe. Three dry holes in the Trico pool in Rooks County, Kans., were selected for cathodic protection tests. The three holes were in an area where casing failures opposite the Dakota water sand often accur in less than a year. Examination of the electric togs showed the wells to be similar to other wells in the field where casing in four of seven producing wells has failed. The three holes were cleaned out and cased with 75 joints of new 51/2-in. 14-tb J-55. Each joint was visually inspected and marked before it as run. The casing was bull plugged and floated in the hole 50 that the inside might remain dry and free of excessive attack. Also, if a leak occurred, a pressure increase could be observed on gawge at the surface. Extensive testing was done, including potential profiles, log current-potentid curves and electrode measurements from both surface and downhole connections. Based on these data, a current of 12 amps was applied to one well and 4 amps to mother. The third well was left to corrode. During the two-year period when the casing was in the ground, [he applied current was checked weekly, and reference electrode measurements were made about every two months. Three sets of casing potential profi1e.c were run. When the three strings were pulled, each joint was examined for type of scale formed, presence of sulfate-reducing bacteria, extent of corrosion nttnck and pit depth. Since the pipe was new when run, quantitative determination of the protection provided by current was possible. This is the first concrete field evidence to help resolve the many arguments about the proper method for selecting adequate current for cathodic protection of oilwell (-using. INTRODUCTION A casing string is run when a well is drilled. This pipe is supposed to protect this valuable "hole in the ground" for the life of the well. Often the casing does not last the life of the well; it is with these casing failures that this work is concerned. The cost of repairing a casing failure varies from field to field—from as much as a $30,000 per leak average in California to $5,000 per leak in Kansas. Additional costs other than actual repairs are also important. These include formation damage, lost production, etc. Casing damage caused by internal corrosion is important in some areas. Treatment normally consists of flushing inhibitor down the annulus, but further research is being done on control measures. The test described in this paper is concerned only with external corrosion. The problem of casing failure from external attack has appeared in several areas including western Kansas, California, Montana, Wyoming, Texas, Arkansas and Mississippi. Cathodic protection is currently being used in an attempt to control external corrosion. From reports in the NACE there are thousands of wells currently under cathodic protection. The quantity of current being applied ranges from 27 amps on some deep California wells to a few tenths of an amp being supplied from magnesium anodes on wells in Texas and Kansas. Considerable field and laboratory effort1,9,5,6 was exented on the problem of cathodic prctection of casing, and it became fairly obvious that this method could be used to protect wells. Early workers showed that current applied to a well distributed itself over the length of the casing and was not concentrated on the upper few hundred feet. Basic cathodic protection theory had shown that corrosion attack could be stopped by applying sufficient current. The problem resolved itself, then, into one of trying to decide just how much current was necessary. Various criteria were utilized in installing the many existing cathodic protection installations. These methods included the following. 1. Applying sufficient current to remove the anodic slope as shown by the potential profile." 7. Applying enough current to maintain all areas of the casing at a pipe-to-soil potential of .85 v.&apos; 3. Applying the current indicated by a log current-potential (or E log I) curve." 4. Supplying the current necessary to shift the pipe to-soil potential .3 v." 5. Applying 2 or 3 milliamps of current per sq ft of casing."

By Harry A. Lipsitt, Douglas Y. Wang

A fatigue study in completely reversed axial tension-compression has been perforried on high-purity titanium and on three high-purity alloys of titanium. The alloys each contain approxi7nately 0.75 at. pct of a single interstitial element; carbon, nitrogen, and oxygen, respectivley. The results corroborate a previously published theory which proposed that strain aging under alternating stress was responsible for the fatigue limit behavior of certain alloys. The present data indicate that in these alloys an increasing strain-talline aging effect under alternating stress is provided by oxygen, carbon, and nitrogen, respectively. CURRENT research on the nature of the fatigue limit in metals suggests that the presence of a fatigue limit in metallic materials is a manifestation of strain aging that occurs under alternating stress.lm5 A comprehensive theoretical model based on the above hypothesis has been developed to explain the existence of a fatigue limit.&apos; This model also provides increased insight into several other fatigue phenomena as under stressing, overstressing, and coaxing effects. The theory, as well, provides equal understanding for those cases where no real fatigue limit is observed. Briefly, this theory assumes that the S-N curve for a pure metal is a smooth function of the applied stress, and the effect of adding an element that is soluble (or forms a precipitate) in the pure metal is simply to shift the S-N curve to the right. If the added element confers the power to strain age, the result is a further shift of the S-N curve, this time upward and to the right. Since strain aging is not expected to be a strong function of stress, and since damage per cycle is known to be quite stress dependent, it is to be expected that there will be some limiting lower stress at which the strengthening due to strain aging will balance the damage due to crack propagation. This stress is the fatigue limit. The position of the fatigue-limit knee was thought to be a function of the magnitude of the strain-aging effect on both the finite and infinite life portions of the S-N curve. Although the strain aging hypothesis seems to be reasonably valid for bcc materials,2&apos;6 it needed to be tested for both fcc and cph metals. This report is the first of a series concerning the fatigue-limit behavior of titanium with varying amounts of the interstitial solutes (C, N,, and 4) that are known to cause static strain aging in titanium. Yield-point effects have been reported for polycrys-talline high-purity titanium alloys containing either carbon, nitrogen, or oxygen.7&apos;9 These effects were observed at testing temperatures in the range 100 to 300&apos;. In addition yield-point and strain-aging effects have been reported for single crystals of titanium containing 0.1 wt pct C plus N.&apos; These yield points were observed over a wide temperature range, but no room-temperature aging occurred. Aging at 180&apos; was required to cause the return of the yield point. The magnitude of the yield phenomena in titanium containing interstitials is not expected to be as large as is observed in bcc metals because of several factors. Titanium has a very high chemical affinity for oxygen and nitrogen. The thermodynamic stability of solutions of oxygen or nitrogen in titanium is recognized. Lattice parameter measurements of titanium containing arbon, oxygen,1° or nitrogen" show that the "c" parameter is expanded more than the "a" parameter, but that up to about 2 wt pct this results in an insignificant change of the axial ratio &apos;c/a." Ehrlich" has shown that the sites occupied by interstitial atoms in titanium are spherically symmetrical and therefore a lattice expansion, at a constant c/a ratio, results in a simple dilation of the interstitial site. Such a dilation involving no shear has been shown to react only with edge components of dislocations.13 This causes only a weak pinning action. Shear stresses would be anticipated locally when only one of the two interstitial positions was occupied. The carbon atom will cause a symmetrical distortion of the lattice whereas the oxygen and nitrogen atoms have, in addition, the previously mentioned chemical affinity of titanium for these elements. These factors will result in a considerably smaller reduction of free energy upon the association of interstitial atoms with dislocations, and therefore a much weaker pinning than has been observed for the bcc metals. These considerations would lead to the hypothesis that of the interstitial elements considered here carbon would cause the strongest pinning effect in titanium where the amount of interstitial in solution is constant. This hypothesis will be borne out in the analysis of the present results.

Jan 1, 1962

By Frederick Laist

About six years ago the Anaconda Copper Mining Co. decided to investigate the possibility of extracting zinc from the ores of certain mines in the Butte district. These ores are of a complex character and contain so much iron and lead that the concentrate contains only 33 to 35 per cent. zinc. Investigations showed that while a high-grade concentrate could not be obtained by ordinary methods, such as tabling and magnetic treatment, a fair grade could be made by the Horwood process. In this method, the concentrate resulting from the flotation of all of the sulfides is given a light roast and this calcine is subjected to flotation in the presence of a large amount of sulfuric acid; the resulting concentrate contains most of the zinc and a residue contains most of the iron. The fact that the lead, copper, and silver are divided approximately equally between the zinc concentrate and the iron residue and the large consumption of acid, which ranged from 50 to 100 lb. (22 to 45 kg.) per ton of concentrates, were serious objections to this plan. The zinc recovery, moreover, was low, as a considerable percentage invariably accompanied the iron. While a profit might be made on the ores by the use of this process, it was thought that other and more promising methods might be devised. After carefully studying the field and doing some laboratory work on various processes that had been suggested, it was decided that the electrolysis of sulfate solutions was the most promising. We soon found, as have other investigators, that the only way to obtain a good zinc deposit is to have the electrolyte free from all metals more electronegative than zinc, such as copper, cadmium, lead, arsenic, antimony, etc. Arsenic and antimony are particularly injurious, causing very poor current efficiency and small yield per horsepower when present in amounts so small as almost to defy detection—1 mg. or less per liter. A pure zinc is soluble only with difficulty in sulfuric acid; an impure zinc dissolves very readily. Electrolytic zinc deposited from pure solutions is, of course, extremely pure and dissolves only about one-fiftieth

Jan 1, 1921

By Carville E. Sparks, Rollin Farmin

TRIAL installations of rock bolts, of the slit-rod-and-wedge type, were under way at several units of Day Mines, Inc., when Korean hostilities interrupted the already slow deliveries of steel bars to the Coeur d&apos;Alene district. Factory-made bolts had not yet been put on the local market, so the program was halted for lack of supplies. Interest was revived by a visitor&apos;s description of wooden roof bolts. These were said to have been used briefly with apparent success in a coal mine, until apprehension voiced by the U. S. Bureau of Mines caused the practice to be suspended. To make wooden bolts for trial in ground support, Day Mines acquired a second-hand doweling machine equipped with two cutting heads, one to turn out the desired round rods of 2-in. diam, the other to turn out 1-in. rods to be used as powder-tamping sticks. This machine was installed in the all-weather sawmill of the Hercules mine unit at Burke, Idaho, where fabrication of the wooden bolts commenced early in 1951. Most of the mining in the Coeur d&apos;Alene district is along steeply dipping veins in shaly quartzite and argillite of Algonkian age. Ground support commonly is required in zones where the rocks have been sheared, brecciated, and hydrothermally altered. Pressure from the sidewalls is more troublesome than weight overhead, but both increase with the size of the mine opening. Caving may come from a progressive sloughing of irregular rock fragments or from an exfoliation and buckling of the layered wall rocks. The disintegration is thought to develop from an initial elastic expansion of the rock toward the newly-created mine opening, followed by the dilation of many tiny partings in the rock by absorption of water. As the partings widen, masses of rock develop weight and become free to fall. The function of rock bolts is to prevent or retard widening of partings in the rock supported. Wooden Bolts, Wedges and Headboards Bolt assembly used by Day Mines consists of a bolt 4 or 6 ft long, two wedges 16 in. long, and a headboard 30 in. long, Fig. 1. All four pieces are made of local red (Douglas) fir, either green or well-soaked in the mill pond before it enters the sawmill. Bolts are fabricated from cants, 2 1/4 in. sq, cut from relatively straight-grained timber with a minimum of knots and trimmed to 4- and 6-ft lengths. The bolt then is turned in the doweling machine from 21/4 in. sq to 2 in. diam round, except for a 4-in. length at one end which is left full square to provide the striking head and the shoulder that holds the headboard in position for wedging. The foot end of the bolt is slit with a thin saw for a length of about 16 in., thereby making a slot to receive the wedge against which the bolt is driven for anchorage at the bottom of the rock hole. A similar slit, 12 in. long, is made in the opposite (head) end of the bolt to receive the second wedge, which crowds the headboard against the ground at the collar of the rock hole and puts the bolt in tension. The second slot is aligned 90" from the plane of the first slot to avoid Longitudinal splitting and is notched out slightly to allow easier insertion of the collar wedge after the bolt has been driven to bottom. To prevent splitting the headboard by spreading action of the head wedge, this slot is oriented at 90" to the grain of the headboard when the pieces are assembled, Fig. 2. The wedges are similar to standard mine wedges, but more slender; they are cut 1 7/8 in. wide and 1 in. thick at the heel and taper out in 16 in. of length. The headboard, or bearing plate, is not necessary for some types of ground but generally is desirable because it helps the bolt to support an area of loose, friable rock and reduces the tendency for the rock at the collar of the hole to split away from the wedged head by distributing the pressure over a wider rock surface. The headboard may be a 24-to 30-in. length of 3-in. plank, 8 to 12 in. wide, but a similar length of rounded sawmill slab serves equally well at 20 pct of the cost. A hole of 2-in. diam is bored or punched through the center of the headboard, either at 90" or at various high angles to its surface. The bolt is inserted to its shoulder through this hole, then driven into the rock hole. Bolts, wedges, and headboards are given a full timber preservative treatment to inhibit rot. Bundles of each are immersed in a warm saturated solution of Osmose salts in water for 48 hr, removed, dripped dry, and stored in a relatively humid underground depot to cure. Most wooden rock bolts used by Day Mines are 4 ft long. Holes to receive them, about 42 in deep and 2 1/8 in. in diam, are drilled into the rock&apos; to be supported, nearly normal to the periphery of the mine opening. The type of drill used is dictated by convenience: stoper, jackleg, or jumbo-mounted drifter. Correct depth of the hole is assured by use of a measuring stick that has been cut to the proper distance from drill chuck to the ground at the collar of the hole when a standard length drill rod is at the bottom. The bolt is seated to the shoulder through the hole in the headboard, the foot-end wedge is placed in its slot, and the assembly is inserted into the rock hole. Then the bolt is driven until it is seated solidly on the wedge against the bottom of the rock hole. Driving may be by hand with a sledge, or

Jan 1, 1954

By G. E. Johnson

E. D. HYMAN*—How much sorting of scrap is done ? G. E. JOHNSON (author&apos;s reply)—We do practically no sorting. We charge "run of mine" scrap to the furnace. The unmeltables, mostly iron, are in such demand today that there is no difficulty in disposing of them. It may soon be desirable to sort out from the unmeltables as much of the brass as possible. J. J. BRUGMAN†—We have somewhat similar problems in the secondary aluminum business. What is your method of removing the unmelted material from the furnaces? Why have you such an apparently small space in which to charge your materials? Do you find that you have to seal that opening, or can you have it open and continuously charge at one end and pull out the other ? G. E. JOHNSON—Our means of melting scrap is efficient only to the extent that we use the waste heat from the vaporizing chamber to do the job. It is a batch process. We open the charge door and place the scrap on the hearth by hand shoveling. The door is then closed during the melting down period. After the melting is complete, the opposite door is opened and the unmeltables are raked out. The doors are approximately 3½ X 4½ ft and are not sealed during the process only closed. They are nominally tight. Some metal is oxidized in the process. We have visualized a means of conveying the materials through this melting unit with the metals that are melted trickling out during its travel. T. H. WELDON‡—Mr. Johnson, in line with the last question, is it necessary to seal the furnace between the melting down and the vaporizing unit, or have you got an inverted syphon in the bottom of the chamber? G. E. JOHNSON—That was one of the first things we encountered. We had to have a sealed opening, and it is a molten metal seal. You have indirectly asked me another question, which was: "Do you have to seal up the melting unit?" I would say we should exclude as much air as possible, although we are not too efficient in doing that. We allow the melting unit doors to be open when we charge and when we remove unmeltables. You can readily see that that would lead to the idea of having a controlled atmosphere in the melting unit, and I think this would do a more efficient job of melting the scrap. T. H. WELDON—How often do you charge the furnace? G. E. JOHNSON—We charge the melting unit, and rake out the unmeltables, about every hour. H. R. HANLEY*—Are any provisions made for controlling the rate of oxidation for the production of various size particles for certain characteristics of the zinc oxide product? G. E. JOHNSON—Yes, there are many. You are getting pretty much into the fine points of zinc oxide manufacture. Some of us still think we have something to learn about that. In general, this muffle furnace as I have described it to you produces a rounded particle of zinc oxide which is generally formed by a rapid oxidation of the zinc vapor, followed by rapid cooling. We have gone to the other extreme in some of our experiments. We have changed the furnace to produce a type of zinc oxide, such as we thought was peculiar to American process zinc oxide, by controlling the temperature at the point of oxidation and maintaining that temperature for a much longer period of time than we do when we make the rounded shape. There are other relationships that this furnace readily provides. One of the important factors is the ratio of air to zinc vapors. We can vary that by varying the air supply to the baghouse, or vary the rate at which we are vaporizing the zinc by the simple expedient of regulating the temperature over the carborundum arch. We have a number of variables that permit us to produce all of the grades of French process zinc oxide from lead-free up through the highest grades of seal oxides. There are many controls that we can apply to the operation. What I have said is but a brief condensation. K. MORGAN*—Can Mr. Johnson give us some idea of the fuel consumption of the furnace ? How much oil does he use per ton of zinc distilled? I am also interested to know what sort of heat transmission he gets through the arch? What is the thickness of the tiles used to construct the arch? Some time ago we built a small furnace for a different purpose, using a carborundum arch, and we found that the reflectivity of the molten zinc surface was so great we had to use a very high arch temperature. We found we made an improvement by having a layer of carbon on the surface of the zinc. Has Mr. Johnson had any experience on these points ? Does he make any sort of insolu-bles which he leaves in the furnace which he cannot tap out ? G. E. JOHNSON—I believe your first question was the fuel consumption. If I recall, somewhere in this paper there is a test that I quote. I believe we used 800 gal in a given period of time. Offhand I cannot translate that into tons of metal. I might also state that we have this understanding; that the carborundum arch, as the temperature becomes higher, becomes more efficient in heat transmission. As a matter of fact, I believe it is at about 2600°F or higher that the highest efficiency of heat transmission becomes available. We have calculations that I cannot quote from memory which indicate that the carborundum arch does a really very fine job for this type of furnace. Another point that we had considered was the fact that this furnace could be readily constructed so as to furnish an ideal source of heat for waste heat boilers. If a carborundum arch was used over the melting unit, we would have no zinc vapors in the gases at all— just clean combustion gases from which we would have removed some of the heat. L. P. DAVIDSON†— The insolubles

Jan 1, 1950