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By Josiah Royce

To evaluate chemically the sample of rock obtained by diamond drilling, it has long been recognized that the analyses of the two components of the sample, core and sludge, must be given appropriate influence in computing the average analysis of any unit of depth. The purpose of this investigation is to set forth what means are available for apportioning the effect of core and sludge on the final analysis, what variables affect the problem, and what combination of applied mathematics will closest approximate the truth under each condition as these variables proceed within their limitations. A drill hole is bored in iron ore exploration principally to test variations in rock composition with depth and is usually directed as nearly normal to the bedding of a horizon to be tested as possible. This practice has a tendency to minimize variation in composition laterally which in any event is not likely to be great. It is obvious that the opportunity for change in analysis of a particular rock is not statistically as great radially in a diamond drill hole where the distance in which such a change may occur is from 0.719 in. (EX bit) to 1.469 in. (NX bit) as there would be longitudinally even in a' run as short as 5 ft. Variations in composition of bedded or layered rocks are usually greater normal to the bedding than parallel thereto. Even in massive rocks, like porphyries, variations are functions of distance. Hence. in either case, variations along the hole are of greater effect than across it. Let us examine Fig 1 briefly to observe a cross section of a unit of depth of a typical diamond drill hole. If we neglect radial change in chemical composition, which we have seen is small compared to lengthwise variation, we can see that if core recovery was 100 pct, the core and its surrounding area, which would be recovered as cuttings (assuming 100 pct sludge recovery), must analyze the same if the sampling is perfect. This is the foundation of this paper, namely, that if core recovery is complete we may assume that the core constitutes as nearly as possible a perfect sample of the ground drilled. Now let us pass to the methods of weighting core and sludge in the final analysis and then develop each in turn. One might employ core analyses only, sludge analyses only, or apportion the influence of each by one of several methods. The most common apportionment is by direct proportion to relative theoretical vol- ' ume occupied by each component in the cylinder hollowed out by the drill, known as the Longyear formula. Another logical treatment would be to consider core and sludge in the final analysis according to the weight of each recovered. This procedure was elaborately set forth and refined by R. S. Moeh1man.l Then to be sure that we have embraced all the possibilities, we must admit that some other method or methods may be devised empirically or by mathematical maneuvers. Should a drill machine be capable of recovering 100 pct of the core in all types of rock, certainly core alone need be analyzed and no complicated mathematics are required; but although some companies have had fair success in obtaining high percentages of core in certain homogeneous ores on the Mar-quette Range, their same methods have proved disappointing on the Menominee, Cuyuna, and Gogebic Ranges where the iron formation often varies widely from flinty chert beds interstratified with soft hematite to wholly leached ore material composed of an unpredictable mixture of hematite and limonite with occasional zones of sugary, recrystallized chert. In spite of numerous mechanical improvements in core barrels, few drilling programs can count on complete core recovery. The sludge alone might be analyzed but for practical reasons this is inadvisable when core is obtained due to the numerous opportunities for contaminating or losing portions of the cuttings. The Longyear formula involves a weighting of the core and sludge in proportion to the theoretical volume of each, that is, where the volume of the core recovered is one-third of the total cubic volume of the cylindrical hole made by the drill, the analysis of the core is given one-third of the weight in the final analysis. This approach to

Jan 1, 1950

Masjid-i-Su1aiman.—There have been no new developments in the Masjid-i-Sulaiman field during the year. Drilling, deepcning and acidizing operations for maintenance of production havc continued normally. Reservoir conditions have been unchanged, the rate of fall of dome prcssure remaining very low—at about 0.4 lb. per sq. in. per million tons net production. Drilling on the Lali structure northwest of Masjid-i-Sulaiman has continued but oil has not been encountered in commercial quantities. Haft Kel.—The progressive drilling program extending the production capacity of the Haft Kel field was completed carly in the year and the field is now on a routine maintenance basis. Drilling has continued on the white-oil springs structurc northwest of Haft Kel. Naft-i-Shah.—No developments of interest have occurred in Naft-i-Shah field. Offtake is for local markets only. A further large produeer was completed during the year. Gach Saran.—By the end of 1939, work on plant and pipe lines to put, the field on a production basis was approaching completion. Two substantial producers were also drilled in the initial production area. Pazanun and Agha Jari.—No further drilling was carried out on the Pazanun structure during the year, gas only having been obtained to depths exceeding 8000 ft. On the adjacent Agha Jari structure, however, a second satisfactory oil producer was completed.

Jan 1, 1940

Masjid-i-Su1aiman.—There have been no new developments in the Masjid-i-Sulaiman field during the year. Drilling, deepcning and acidizing operations for maintenance of production havc continued normally. Reservoir conditions have been unchanged, the rate of fall of dome prcssure remaining very low—at about 0.4 lb. per sq. in. per million tons net production. Drilling on the Lali structure northwest of Masjid-i-Sulaiman has continued but oil has not been encountered in commercial quantities. Haft Kel.—The progressive drilling program extending the production capacity of the Haft Kel field was completed carly in the year and the field is now on a routine maintenance basis. Drilling has continued on the white-oil springs structurc northwest of Haft Kel. Naft-i-Shah.—No developments of interest have occurred in Naft-i-Shah field. Offtake is for local markets only. A further large produeer was completed during the year. Gach Saran.—By the end of 1939, work on plant and pipe lines to put, the field on a production basis was approaching completion. Two substantial producers were also drilled in the initial production area. Pazanun and Agha Jari.—No further drilling was carried out on the Pazanun structure during the year, gas only having been obtained to depths exceeding 8000 ft. On the adjacent Agha Jari structure, however, a second satisfactory oil producer was completed.

Jan 1, 1940

By H. W. Mossman

Three aspects of magnetite smelting are discussed. The first is the working out of equilibrium conditions for eliminating sulfur. The second is the influence of magnetite solubility on the difficulty of tapping the reverb matte. The third is an approximation of the equilibrium conditions in the reverb gases which govern whether magnetite is mode or reduced in the reverb slag by these gases and by any iron sulfide in the slag. MAGNETITE has had a varied history in the Hurley Smelter since its start in 1939. Magnetite determinations on the smelter products are made regularly only on the monthly composite samples. Variations on the monthly averages are shown in Table I. Magnetite which drops from the slag and matte in the reverb has some slight bottom buildup which comes and goes, but no substantial accumulation from this source has been found at the end of a normal nine months' furnace campaign. However, there has been some low grade magnetite bearing material mixed with considerable A1,0,, which has slid down from the bottom of the sloping flue between the reverberatory furnace and the waste heat boilers. This accretion has required drilling and blasting near the skimming end of the furnace. The magnetite has interfered with tapping at times. When the smelter was first started, tapping trouble from magnetite was extremely severe. Increasing the reverberatory furnace temperature by putting in an air preheater and a Dutch oven has helped greatly, although there still is occasional tapping trouble. When the present series of physical chemistry articles on copper smelting started coming out in 1950, they were read with interest, but no immediate application was seen for them. Results of some laboratory work in 1952 aroused a much stronger interest in this physical chemistry. A series of melts was made on some converter slags, which had magnetite in very large grain sizes, with the object of reducing the grain sizes in the slag, as it was known that it was easier to handle in the reverb in that condition. Anything done in the tests greatly reduced the grain sizes—even in the controls, where nothing was done except melt the slag and cast it. There was more magnetite in the slags after the tests than before, and with wide variations. There were no obvious reasons lor much of what happened in these tests. Much of the base material published in English in this field was made available for study. Recalculations were made on many of the type problems, and part of the data was reduced to local temperatures and compositions. Explanations were found for what happened in the 1952 series of tests on converter slags, and the same principles turned out to be a description of much of what magnetite does in the reverb. This article is to present the results of that study, from the viewpoint of applying the technical material in definite numerical form to the operating conditions in both the converters and the reverberatory furnaces at the Hurley smelter. Table I. Magnetite Variations on Monthly Averages, 1939 to 1955 Pet Magnetite Lowest Highest Average Converter slag 13.6 43.3 25.4 Roverb slaa 2.7 20.9 8.7 Matte 28 15.9 98 In general it was found that magnetite is made or reduced in both the converters and the rever-beratory furnace, depending on variations of temperature, matte composition, and reverb gas composition occurring in ordinary plant operation. Within reasonable limits, the field conditions for formation or reduction can be predicted, and probably can be set up and maintained. Converter conditions affecting magnetite formation can be put into numerical values better than for the reverb from purely technical calculations. The converter can be operated so as to keep the magnetite in the slag down to between 12 and 14 pct and still give satisfactory life for the converter brick. This depends upon having converter flux available which will make a slag with a good separation without raising the temperature too high. In the Hurley reverb and others with similar conditions, it is likely that a compromise of conditions will give a reasonably good control of combustion and still keep the magnetite from building up on the bottom. This discussion consists of three main parts. The first is the working out of the equilibrium conditions in the converter for determining in which direction the reaction 3 Fe,,O, (s) + FeS (1) F? 10 FeO (1) + SO, will go under actual converter operating conditions. The second deals with the influence of the solubility of magnetite in the slag and matte in the reverb on the difficulty of tapping matte. The third is an approximation of the equilibrium conditions in the

Jan 1, 1957

By Vittal S. Bhandary, B. D. Cullity

Swaged iron wire has a cylindrical {001} <110> texture. The texture is also cylindrical after re-crystallization in the absence of a magnetic field, but <111> and <112> components are added to this texture when recrystallization occurs in a field. The mecizanical properties in tension and in torsion are not greatly altered by these changes in texture. AS shown in a previous paper,1 cold-worked wires of the two fcc metals copper and aluminum can be made relatively strong in torsion and weak in tension, or vice versa, by proper control of preferred orientation (texture). The deformation texture can be controlled by selection of the starting texture (texture before deformation), because certain initial orientations are stable during deformation. The present paper reports on similar work performed on bcc iron. In this case it was clear at the outset that there was no hope of controlling the deformation texture, which is one in which <110> directions are aligned parallel to the wire axis. (1t has usually been regarded as a fiber texture, but Leber2 has recently shown that it is a cylindrical texture of the type {001} <110>. In either case, <110> directions are parallel to the wire axis.) There is general agreement on this texture among a large number of investigators, which in itself suggests that the starting texture has no influence on the deformation texture. More direct evidence was produced by Barrett and Levenson,3 who reported that iron single crystals of widely varying initial orientations all had a single <110> texture when cold-worked into wire. Thus <110> is a truly stable end orientation for iron and probably for other bcc metals as well. Under these circumstances attention was directed to the possibility of controlling the recrystallization texture. This texture is normally <110> in iron,4 just like the deformation texture. However, it is conceivable that this texture could be modified by a proper choice of the time, the temperature, and what might loosely be called the "environment" of the recrystallization heat treatment. In the present work the environmental factor studied was a magnetic field. The effect of heating in a magnetic field ("magnetic annealing") on recrystallization texture has been investigated by Smoluchowski and Turner.5 They found that a magnetic field produced certain changes in the recrystallization texture of a cold-rolled Fe-Co alloy. The texture of this material is normally a mixture of three components, and the effect of the field was to increase the amount of one component at the expense of the other two. Smoluchowski and Turner concluded that the effect was due to magnetostriction. With the applied field parallel to the rolling direction, the observed effect was an increase in the amount of the texture component which had <110> parallel to the rolling direction. In the Fe-Co alloy they studied, the magnetostriction is low in the <110> direction and high in the <100> direction. Thus nuclei oriented with <110> parallel to the rolling direction will have less strain energy than those with <100> orientations and will therefore be more likely to grow. In a later paper on the same subject, Sawyer and Smoluchowski6 ascribed the effect to magneto-crystalline anisotropy and made no mention of magnetostriction. In the papers of Smoluchowski et al. the intensity of the magnetic field was not reported but it was presumably large, inasmuch as it was produced by an electromagnet. In the second paper6 it is specifically mentioned that the specimens were magnetically saturated. But if magnetostriction has a selective action on the genesis of stable nuclei during recrystallization, that selectivity must depend only on differences in magneto-strictive strains between different crystal orientations and not on the absolute values of those strains. Thus the saturated state does not necessarily produce the greatest selectivity, because the relative difference in magnetostrictive strains between different crystal directions may be larger for partially magnetized crystals than for fully saturated ones.7 In the present work the specimens were subjected to relatively weak fields (0 to 100 oe) produced by solenoids. MATERIALS AND METHODS Armco ingot iron rod (containing 0.02 pct C and 0.19 pct other impurities) was swaged from 0.25 in. in diam. to 0.05 in., a reduction in area of 96 pct. The mechanical properties in tension and torsion were measured as described previously.&apos; Textures were measured quantitatively with chromium or iron radiation and an X-ray diffractometer,8,1 and

Jan 1, 1962

By B. F. Oliver

Equilibrium and kinetic segregation coefficients for the dilute high-temperature system tantalum in iron have been experimentally determined in a levitating zone melter. The equilibrium segregation coefficient, ko, is 0.43 * 0.03. Planar interface solidification is possible up to a freezing velocity of 4 in. per hr but not at 6 in. per hr. Precise concentration control of the solid is possible over this range of freezing velocities. The momentum boundary layer thickness, and the diffusion boundary layer thickness, 6, are such that either 6, > 6 or ALTHOUGH considerable data exists in the literature concerning the stability of planar-solidification fronts, little data exists for high-temperature metallic systems. The study of fundamental aspects of solidification in high-temperature iron-base systems is complicated by the extensive solvent power of liquid iron. In order to minimize such effects a levitating zone melter was used to study the segregation of tantalum in iron.&apos; The solute tantalum was selected because: 1) the ko value was, according to the literature, initially thought to be less than 0.1, thus increasing the precision of the method used;2,3 2) the vapor pressure and is a constant, fixed by induction stirring, 6, the diffusion boundary layer, is 5150 u. At 400 rpm and 6 in. per hr freezing velocity the cast structure exhibits circular macroporosity and banding concentric with the axis of the rotation of the interface. Electron-beam microprobe analyses indicate that the tantalum content is highest at the center of rotation (1.2/1) and decreases with increasing radius as the fine-grained bands become sharper. This entire structure exhibits microseg-regation of tantalum. of tantalum in 1 atm of H2 is small, assuring conservation of solute during redistribution; and 3) spec-troscopic analyses were available for the appropriate range of tantalum considered. Additional objectives were 1) to determine kinetic segregation coefficients for well-stirred zones with constant boundary conditions and thus quantitatively calibrate solute-segregation behavior in the levitating zone melter, and 2) to examine the range of freezing velocities over which smooth solid-liquid interfaces could be controlled in an iron-base alloy under the restrictions of the thermal gradients imposed while levitating a zone. The single-pass zone-melting method was used to calculate individual k values.&apos;

Jan 1, 1964

By F. M. Lewis, J. E. Goodman

A larger, slow-speed, under-loaded ball mill and hydraulic classifier have almost doubled grinding efficiency at the lsabella mill. TENNESSEE Copper Co. operates two ore con-A centrators, the London and Isabella mills near Copperhill, Tenn. In 1948 and 1949 the small ball mills and rake classifiers in the London concentrator were replaced by one large ball mill and one hydraulic classifier. This new ball mill was designed oversize so that it could be operated at slower than normal speed. The proper operating conditions were established and the results published.&apos; Later it was found that this mill operated more efficiently with a small ball charge." While this London grinding practice was being developed, the Isabella grinding circuit was not changed in any way. It remained a conventional two-stage rod mill—ball mill combination, the rod mill in open circuit and the ball mill in closed circuit with a rake classifier. Study of the data indicated that grinding cost could be lowered by converting to the London practice, but not enough would have been saved to warrant the expense of converting. No plan for improving this grinding operation could be developed. In 1953 this study was reopened when plans were made to increase the Isabella mill output from 1150 to 1500 tpd. At this time the grinding circuit consisted of a 6x12 rod mill followed by a 6x12 ball mill in closed circuit with a 6-ft rake classifier. Another 6x12 ball mill and 6-ft rake classifier would have been sufficient equipment and would have been the simplest and cheapest installation. However, this would have offered no improvement in grinding efficiency or operating cost. If, on the other hand, the grinding operation could be converted to the London practice, by installation of one large 101/2x9x9 tricone mill and a 10-ft hydroscillator,2 lower operating costs would justify the additional investment. Economics: Table I presents estimates for the two schemes for enlarging the Isabella mill. In the first scheme, column 1, one 6x12 ball mill and one 6-ft rake classifier were to be added. In the second scheme, column 2, the existing small ball mill and rake classifier were to be retired and one large mill and hydroscillator were to be installed. Estimated savings from the difference in operating costs made an attractive return on the additional investment for the large mill and hydroscillator. Actual costs of carrying out this plan are tabulated in column 3b. It will be seen that these costs follow the estimates in column 3a very Closely. The return on the additional investment is calculated from the difference in the operating cost in column 1 and the actual operating cost in column 3b. This too come very close to the estimate. Power and Steel: Power requirements and steel consumption for the rod mills and ball mills, both actual and estimated, are presented in Table 11.

Jan 1, 1958

By F. O. Garrabrant

POWER is furnished to the Climax Molybdenum Co. by the Public Service Co. of Colorado over two 100,000-volt line to a bank of three 3333-kva. Transformers 100/13.8 kv. These transformers arc so designed that with the addition of forced cooling their capacity may be increased 33 1/3 per cent at 12,000-ft. altitude. Under present conditions, these transformers are operated at 140 per cent of their rating with forced air cooling. On the secondary side of this bank there is a 15-kv., 1200- amp. Westinghouse oil circuit breaker provided with automatic reclosing relays allowing three successive short circuits before lockout. From this breaker 13.8-kv. power is transmitted to a central switching station (Fig. I) where all circuits radiate to the different operations of the property. Each circuit is protected by a 23-kv., 600-amp. oil circuit breaker with by-pass and isolating disconnecting switches. MINE Power at 13.8 kv. enters the mine through a ventilation raise over a three-conductor, size 1-0 varnished cambric insulated, leaded, steel-wire armored cable, insulated from 17 kv. This power is received and distributed through one switching station and four underground substations, shown in Fig. 2. No. 370 substation (Fig. 3) contains three 250-kva, 13,800/440-volt, single-phase Pyranol transformers protected on the high-voltage side by a 600-amp. manually operated oil circuit breaker. This station serves 20 slusher-hoist motors, a 45-kw., three-phase, 220-volt electric furnace, a Massco hot miller for tempering and milling Timken detachable bits and a hoist with 175-hp. motor on the No. 3 development shaft. Also at this shaft are three pumps. One two-stage pump, 1200 gal, per min., 100-ft. head, 3600 r.p.m., driven by a 150-hp. motor, is at the bottom of the shaft. Two deep-well pumps, 500 gal. per min., 500-ft. head, are at the collar of the shaft. Under normal operation the one pumping 1200 gal. per min. is controlled by a float switch to take care of the water. If this pump fails, or if its capacity is insufficient, the first 500-gal. pump is automatically started, and if still more capacity is needed the second 500-gal. pump automatically starts. Time delay relays are provided on the deep-well pumps, so that if power fails the column will have time to drain before the pumps restart. On failure of any of these, an alarm is sounded in the train dispatcher&apos;s office, so that mechanics can be sent to ascertain the cause of failure and make repairs. The cable from No. 370 substation is run to the switching station, in which are four15-kv., 600-amp. direct-current solenoid-operated oil circuit breakers. The current for operating and tripping is furnished by a 125-volt storage battery. All breakers are operated from the switchboard in the compressor room. One circuit from this switching station goes to the

Jan 1, 1944

By C. M. Marquardt

Tramp iron and steel moving on a conveyor belt cause small currents to be generated in a coil situated in a strong magnetic field, which are converted to an alternating current and are amplified. The output voltage from the amplifier fires a thyratron with a relay in its anode circuit, which actuates a howler and simultaneously drops a spot of marker material on the belt. THE problem of tramp iron removal from moving ore belts is a long standing one. When heavy ore streams are carried on a belt, magnetic pulleys and strong surface magnets fail to remove tramp buried in the ore stream. Tramp iron buried in the ore stream cannot be pulled from the bed by surface magnets and is carried past the magnetic pulley by the falling ore stream. With the increased use of detachable bits the problem of the detection and removal of tramp has become more necessary and difficult. Several types of tramp detectors have been developed. It would serve no practical purpose here to review exhaustively the literature on the subject. Methods of tramp detection used are: (1) The magnetic method, wherein the small current generated by the magnetized tramp passing a Coil is used. (2) The unbalanced oscillator method wherein the tank circuit of a stable radio- or audio-frequency oscillator is unbalanced causing a change of frequency or a change in plate current due to changes in eddy currents, hysteresis, or dielectric because of the presence of tramp. (3) The bridge methods wherein the impedance of one leg of an alternating current inductive bridge is changed due to the presence of conducting tramp. Each of these methods of tramp detection has its field of usefulness. The second and third methods are excellent for oxide iron ores, coal, sand and gravel, grain, etc. However, these latter methods are not suitable for use on ores that contain rich conducting sulphides, since a large piece of pyrite or galena will cause the same detector response as a piece of tramp iron. At the Caselton, Nevada, plant of the Combined Metals Reduction Co., sulphide ores are treated; therefore, it was necessary that a tramp detector operating on only the magnetic properties of the tramp iron be used. Tramp iron detectors of this type operate on the principle that if a piece of tramp iron moves near a coil in a high intensity, steady magnetic field, the presence of the moving tramp iron causes the magnetic flux lines through the coil to change. This induces a mall current in the Coil. In series with the Coil is generally placed a relay sensitive to currents of 1 to 3 microamp. When the tramp iron passes near the coil the flux linkages change, causing this very sensitive relay to actuate. Since the contacts of such a relay are very small it must actuate a second relay capable of breaking a larger current

Jan 1, 1951

By C. M. Marquardt

Tramp iron and steel moving on a conveyor belt cause small currents to be generated in a coil situated in a strong magnetic field, which are converted to an alternating current and are amplified. The output voltage from the amplifier fires a thyratron with a relay in its anode circuit, which actuates a howler and simultaneously drops a spot of marker material on the belt. THE problem of tramp iron removal from moving ore belts is a long standing one. When heavy ore streams are carried on a belt, magnetic pulleys and strong surface magnets fail to remove tramp buried in the ore stream. Tramp iron buried in the ore stream cannot be pulled from the bed by surface magnets and is carried past the magnetic pulley by the falling ore stream. With the increased use of detachable bits the problem of the detection and removal of tramp has become more necessary and difficult. Several types of tramp detectors have been developed. It would serve no practical purpose here to review exhaustively the literature on the subject. Methods of tramp detection used are: (1) The magnetic method, wherein the small current generated by the magnetized tramp passing a Coil is used. (2) The unbalanced oscillator method wherein the tank circuit of a stable radio- or audio-frequency oscillator is unbalanced causing a change of frequency or a change in plate current due to changes in eddy currents, hysteresis, or dielectric because of the presence of tramp. (3) The bridge methods wherein the impedance of one leg of an alternating current inductive bridge is changed due to the presence of conducting tramp. Each of these methods of tramp detection has its field of usefulness. The second and third methods are excellent for oxide iron ores, coal, sand and gravel, grain, etc. However, these latter methods are not suitable for use on ores that contain rich conducting sulphides, since a large piece of pyrite or galena will cause the same detector response as a piece of tramp iron. At the Caselton, Nevada, plant of the Combined Metals Reduction Co., sulphide ores are treated; therefore, it was necessary that a tramp detector operating on only the magnetic properties of the tramp iron be used. Tramp iron detectors of this type operate on the principle that if a piece of tramp iron moves near a coil in a high intensity, steady magnetic field, the presence of the moving tramp iron causes the magnetic flux lines through the coil to change. This induces a mall current in the Coil. In series with the Coil is generally placed a relay sensitive to currents of 1 to 3 microamp. When the tramp iron passes near the coil the flux linkages change, causing this very sensitive relay to actuate. Since the contacts of such a relay are very small it must actuate a second relay capable of breaking a larger current

Jan 1, 1951

By C. E. Birchenall, M. H. Davis

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. &apos;The linear rate law obtained is explained by interface reaction control of the process. Tracer experiments indicate the oxygen diffuses in at least one phase of the scale. THE kinetics of oxidation of titanium, principally at low temperatures and under varying oxygen pressures, have been reported.¹,² In the present investigation the rates of oxidation of titanium have been determined by the gravimetric method in the temperature range 650" to 1000°C under 1 atm of oxygen. Some of the scales formed were powdered and an endeavor was made to identify the phases present by X-ray diffraction. Alexander and Pigeon1 ascribe a logarithmic rate law to the growth of thick films formed at temperatures up to 565"C, and Gulbransen and Andrew&apos; suggest that the parabolic rate law holds up to 600°C. In both cases large initial deviations from those relationships are apparent and no explanation is offered. In the present experiments it is shown that a linear rate law holds in the temperature range 650" to 1000°C, and it is suggested that the initial deviations observed are due in part to a spurious surface area effect and also to the high solubility of oxygen in titanium metal. Positive information on the mechanism of oxidation is not available, but oxygen ion diffusion through the lattice is inferred from the re- sults of trace experiments. X-ray analysis of the scale confirms Gulbransen and Hickman&apos;s&apos; observation on the presence of rutile TiO². Experimental Details The titanium used in these experiments was prepared by the reduction of titanium tetrachloride with magnesium and was used in the form of rolled sheet. Samples approximately 0.040x0.5x0.75 in. were cut and polished to a fineness of 4/0 on metal-lographic polishing papers. Individual samples, suspended on a platinum wire, were lowered into the hot zone of a furnace, in vacuo, by means of a winch, and oxygen was admitted after the desired temperature was attained. The increase of weight of single samples oxidized for fixed times at certain temperatures was determined by weighing the sample before and after oxidation on a chemical balance. In these instances the sample was used for only one time at one temperature. In some cases the course of oxidation was followed by attaching the sample to a sensitive spring balance and noting periodically the extension of the spring with time of oxidation. Kirkendall type experiments were carried out by marking the surface of the titanium prior to oxidation with a solution containing radioactive silver. After drying, the specimen was heated in vacuo to decompose the silver nitrate used, leaving a small amount of metallic radioactive silver on the surface. Following oxidation, these samples were mounted, ground, and then placed in intimate contact with

Jan 1, 1952

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2&apos;3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By Alexander L. Field

IN a previous paper,&apos; the experimental methods used and some of the results obtained in an extensive investigation of steels containing zirconium were described. The present paper considers in greater detail one of the most interesting of these effects, namely, the elimination of " red shortness" and the occurrence in steel of a compound of zirconium and sulfur. A consideration of the actual percentages of zirconium, manganese, and sulfur in numerous steels in the light of behavior during rolling has led to new conclusions of the most practical import regarding the reciprocal relationships of these elements. The microscopic examination of high-sulfur steels containing zirconium has also been productive of interesting results. Before discussing the experimental data in question, it may be stated, briefly, that the rettetion between zirconium and sulfur in molten steel may be represented by the simple equation, Zr + 25 = ZrS², and that the zirconium sulfide thus formed occurs in the finished steel in the form of gray-colored inclusions, closely resembling manganese sulfide and, like the latter, exhibiting plasticity at rolling temperatures. Molten steel containing zirconium retains such a negligibly small amount of oxygen in solution that the foregoing reaction goes to completion. Hot-rolling Properties of High-sulfur Steels with and without Zirconium The chemical composition of twenty-eight steel ingots embracing eleven heats made in a basic-lined electric furnace is shown in Table 1. The practice followed in the manufacture of these high-sulfur steels was described in the previous paper. Table 1 also gives the behavior of the

Jan 1, 1924

By H. C. Fiedler

X HE development of the cube-on edge secondary re-crystallization texture in Si-Fe strip requires that normal grain growth be restrained. It has been shown that the degree of restraint and hence the completeness of secondary recrystallization depends upon the size and number of second-phase particles, which in turn is dependent upon the prior processing history.1y2 The purpose of this note is to show that, for heats in which manganese sulfide particles are providing the restraint to grain growth, the choice of hot rolling temperature depends upon the manganese content. The making and processing of the heats to the final gage of 0.012 in. has been described.3 The compositions are given in Table I. Apparent in Fig. 1 is the decrease in the ability of strips hot-rolled from 1175°C to undergo secondary recrystallization as the manganese content increases. It has been shown that 1175°C is below the solubility temperature of 0.014 pet S in even the 0.038 pct Mn alloy: and the observed behavior is attributed to an increasing fraction of the sulfur forming large manganese sulfide particles at the heating temperature for hot rolling. This fraction of the sulfur is thus unavailable to subsequently form the small, uniformly dispersed particles which are needed to restrain normal grain growth. Since the sulfur is completely in solution at 1325°C,3 strips from all three alloys show strong secondary recrystallization behavior when hot-rolled from that temperature.

Jan 1, 1969

By R. E. H. Pomeroy

EARLY in 1917, it became evident, owing to existing and pending market conditions, that a substitute for crude petroleum must be found for firing the smelter furnaces. After a review of the plants then existing, it was deemed advisable to depart from their practice and to adopt the following described system of distributing pulverized coal to the furnaces. The principal advantages of the proposed system, which influenced this decision, were: (1) Equal safety; no pulverized coal is stored at the furnaces; (2) greater ease of operation, furnace fires being controlled by regulating valves in burner branches, as in gas firing; (3) better organization; all machinery, including pulverized coal feed, is under one roof, and the organization is separate from the furnace department; (4) greater cleanliness; all machinery is under vacuum; (5) greater flexibility of application; the coal and air mixture can be piped where needed. The design of the plant is the result of the combined efforts of the local engineering staff and of the machinery manufacturers. Many new features were embodied in this design to insure greater safety, cleanliness, and efficiency of handling. After 14 months of continuous operation, the plant has proved entirely satisfactory. The building is of structural steel, covered with corrugated steel, with many windows and is painted light gray inside and out. The building floor is of concrete with ample drains to the sewer, and the building is equipped with fire and service water piping. Fig. 1 shows the east side of the building and the incline conveyor from the raw-coal bins.

Jan 2, 1920

By D. J. Bourne, G. E. Atwood

The new potash refinery of Duval Sulphur & Potash Co. produced its first tonnage of muriate of potash in November 1951. Full capacity was attained in early 1952. Excellent extraction efficiency is being obtained by the process, which is basically froth flotation. System temperature control is practiced and has proved to be of great metallurgical value through high potassium recovery and. low reagent cost. WHEN Duval Sulphur and Potash Co. recently entered the established potash industry, the vast amount of pioneer work essential in an entirely new endeavor was unnecessary. Thus it was possible to screen and assemble proved techniques into a highly efficient process based on the combined knowledge of the industry. It is hoped that the refinements Duval has added to these cumulative achievements will contribute to the rapid advance of the potash industry and related enterprises. The process selected utilizes as raw material syl-vinite ore typical of the Permian Basin. This ore is principally comprised of interlocked crystals of potassium chloride, about 40 pct, and sodium chloride. Also there is as much as 1 1/2 pct of dispersed clay slime which, because of its nature, highly complicates beneficiation of these ores. The refining method is basically flotation in which the mineral sylvite is floated away from the halite-clay gangue to produce a 60 pct K,O muriate of potash product for the plant-food trade. It departs from established practice in the use of an improved reagent scheme, developed by the company&apos;s technical staff, and in

Jan 1, 1954

By F. R. Hensel

Up to the present time few attempts have been made to produce hard nonmagnetic materials by heat treatment of austenitic steels. The usual result has been to cause them to pass into the martensitic stage, thus destroying to a great extent the typical austenitic properties, since this involves a transition of a portion of the iron from a face-centered to a body-centered type of atomic arrangement. High-strength nonmagnetic materials such as might be provided by properly hardening austenite are required in the electrical industry for different machine parts. In Europe nonmagnetic retainer rings for restraining the end-turns of the rotor windings in turbo-alternators have been developed as a special application of high-strength austenite. In testing1 a 28,000-kva. three-phase Siemens turbogenerator running at 3000 r.p.m. at full load current, the losses in the short-circuit test were 450 kw. for the magnetic ring and 286 kw. for the nonmagnetic, and the difference should be attributable to the magnetic ring. The differences in temperatures during the same test are given in Table 1 and these show the advantage of a nonmagnetic over a magnetic retainer ring. Hardening in this case was obtained by cold working, such as hammering, rolling or some means for stretching the steel while at a temperature near 500" C. One means for stretching2 is to rotate the forged or rolled ring in a centrifugal machine so as to develop within it stress higher than

Jan 1, 1931

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941