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By Foster Fraas

MOST commercial electrostatic separators utilize the electrical property of conductivity, but although based on the same principles, they are constructed in a variety of forms, a common one being the simple roll type. Some information obtained during an investigation of that type of separator, and which indirectly is applicable to other types, is presented here. NUMERICAL RELATIONSHIP In Fig. I material discharged from hopper 6 is fed onto grounded rotating roll 2. Electrode 3 is at a high electrical potential with respect to roll 2, and any conductive particle in contact with roll 2 therefore acquires an electrical charge of such polarity that, when present in the electrical field, the force on it is in the direction of electrode 3. A detailed description of the charging by conductance as utilized in electrostatic separators may be found in a previous publication.1 As a result of this force, the path of the projected particle is changed in increasing amounts in the direction toward region C as the magnitude of the charge is increased. With the dividing edge 4 the projected particles may be divided into two fractions -those in region C designated as "deflected" or " deflectant " and those in region B designated as "residue." When material is passed over the roll only once, a complete separation is seldom obtained, therefore most commercial separators contain several roll-separator units in [ ] series, and some practical machines use as many as 12. In this paper a "pass" means the passage of material over a single-roll unit. The procedure is to repass either residue B with a low potential on electrode 3 or deflectant C with a high potential on 3. Most electrostatic separations follow a flowsheet of roughing and cleaning either the concentrate or the tailing, on both. In a specific instance, a dry, heated mixture of wet cleaned chromite and garnet from an

Jan 1, 1942

By H. O. Pickard

The Hoover and Mason Phosphate Co. made extensive tests with a rig manufactured by the Paris Manufacturing CO. as shown in Fig I. It is powered by a 20-hp Wisconsin air-cooled gasoline engine, through a single reduction gear and flexible coupling. The machine operates a 4-in. auger with a detachable cutting head, as shown in Fig I. The auger length is 3 ft 4 in. and the cutting head averages 7 in. The unit has a drilling capacity of 100 ft and can drill an average prospect hole in less than 15 min. The weight of the motor is used for the thrust feed for driving the auger and head down, aided by the spiral shape of the auger. The rate of downward motion—i.e., the feed—is regulated by a handwheel. The string of tools is withdrawn from the hole by a gear train controlled by a hand-operated clutch. In fairly dry strata, not of the consistency of mud, the action of the auger

Jan 1, 1948

By H. O. Pickard

The Hoover and Mason Phosphate Co. made extensive tests with a rig manufactured by the Paris Manufacturing CO. as shown in Fig I. It is powered by a 20-hp Wisconsin air-cooled gasoline engine, through a single reduction gear and flexible coupling. The machine operates a 4-in. auger with a detachable cutting head, as shown in Fig I. The auger length is 3 ft 4 in. and the cutting head averages 7 in. The unit has a drilling capacity of 100 ft and can drill an average prospect hole in less than 15 min. The weight of the motor is used for the thrust feed for driving the auger and head down, aided by the spiral shape of the auger. The rate of downward motion—i.e., the feed—is regulated by a handwheel. The string of tools is withdrawn from the hole by a gear train controlled by a hand-operated clutch. In fairly dry strata, not of the consistency of mud, the action of the auger

Jan 1, 1948

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,' and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.' Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By H. T. Sumsion, A. U. Seybolt

The results of an investigation of vanadium-rich V-O solid solutions are presented, indicating the structure and lattice parameters of two solutions, a and ß, and their approximate temperature-composition existence. The a solution is the terminal body-centered cubic one, and contains up to 3.2 atomic pct 0. The ß solution has an ordered body-centered tetragonal structure, is formed at 1270°C, and exists from about 15 to 22 atomic pct 0. From the evidence available, the various phase boundaries have no appreciable temperature dependence. Evidence has been found for a polymorphic transformation in pure vanadium at 1550°C. IN an earlier investigation' dealing with the preparation of pure vanadium by calcium reduction of the oxide, it was found that small amounts of oxygen drastically reduced the ductility of the metal. Because this effect was so marked, it was decided to make a study of the solubility of oxygen in solid vanadium. This report deals principally with this solubility and the nature of the phase relationships in the vanadium-rich region, particularly at temperatures below 1300 °C. However, during the investigation enough data on the V-0 system were obtained to make it appear worthwhile to present a tentative phase diagram up to the composition VO. The only significant prior work found on this system are the contributions of Klemm and Grimm,' and Mathewson et al.3 Klemm and Grimm prepared a wide range of V-O compositions by powder techniques including the compositions VO.l, VO.2, VO.3 and VO4 (9.1, 16.8, 23, and 28.6 atomic pct 0, respectively). The first three compositions were found to consist of a body-centered tetragonal solid solution, while the last also showed lines of VO (NaCl structure). They found that the parameter c, increased and the parameter a, decreased with increasing concentration of oxygen. For their composition VO.27, or about 16.8 atomic pct O, they cite the values a, = 2.948A, c, = 3.53A, and c/a = 1.2. Klemm and Grimm made no attempt to determine the solid solubility limit nor to construct a phase diagram. They did, however, give some data on the homogeneity range of VO, and they proposed a structure for the body-centered tetragonal solid solution; these points will be taken up later. Materials and Preparation of Samples The vanadium used in this investigation was prepared in the laboratory by the method previously mentioned.' A typical analysis is as follows: Fe, 0.007 pct; Si, 0.02; Ca, 0.06; C, 0.224; O2, 0.044; N,, 0.0017; H2, 0.003; and V, 99.34 ±0.3 (assay). The vanadium assay is probably low by about the error given. The impurities total about 0.36 which, if subtracted from 100, gives a purity of about 99.6. At the time material was being prepared for this work no suitable technique was available for melting vanadium without appreciable contamination. The procedure adopted therefore was to cut the calcium-reduced regulii into slices which were then rolled to strip about 0.025 in. thick for oxygen diffusion. Pieces of rolled vanadium of approximately 0.025xY4xl in. and weighing about 0.3 g were suspended in a vertical fused-silica tube which was part of an ordinary gas absorption apparatus. The silica tube was heated by an electric resistance-tube furnace which could be raised around the silica tube or lowered away from it as desired. This apparatus had no novel features which require detailed description. Other than the silica tube and furnace, it consisted of a glass system evacuated by a liquid nitrogen trapped mercury diffusion pump, a mercury-operated gas burette, a McLeod and a Pirani gage, and a mercury manometer. It was also equipped with suitably located stopcocks for isolating various parts of the system; the vacuum ordinarily attained was between 10" and 10-6 mm of mercury. Oxygen generated by decomposing MnO2 was passed through anhydrous magnesium perchlo-rate before introducing it into the gas burette and thence to the absorption chamber.

Jan 1, 1954

By A. C. D. Chaklader, Ashok K. Kakar

The basic density equation originally dericed ' to predict the increase in density of a compact of spherical particles with the progressive deformation at the points of contact has been further modified to include the yield strength of the material. This has been done by assuming that the contact areas grow to stable sizes under a fixed stress which is equal to three times the yield strength. The final equation has the form: where Do and D me the initial and final bulk densities of the compact, u is the applied pressure, and Y is the yield strength of the material. This equation was tested with the data obtained on spheres of lead, K-Monel, and sapphire. The calculated yield strength t~alues for lead and sapphire are within the range of values reported in the literature. A few of the earliest hot pressing models proposed to explain the mechanism by Murray, Livey, and williams2 and then by McClelland3 are based on a plastic flow mechanism. However, more recent investigations suggest that the overall densification process is a combination of several mechanisms, such as particle rearrangement, fragmentation, plastic flow, and stress-enhanced diffusional creep. While fragmentation and particle rearrangement are considered to be responsible for the densification in the early stages,"475 it has been concluded that the final stages of hot pressing are controlled by stress-enhanced diffusional creep.516 The manner in which the densification takes place, i.e., by fragmentation, particle rearrangement, plastic flow, or stress-enhanced diffusional creep, would depend upon the type of material, the temperature, and the stress level used during the hot-pressing experiments. Metal compacts can be expected to have a much greater contribution from plastic flow than ceramic oxides. Also, plastic flow would be a significant contributing factor to densification at high temperatures and high stresses. Most of these works, directed towards elucidation of densification mechanism, have dealt with kinetics of the process. The results of most of the authors vary from one another and they have proposed either new empirical or semiempirical equations to fit their data. The densification rate was found to vary with the type of the powder, shape and size of the powder, initial packing density of the compact, and a few other factors such as rate of heating, pressure, and so forth. Beyond the initial stages, the densification process has been considered to be as time-dependent flow, controlled by a diffusional process, e.g., Nabarro-Herring creep. Palm our, Bradley, and johnson' have attempted to use modified creep rate equations to interpret the data of densification under hot-pressing conditions. Beyond the initial stages, however, the densification would be controlled by a process depending upon the temperature, pressure, and size of the powders. It is the authors' belief that such densification cannot be exclusively controlled by a single process and so attempts should be made to study some observable phenomenon like microstructure, yield strength, and so forth. The emphasis of this work has been toward studying the densification problem from a more fundamental point of view. Some of the principal variables, like initial packing density, mode of packing, and size of the powders, have been controlled to a great extent. The total strain produced on pressure application (instantaneous) in such a case can be considered to be due to plastic and elastic deformation. The elastic component of the strain can be determined by decreasing the load to the initial value. The strain remaining then can be correlated with the contact areas produced by deformation and the corresponding applied load. In a previous paper,' the possible deformation behavior of spheres in a compact has been theoretically analyzed and experimentally tested. The change in contact area radius a relative to the particle radius R was related to the bulk density and the bulk strain for simple and systematic modes of packing. Tt was found that a density equation relating the above parameters can be represented by: where D and Do are the bulk densities of the compact at any value of a/R and a/R = 0, respectively. This basic equation should hold for any material as it was derived from geometrical considerations alone. An attempt has been made in this work to include the yield strength in the above density equation, so that a knowledge of the properties of any material can be used in predicting the densification behavior during the hot-pressing process. THEORETICAL CONSIDERATTONS The deformation of two spheres in contact under a static load can be compared to the deformation occurring between a hard spherical indentor and the flat face of a softer metal. Tt has been shown theoretically by both ~encky~ and lshlinskyg and experimentally by ~abor" that, for a material incapable of appreciable work hardening, the mean pressure required to produce plastic yielding (for deformation occurring between flat face and a hemispherical indentor) is approximately equal to three times the elastic limit, Y, of the material (in tension or compression experiments). Tabor has further observed that the same relationship is valid in the case of work-hardening materials, if the elastic limit at the edge of the indenta-

Jan 1, 1969

By T. S. Lundy, C. J. McHargue

HE diffusion rate of v48 in single crystals of bee vanadium has been determined at temperatures from 1002° to 1888°C. Standard techniques of lathe sectioning were used for specimens annealed above 1500°C while sectioning by grinding was used for specimens annealed at lower temperatures. As will be seen, the lower-temperature data is enhanced on an Arrhenius-type plot relative to values expected by extrapolation of the high-temperature data. Single crystals were obtained from Linde Co. In Table I the analysis supplied by the vendor is compared with an analysis at Oak Ridge National Laboratory of a sample after a diffusion anneal. The isotope v4' was prepared by the Isotopes Division of Oak Ridge National Laboratory. Proton bombardment of a titanium target in the 86-Inch ORNL Cyclotron was followed by a carrier-free chemical separation. Nineteen specimens, 1/2 in. diam and 3/8 in. long, were cut from the as-received vanadium single crystals. Each specimen was machined with the flat face perpendicular to the longitudinal axis. Specimens were polished through 1/0 emery paper and were etched with 25 pct HF-10 pct H2SO4-10 pct HNO3-55 pct H2O. The polishing and etching steps were repeated until a satisfactory surface finish was achieved. The isotope was electroplated onto the specimens from a neutral solution. Counting rates of the deposited layers were approximately 100 counts per sec. At temperatures above 1200°C specimens were annealed in a tantalum resistance furnace under an argon atmosphere. Temperatures were measured with a Pyro micro-optical pyrometer and a Pt-Pt 10 pct Rh thermocouple. At lower temperatures the specimens were sealed in evacuated quartz ampoules and annealed in Kanthal wire-wound horizontal tube furnaces. A severe reaction occurred at 1200°C between the quartz and the vanadium. This

Jan 1, 1965

By J. L. Wyatt

The electrical resistance of titanium as a function of purity and temperature was measured from —325" to 2800°F. Two points of inflection in the data plots were found, and an increase in resistance with increase in temperature above the transformation was observed. IN 1948 Greiner and Ellis' reported on the thermal and electrical properties of titanium, including a study of the effect of temperature on the electrical resistance. The materials used in the research were obtained from the United States Bureau of Mines, where powder metallurgy techniques were being employed for consolidation purposes. These authors found a decreasing resistance with increasing temperature above 1625°F, and concluded that the latter temperature represented the point of transformation from hexagonal close-packed to body-centered cubic structure on heating. They reported a specific resistivity value of 55x10-6 ohm-cm, and showed that dp/dt was positive, decreasing with increasing temperature above ambient. In one of his early texts Hume-Rothery2 mentioned that certain metals, including titanium, exhibited minima in plots of resistance vs temperature. He indicated that this occurred at 212°F. Reporting many years ago on the effect of temperature on the electrical resistance of zirconium, de Boer and Fast³ showed that phase transformation in this sister metal occurred over a range of temperatures, the extent varying with its purity. Graphs of resistance vs temperature, showing transformation effects over a range of several hundred degrees, were presented for relatively impure metal. In the latter case the resistance decreased with increasing temperature throughout the region of partial phase transformation, thereafter increasing as predicted for normal metals by modern theories of the solid state. Since the quality of metal used in previous studies was substandard compared with iodide-type titanium, and in view of the fact that there seemed to be some rather unusual observations in the reported literature, it was decided to undertake a more extensive study of the thermal effects using high purity titanium, and to include temperature ranges beyond those which had been studied in order to ascertain whether or not the characteristics of zirconium would be duplicated. Experimental Materials Materials used in this investigation included commercial quality titanium (Ti-75A produced by the Titanium Metals Corp. of America) in the form of ¼ in. diam rods, and high purity iodide titanium (produced by the Foote Mineral Co.) in the form of crystal bar of irregular size. The latter was cold-swaged into rod form and machined to the desired size. Lead wires to all specimens consisted of 18 gage Ti-75A. Chemical analyses of the stock materials are given in Table I. Experimental Procedures Specimens 2½ to 3 in. in length were prepared with diameters nominally 0.15 to 0.20 in. Two holes,

Jan 1, 1954

By W. C. Phalen

SALT-MAKING PROCESSES THE production of salt in the United States divides itself at the outset into two distinct classes: (1) The mining of rock salt and its purification and separation into marketable sizes, and (2) the production of salt by evaporation from brines, bitterns, and other solutions. The processes employed at the present time in the manufacture of salt by evaporation may be outlined as follows: 1. Solar evaporation. 2. Direct-heat evaporation (a) in open kettles; (b) in open pans. 3. Steam evaporation, (a) in jacketed kettles, (b) in grainers. 4. Vacuum-pan evaporation. In this paper only the solar-evaporation processes practised in different parts of the United States will be described. SOLAR EVAPORATION Localities In the Eastern States the solar-evaporation process is not generally employed for climatic reasons. In the Western States, particularly in California and Utah, the great bulk of the salt produced originates in the solar-evaporation process. Of the Eastern States producing salt, this process, so far as the writer is aware, is employed in New York State only.

Jan 9, 1914

By F. J. Longworth

For a number of years an intensive study has been made to improve the blast-furnace practice at Copperhill not only as to costs but to provide a good grade of gas for the acid plants. This study, took us back to the fundamentals of successful pyrite smelting; namely, a blast furnace working on a clean sulfide ore, free from fines, and the use of quartz high in silica as a flux. In 1919, the quality of the flux was improved and its effect on the metallurgy was very marked. To improve the practice further, it was necessary to work out some method of treatment for the sulfide fines and the siliceous and refractory ores, other than in the blast furnace. A series of milling tests indicated that these products could be successfully treated by differential flotation, and in 1922 plans were made and a flotation plant built. It was estimated that the flotation plant would deliver to the smelter 40 to 50 tons of concentrates per day; the problem was what to do with these concentrates. It was out of the question to attempt to smelt them in a blast furnace because of the dust losses and, because our practice demands a charge free from fines for satisfactory operation. There is no custom smelter in the vicinity to which concentrates may be sold, pending the time when the tonnage will be sufficient to warrant roasters and a reverbatory furnace. Sintering and nodulizing were investigated but neither method fitted into our scheme of metallurgy. A close study of the converter practice was then made to see if some method could not be evolved to smelt this tonnage of concentrates in a converter without preliminary treatment. At that time, the converter installation consisted of two 12-ft. Great Falls converters, which were handling 12 to 14 per cent. matte. The heat balance of the converters working with 12 to 14 per cent. matte was more than sufficient to smelt the contemplated tonnage of concentrates but the mechanical difficulties. of feeding fines into the Great Falls converter made the use of this type of converter impractical.

Jan 9, 1924

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

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. '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' 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's' 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 S. W. Parr, T. E. Layng

The low-temperature carbonization of coal involves the carrying out of the coking process under conditions wherein neither the coal mass nor any of the passageways through which the volatile products pass are heated above 700" or 800" C. For convenience in this discussion, the single number 750" will be used to designate the maximum range. This temperature is not selected arbitrarily; it is the result of certain natural conditions that are inherent in the substances involved. Two of these conditions arc sufficiently pronounced to suggest a line of demarcation at this point as follows: (1) Below 750°, all the heavy hydrocarbons are expelled, which means that, at these lower temperatures, the illuminants, the gases of high calorific value, and the condensible oils are discharged; above 750") there are given off the lean, non-illuminating gases consisting for the most part of hydrogen and marsh gas and having no condensible constituents present. (2) Below 750") there is substantially no secondary decomposition; above 750") the volatile products are readily decomposed, forming tars, naphthalene, free carbon, etc. It is not intended to maintain that no secondary decompositions occur below 750". Many recent studies have demonstrated the practicability, especially in the presence of catalytic substances, of cracking certain of the hydrocarbon compounds; but at these lower temperatures the step is a moderate one, as, for- example, from xylene to toluene or from toluene to an anthracene. These changes are moderate in amount. Not only do the reactions proceed slowly but they are subjected to the decomposing . conditions for only a short time. This is evident when it is recalled that at these initial temperatures the decomposition of the coal is very rapid and, if anywhere near a neutral pressure is maintained, the movement of the evolved gases is lively and reduces, correspondingly, the time for the retention of the gases in the passageways where these milder decomposing conditions exist. It is acknowledged that the maintenance of these temperature conditions at the present time has only an ideal and not a practical status. Actual operations under these conditions, as a? industrial accomplish-

Jan 1, 1920

By R. L. Jones, H. Conrad

The effects of gain size on the room-temperature tensile properties of commercial(A- 70)-purity and iodide-purity titanium were investigated by concurrent tensile testing and thin-foil electron transmission studies. The mechanical tests showed that the effect of grain size on the yield, flow, and fracture stresses could be expressed by relations of the Hall-Petch type. The magnitude of the grain size effect on the yield stress was larger for commercial-purity than for high-purity titanium, but in both materials it was intermediate between that typically observed for fcc and for bcc metals. The effect of strain on the gain size sensitivity of the flow stress was found to reflect the grain size dependence of strain hardening. The electron transmission study indicated that the tensile behavior could be accounted for in terms of the dislocation densities and distributions formed during deformation. It was concluded that the effect of grain size on strength could be attributed to a relationship between grain size and the dislocation densities generated in initiating and sustaining plastic flow, the difference in stress levels being due to strain hardening. The relationships between recrystallized grain size, uniaxial tensile properties, and dislocation substructure have not been explored in any detail for a titanium. With titanium and its alloys finding increasing applications in aerospace systems, such information has become essential. The research described in this paper had two objectives: first, to document the effect of grain size on the yield, flow, and fracture stresses of unalloyed a titanium by the tensile testing of recrystalliied specimens at room temperature; second, to attempt an interpretation of the mechanical test behavior in terms of the dislocation structures formed on deformation, as observed by transmission electron microscopy of thin foils prepared from deformed tensile specimens. The observations reported here are restricted to room-temperature deformation; the effect of temperature on the yield and flow stresses of a titanium and the athermal nature of the contribution of grain size to the flow stress have been discussed elsewhere.1"3 EXPERIMENTAL DETAILS Two purity grades of unalloyed titanium have been investigated: Crucible Steel A-70, a typical commer- cial-purity product, and a high-purity iodide grade supplied by the Foote Mineral Co. Chemical analyses for interstitial impurity contents are given in Table I, together with values for the total interstitial atom fractions in terms of oxygen equivalents, which were calculated by the method outlined previously.4 ,5 According to the manufacturer's nominal analysis, the A-70 grade also contains about 3700 ppm of Fe. The A-70 grade was supplied as 1/4-in.-diam centerless-ground rod. The iodide grade was supplied as crystal bar which was consolidated to approximately 1/4-in.-diam rod by a single, rapid, molten zone pass, using electron beam heating. The 1/4-in. rods were cold-swaged to 0.078-in.-diam wires and 2-in. lengths were recrystallized in a vacuum of -5 x 10-5 torr, giving grain sizes in the range 0.8 to 30 . The thermal treatments and resulting grain sizes are summarized in Table 11. Since there was in no case any obvious sign of a bimodal dis tribution of grain sizes, the grain size values quoted in Table I1 are those obtained from mean linear intercept measurements involving >I00 grains. For the two coarse grain sizes the measurements were made using conventional optical techniques. It was noted during these determinations that the etchants used (10 pct HF; 30 pct HN03; 60 pct H20 and 2 pct HF; 2 pct H202; 96 pct H20 were both tried) etched grain boundaries very nonuniformly and optical polarization effects had to be employed to reveal boundaries which might otherwise have been missed. It was found that this problem became more acute with the finer grain sizes as the usefulness of polarization diminished.

Jan 1, 1970

By Walter Crafts, D. C. Hilty

The liquidus diagram for the iron field of the Fe-S-O system has been derived experimentally. The solubility of oxygen in molten Fe-S alloys has been measured at several temperatures and found first to decrease slightly and then increase rapidly with increasing sulphur content. IT is well-known that the types, distribution, and amount of inclusions in any given steel are closely allied with the oxygen and sulphur contents of the metal, so that the term "deoxidation" as conventionally applied in steelmaking refers not only to the control of oxygen and oxide inclusions but to collateral modification of sulphide inclusions as well. Inclusions commonly occur in steel as mixtures of oxides and sulphides, sometimes closely associated and sometimes apparently completely divorced. Their effects on the properties of the metal may vary widely depending on their types and distribution as well as on their quantity. The mechanism by which inclusions form, however, and the means for controlling it are exceedingly complex and not well understood. Nevertheless, as described by Benedicts and Lofquist' and by Wentrup' all oxide and sulphide inclusions, excluding mechanically entrained matter, must result from specific modifications of the basic equilibria of the Fe-S-O system. In an investigation of the mechanism of deoxidation and inclusion formation being carried out at the Union Carbide and Carbon Research Laboratories, it became evident that quantitative data for the fundamental Fe-S-O system were essential to a better understanding of the problem. Consequently, the liquidus surface of the portion of the Fe-S-O diagram of interest in steelmaking has been determined, and the solubility of oxygen in liquid iron containing sulphur has been measured. Fe-S-O Diagram The portion of the Fe-S-O diagram of specific interest in steelmaking is the Fe-FeS-FeO corner. Of the contiguous binary diagrams for this partial system, only those for Fe-FeO and Fe-FeS are known with reasonable certainty.3 Several attempts to derive the FeO-FeS diagram have been made, chief among them being the work of Giani as reported by Oberhoffer,4 and, more recently, that of Vogel and Fulling." Although both Giani and Vogel and Fulling published diagrams for the FeO-FeS system, their observations indicated that the oxide component approximated Fe3O4 rather than FeO, so that there is doubt whether the system is truly binary. Benedicts and Lofquist and also Wentrup published qualitative sketches of the ternary diagram based on the assumption that it was of the type described by Marsh for a ternary system in which two of the contiguous binary systems are simple eutectic systems and the third exhibits a solubility gap in the liquid. Apparently, however, the only previous effort to establish the diagram experimentally was that of Vogel and Fülling whose results are reproduced in Fig. 1. Although defining approximately the limits of the miscibility gap and the location of the ternary eutectic, point E in Fig. I, Vogel and Fülling's diagram must be considered only semiquantitative. It was derived from a limited number of observations mainly along two quasi-binary sections, and the directions of the tie-lines and the location of the critical point, K in Fig. 1, were estimated by computation. Experimental Procedure The experimental technique employed for the present investigation involved melting mixtures of ferrous sulphide and ferric oxide in contact with iron. Since it was considered that in this part of the system the vapor pressures of sulphur and SO, are so low that they would not affect the results significantly, the melting was carried out in a current of argon to sweep out products of any initial re-

Jan 1, 1953

By G. Wakefield, A. H. Daane, D. H. Dennison, F. H. Spedding

Preparation of pure scandium metal was accomplished by calcium reduction of the fluoride by two methods; a low-temperatzdre alloy process and direct reduction with subsequent distillation of the product. The following properties were determined: melting point: 1181OK; boiling point (calculated): 3000°K; lattice constants at 298°K (hexagonal lattice): a = 3.308 * 0.001 A, c = 5.267 * 0.003A; calculated density at 298°K, g per cm3: 2,990 + 0.007; electrical resistivity, ohm-cm: 299°K, 66.6 ± 0.2 x 10 -6; 373oK, 77.4 * 0.2 x 10 -6; thermal coefficient at 299°K, ohm-cm per deg: 5.4 X x; heat of sublimation at 298°K, kcal pel- mole: 80.79. The vapor pressure was determined as a function of temperature between 1505o and 1748°K, with the data fitted to a straight line shielding the equation: Log Pmm = -1.718 X 104/ToK + 8.298. SCANDIUM, element number 21, was first discovered by Nilson in 1879 and was recognized as the Ekaboron as predicted by Mendeleff. As it is in group III of the periodic table, the general properties are a little like aluminum and also resemble quite closely the properties of yttrium and the rare-earth metals, in both the metallic and ionic form. Although the earth's crust contains approximately 5 ppm of scandium (the element is as abundant as arsenic and twice as abundant as boron) it generally occurs so widely distributed that it has earned the reputation of being very rare. The one exception to this is the mineral thortveitite, which has been found in Madagascar (20 pct Sc2O3) and in Norway (35 pct Sc2O3). Scandium also occurs in small but distinct amounts in uranium and rare-earth ores; the recent larger scale processing of these materials has made some scandium available from these sources. As with other naturally-occurring monoisotopic elements (except Be), scandium contains an odd number of protons and an even number of neutrons. Scandium metal was first prepared by Fischer and coworkers1 in 1937 by electrolysis of scandium chloride in a molten eutectic mixture of lithium and potassium chlorides, using molten zinc as a cathode and collector of the scandium metal produced. The zinc was removed from the Zn-2 pct Sc alloy by vacuum distillation, leaving a product reported to be 94 to 98 pct Sc, with the main impurities being iron and silicon. They reported a melting point of 1400° C for this material. Scandium has also been prepared by the reduction of scandium chloride with potassium metal in a glass apparatus by Bommer and Hohmann in 1941,' resulting in a mixture of metal and potassium chloride; these workers did not isolate the metal proper, but the X-ray diffraction of the slag-metal mixture showed it to be hexagonal with a = 3.30A, c = 5.45A. petru3, 4 and coworkers have recently reported the preparation of the metal in a compact form by the reduction of either ScF3 or ScC13 with calcium metal and subsequent distillation of the product. This process probably yielded a metal of high purity, but they list no chemical analysis nor do they list any of the properties of their product. Previous related work in this Laboratory has been concerned with the production of yttrium and the rare-earth metals and the determination of their physical properties. Because of its similarity to these metals, scandium is being included in this study. PREPARATION OF SCANDIUM METAL The preparation of yttrium and the rare-earth metals may be accomplished by reduction of their fluorides with calcium metal in tantalum crucibles.5 This process leads to the introduction of tantalum (up to 0.5 pct) as an impurity in the higher melting rare earths, but since the tantalum occurs as dendrites, uncombined with the rare-earth metals, its presence is not objectionable in some cases. The preparation of scandium metal in this manner, however, was found to yield a product containing 2 to 5 pct Ta. To obtain a purer product, the following two methods were developed for the reduction of scandium fluoride with calcium metal: i) a low-temperature process utilizing zinc to form a low

Jan 1, 1961

By G. K. Engelhart

A multi-stage counterflow process developed in Germany preheats dry pulverized portland cement raw materials held in suspension in rotary kiln waste gases. Capacity of the first kiln installed for this purpose in the United States has been increased from 860 to 1500 bbl per day, with fuel reductions from 1,100,000 Btu to 650,000 or 700,000 Btu per bbl. Sixty percent of total waste gas is used. As full use of the gas stream is approached, additional kiln production and fuel economy may be expected. EFFECTIVE use of rotary kiln waste gases to preheat dry pulverized materials has been demonstrated in full-scale operation at the Allentown Portland Cement Co. plant, Evansville, Pa. Pulverized raw materials are preheated in suspension in the gas stream in a multi-stage counterflow process which draws the gases through a series of cyclone collectors. Upon entering the first cyclone stage the material, continuously delivered and suspended in the gas stream, is successively collected and re-suspended until it discharges through the kiln feed pipe. Gas and material contact time is thus prolonged, providing a high degree of heat recuperation with a very low temperature differential between gas and material at the final stage. The suspension preheater, developed by Klock-ner-Humboldt-Deutz AG of Cologne, Germany, was first installed at the Norddeutsche Huette plant, Oslebshausen, Germany. Similar preheaters are now in operation at three other German cement plants. The first American installation, at the Allentown Portland Cement Co. plant, was designed and manufactured by Fuller Co. of Catasauqua, Pa., Humboldt's licensee for the United States, Canada, and Mexico. Design of this installation is essentially the same as the German original, but provision was made for varying the method to adapt the process to specific objectives of American portland cement production. Differences between German and American cement clinker production practices are directly related to differences in three primary production cost items: fuel, labor, and power. Because fuel costs are high in Germany and elsewhere in Europe, thermal efficiency has been the first objective of European cement producers and manufacturers of rotary kilns. The Germans have developed such recuperative equipment as the present suspension preheater, the Miag calcinator, and the Lepol kiln, the invention of 0. G. Lellep. In North America labor is the principal cost item, although rising fuel costs are of growing concern. High clinker production is therefore of first importance. Recent installations of longer dry process cement kilns have been disappointing, failing to make satisfactory reductions in exit gas temperatures when production is held at an acceptable level. The Humboldt suspension preheater satisfies both

Jan 1, 1955

By Alec M. Crowell, Thomas D. Bailey

Although natural gas was first discovered in Northwest Arkansas in 1887, . near Fort Smith, Sebastian County, the literature contains very little information on the region, which is separated distinctly from the oil area of Southern Arkansas. For that reason this brief and concise report is a summary of developments from discovery to the present time. Northwest Arkansas produced 5,736,-ooo,ooo cu. ft. of natural gas during 1942, the trend of production having been generally upward over the past five years, as is shown in Fig. I. Since 1904 a reserve of 237 billion cubic feet of natural gas has been discovered in Northwest Arkansas, of which approximately 162 billion cubic feet have been expended, leaving a reserve of approximately 75 billion cubic feet available as of Jan. 1, 1943. A prolific new field discovered in Pope County Oct. 23, 1942, will add to the reserve of the region materially. Per well reserves, over-all, are unusually high because of the practice of multiple completion. As yet no commercial deposits of oil have been discovered in Northwest Arkansas. but the gas deposits have proved of immense value industrially, principally in the processing of zinc ore mined in the local area as well as that imported from distant states. With the war, new interest in the exploitation of the metallic ores of the region lends new significance to the gas reserves tabulated herein. Geological Discussion The region covered in this report comprises the Arkansas Valley from Pope County weslward to the Arkansas-Oklahoma state line as shown in Fig. 2. This valley is a westward trending structural trough with sharp-topped ridges and mesa-like mountains rising above the valley's undulating surface. It is bounded on the north by the Ozark Highlands and on the south by the Ouachita Mountains. The sedimentary beds of the Arkansas Valley are composed mainly of noniossil-iferous shales and sandstones. The rocks contain a high content of carbonaceous material and many coal beds are found in the region. The Gxed carbon ratios (ratio of fixed carbon to volatile combustible matter of surface coals) are very high and average about 80 per cent over the region covered in this report. Little or no calcareous material is present. Rocks of the Arkansas Valley are sharply folded, and igneous intrusive rocks cut the sedimentary beds at a few places. The Arkansas Geological Survey' made a detailed reconnaissance survey of the Arkansas Valley province in 1927, the purpose being to delineate the major structural features (Fig. 3) and to point out the possibilities of discovering addi. tional gas deposits. More than fifty anticlines were mapped as a result of this survey. The information gained by this

Jan 1, 1943

By Thomas D. Bailey, Alec M. Crowell

Although natural gas was first discovered in Northwest Arkansas in 1887, . near Fort Smith, Sebastian County, the literature contains very little information on the region, which is separated distinctly from the oil area of Southern Arkansas. For that reason this brief and concise report is a summary of developments from discovery to the present time. Northwest Arkansas produced 5,736,-ooo,ooo cu. ft. of natural gas during 1942, the trend of production having been generally upward over the past five years, as is shown in Fig. I. Since 1904 a reserve of 237 billion cubic feet of natural gas has been discovered in Northwest Arkansas, of which approximately 162 billion cubic feet have been expended, leaving a reserve of approximately 75 billion cubic feet available as of Jan. 1, 1943. A prolific new field discovered in Pope County Oct. 23, 1942, will add to the reserve of the region materially. Per well reserves, over-all, are unusually high because of the practice of multiple completion. As yet no commercial deposits of oil have been discovered in Northwest Arkansas. but the gas deposits have proved of immense value industrially, principally in the processing of zinc ore mined in the local area as well as that imported from distant states. With the war, new interest in the exploitation of the metallic ores of the region lends new significance to the gas reserves tabulated herein. Geological Discussion The region covered in this report comprises the Arkansas Valley from Pope County weslward to the Arkansas-Oklahoma state line as shown in Fig. 2. This valley is a westward trending structural trough with sharp-topped ridges and mesa-like mountains rising above the valley's undulating surface. It is bounded on the north by the Ozark Highlands and on the south by the Ouachita Mountains. The sedimentary beds of the Arkansas Valley are composed mainly of noniossil-iferous shales and sandstones. The rocks contain a high content of carbonaceous material and many coal beds are found in the region. The Gxed carbon ratios (ratio of fixed carbon to volatile combustible matter of surface coals) are very high and average about 80 per cent over the region covered in this report. Little or no calcareous material is present. Rocks of the Arkansas Valley are sharply folded, and igneous intrusive rocks cut the sedimentary beds at a few places. The Arkansas Geological Survey' made a detailed reconnaissance survey of the Arkansas Valley province in 1927, the purpose being to delineate the major structural features (Fig. 3) and to point out the possibilities of discovering addi. tional gas deposits. More than fifty anticlines were mapped as a result of this survey. The information gained by this

Jan 1, 1943

By D. T. Goettge, E. L. Robinson

The phase changes occurring in low carbon steel during hot strip mill rolling are shown to be metallurgically significant when related to commonly used temperature control points, particularly finishing and coiling temperatures. In combination, these temperatures are shown to have an important influence on the level and uniformity of hardness, grain size, and carbide characteristics of the finished hot and cold rolled sheets. PRODUCTION of wide flat-rolled products ordinarily requires a number of operations in sequence to prepare the material for shipment to the customer. Most products are tailor-made for specific end uses, with each operation contributing certain properties to the finished material. Since the characteristics imparted to the semifinished product by a given step in processing carry through to the finished product in varying degrees, it is important that the intermediate stages of production of flat-rolled strip be carried out with the same care which characterizes the last or finishing operations. The step of hot strip mill rolling is common to the production of all of the various types of flat-rolled product; therefore, the hot strip rolling is an especially important point at which to recognize and control those variables which have an effect on the surface characteristics and metallurgical properties of the finished product and which influence the ease of conducting subsequent operations. Orders entered at a producing mill usually show an end use or describe an article or part into which the ordered product is to be fabricated. Applying his experience as to the properties necessary in a finished sheet to suit the end use and to perform successfully in the fabrication involved, the metallurgist selects a steel of suitable composition and deoxidation practice, and slabs of appropriate dimensions are produced for rolling on the hot strip mill. At this stage of processing, the metallurgist faces the problem of controlling hot strip mill practice in the light of his diagnosis of the properties necessary to meet the end use, paying due attention to the accompanying problem of producing a strip which can meet processing requirements on subsequent units in the mill. It is the purpose of this paper to describe some of the factors which he must consider in solving these problems and to indicate some of the principles which guide him. Equipment, Physical Requirements of the Strip, and Temperature Measurement The metallurgist must, of course, be familiar with the physical layout of the mill, the temperature-measuring equipment available, and the physical requirements of the hot strip product before he can apply his metallurgical knowledge to the problem; hence, the first section will consist of a brief discussion of these matters. The usual hot strip mill consists of reheating furnaces, five or six roughing stands including a scale-breaker, holding table, and second scalebreaker, six-stand finishing mill, runout table with spray cooling facilities, and coilers. A schematic diagram of a typical layout is shown in Fig. 1. Slab temperatures are primarily a function of heating time and furnace temperatures, while mill speeds, spray practice, drafting practice, available water pressure, temperature of the cooling water, cross sectional dimensions of the strip, coil size, and equipment limitations, either singly or in combination, determine what rolling temperatures are practical on a given hot strip mill unit. Thus, it is possible that a set of temperatures which can be utilized successfully on one mill cannot be used on another. However, adjustments in temperatures and rolling practice can usually be made to develop the desired metallurgical properties. In addition to the metallurgical properties developed through proper temperature control, the hot strip mill must also provide strip with certain physical attributes which may be summarized as follows: Strip Cross Section—The strip contour should conform to a section which will give the best results in the cold reduction operation. This is generally recognized as a strip with 0.001 to 0.003 in. crown or shoulder-to-shoulder convexity depending on width, and freedom from concave, flat, or wedge-shaped cross sections which cause metal buildup in cold reduction. Excessive drop off in thickness at the edges can also be very detrimental in cold reducing to light gages. Gage, Width, and Camber—All of these must be controlled. For example, rundown or increasing thickness from the front to the back of the coil results in nonuniformity in the thickness of hot-rolled sheet product and in added difficulty with gage and welds in cold reduction. Similarly, excessive width variation is the cause of guide trouble and excessive edge scrap at later stages of processing, while excessive camber is the source of a variety of processing troubles. Type of Oxide—Product intended for pickling should have a predominance of the type of oxide most easily removable in sulfuric acid. It is generally recognized that this type is obtained by use of maximum table cooling water and cold coiling

Jan 1, 1957

By L. D. Keller

The application of hydraulic concentration to large scale operations has been effectively accomplished by the use of the SiphonSizer. Operation has been simple, automatic and essentially trouble free. The use of the primary desliming SiphonSizer on magnetic taconites has shown an improvement in grade of concentrate and an increase in recovery over conventional hydroseparators. Magnetic concentrates have been further deslimed and upgraded in SiphonSizers by floating a coarse middling product away from the heavier concentrate. The application of the Siphon-sizer to closed circuit grinding has met with only partial success to date. Hydraulic concentration of minerals has been practiced for a good many years. Until recently, however, the practice has been limited to equipment using a multiplicity of small pockets and relatively low tonnages and flows. The adaptation of the SiphonSizer to the concentration and classification of magnetite has changed this concept. Some fifty commercial units varying in size from a 16-ft diam circular unit to a 25x100-ft rectangular unit are currently in operation on magnetic taconites. Additional units up to 38 ft diam are under construction. Depending upon the application in the flowsheet, upgrading varies from 0.75% to 14% Fe in a single stage. To those not familiar with taconite processing, the importance of the struggle to remove economically as much silica as possible may not be fully appreciated. Perhaps some figures pertaining to transportation costs will underscore this important process. If the silica content of the concentrate from a 10,000,000 ton per year plant could be reduced by I%, a savings in boat freight, at $2.00 per ton, would amount to $200,000 annually! THE SlPHONSlZER The SiphonSizer, as illustrated in Figs. lA, 1B and 2, is a hydraulic classifier in which the hydraulic water is distributed uniformly across the bottom of the vessel by means of a system of headers (1 and 2), jet pipes (3), and nozzles (4). The depth of the teeter bed is automatically maintained by the siphon-float assembly. The feed is introduced through a feed well (5) and separated into two fractions by the effects of rising water and the density of the teetered bed. The magnetite fraction is discharged by the siphon (12) while the fine slime and light middling overflow a peripheral weir (9) to the overflow launder (6). The bed depth is controlled automatically by float valves (7), which are responsive to changes in the height of clear water supported in the superelevation tubes (8) by the density of the teetered bed. On top of the float (7) is a needle valve (10) which permits

Jan 1, 1963