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By Thomas P. Meloy

Floating "fines" differs from floating "sands" because the fines have a much larger surface area compared to their mass. The forces that arise from this large specific surface the key to understanding the behavior and treatment of fine particles. Though the nature of these forces is not thoroughly understood, enough work has been done to give a qualitative picture of what is happening in a flotation cell. It is the purpose of this chapter to re-examine some of the more, recent theoretical work and-to indicate its importance.

Jan 1, 1962

By D. Weinstein

Yieldilzg in annealed arc-cast molybdenunz in torsion was studied as a function of strain rate and tem-perature. The temperature dependence of the yield point for different strain rates was used to calculate a heat of activation for the yield point. The heat of activation was not a constant but was approximately a linear function of the stress at yield. It is proposed that the rate effect in yielding is determined in part by a site place-change of C (or other interstitial atom) in the metal. THE low-temperature embrittlement phenomenon in metals and alloys has been known to exist for a long time. Although a transition from ductile to brit-tle behavior has been observed in some close-packed hexagonal metals1 and a face-centered cubic alloy, the most common class of metals exhibiting this be-havior has a body-centered cubic lattice structure. For example, a ductile to brittle transition has been observed in iron,3 molybdenum,4 chromium,5 colum-bium,6 and tungsten.7 In the present investigation, molybdenum specimens were tested in torsion over a wide range of temperatures at three widely separated strain rates, and the temperature for onset of embrittlement was determined. Characteristic of body-centered cubic metals and closely associated with plastic deformation is the appearance of a sharp upper and lower yield point. Theoretical explanation of the yield point in iron and low-carbon steel is due to Cottrell,8 who attributes the phenomenon to the pinning of dislocations by the formation of impurity atmospheres around the dislocations. These atmospheres tend to lock the dislocations and make them more difficult to move. The stress required to move a dislocation and thereby cause plastic deformation is greatly increased, and thus an upper yield point is observed. In addition, theoretical analysis,9 as well as experimental observations, show that the upper yield point is strongly a function of temperature. The upper yield point is observed to decrease with an increase in testing temperature, and above a certain temperature (-700° K in iron) it no longer appears. This is consistent with the concept that thermal vibrations will help free a dislocation from its atmosphere, so that the external stress required to free a dislocation from its pinning atmosphere decreases with increasing temperature. Furthermore, with increasing temperature the equilibrium concentration of impurity atoms around a dislocation decreases exponentially with the result that the dislocation is less firmly pinned. In Cottrell's theory of yield point a static model is visualized in which the pinning atmospheres, particularly interstitial atoms, are immobile, and the dislocations are anchored to stationary positions in the lattice. However, experiments1,7 show the upper yield point to be time-dependent or a function of the rate of straining, a high strain rate causing a high upper yield point. Present theory does not adequately account for the rate dependence of the yield point, and the exact function of the interstitial atom is not under stood. Nevertheless, observation of the temperature dependence and rate dependence strongly suggests that the upper yield point phenomenon is due to the interaction between dislocations and pinning atoms, and that a diffusion mechanism is important in determining the yield point.

Jan 1, 1962

By L. A. Roe

The year 1867 marks the first year of commercial production of phosphate rock in the United States. South Carolina produced almost all of the domestic output of mineral phosphate until phosphate mining began in Florida in 1888. During the period 1868 to 1949 the total marketed production of domestic phosphate rock was about 186 million long tons of which 71.5 percent was produced in Florida, 18 percent in Tennessee and 7 percent in South Carolina (1). From 1949 through 1960, Florida phosphate rock production has ranged Prom 71 to 77 percent of the total domestic production. Since three-fourths of the domestic phosphate production is from the Florida field, and since most of the phosphate from the Tennessee and Western fields is not processed, but used directly as electric furnace burden, this paper will concern itself almost entirely with water requirements for mining and processing ore from Florida. Figure 1 summarizes phosphate rock production for Florida vs. total United States production over the period 1947-1960.

Jan 1, 1962

By D. W. Bridges

Solvent extraction has become important in recent years as a unit process in extractive metallurgy. The flexibility and simplicity of the technique have attracted widespread attention, and numerous papers describing actual and projected metallurgical applications have been published. However, differences in terminology, procedure, objectives, and standards, as reflected in reports by different operators and investigators, have sometimes made appraisals and comparisons difficult. Consequently, a need appeared for n series of basic reports on the subject. This Bureau of Mines Information Circular is the first of such a series. It deals with the status of solvent extraction in metallurgy, as well as with the rudiments and terminology of the unit operation. In analytical chemistry, extraction of molecular species from aqueous media by immiscible organic solvents has been used for many years to separate and determine chemical elements (61).4 Complex chlorides of iron and other metals are readily soluble in ethers and ketones, as are the nitrates of uranium and thorium. Most metals are extractable as complex salts of some organic reagent, such as dithizone, 8-hydroxyquinoline, or cupferron.

Jan 1, 1962

By John Chipman

HE lecture on 'Thermodynamic Properties of Blast Furnace Slagso prepared in 1959 and published two years later required revision in one particular before it appeared in print. The activity of SiO, was deter mined through studies of the equilibrium: SiO, (in slag) 2C (graphite) = (in Fe) 2C0 (1 atm) The ratio for each experimental temperature was found from the heat of formation of cris-tobalite, the entropies and heat capacities of the re-actants, by virtue of the third law of thermodynamics. Discrepancies between several kinds of data led to investigations regarding other equilibria involving SiO, on the suspicion that there might be an error in the third-law value of its free energy. In particular the equilibrium: was restudied by Kay and Taylor who Confirmed the earlier results of Baird and Tayloron which their SiO, activities depended. The free energy of Sic was also rechecked4 independently. These and other equilibrium measurements led to the conclusion6 that the free energy of SiO, at high temperatures is in error and requires a correction of about -5 kcal. The exact source of the error is uncertain; it could lie either in the entropy of SiO, or in its heat of formation, but it more probably lies in the latter. Adjustment of this free energy lowers the ratio by a factor of approximately 4. Accordingly it will be necessary to multiply by this factor all of the SiO, activities determined by this method.',B Referring to the lecture cited, this correction should be applied in Figs. 8, 9, 10, 19, and 20. It applies also to the experimental data of Fig. 13, bringing these as well as those on the ternary system into good agreement with the work of Taylor and associates. At the same time it eliminates the discrepancy shown in Fig. 11, lowering both lines until the upper

Jan 1, 1962

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry's law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry's law is obeyed, one canthen use the Van't Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors' Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott's results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By F. X. Tartaron

The comparison of actual energy of comminution with theoretical surface energy presents a wide gap. On the other hand, Solid State Theory presents a viewpoint that places actual energy of breakage in understandable relationship with the theoretical strength of materials. Therefore the physical background of comminution theory favors Kick's Law. A11 discussions of comminution theory appear farfetched when comparison is made of the actual energy of crushing with the energy input called for by thermodynamic theory. Quoting Taggart:' "The work required to crush halite was of the general order of 0.10 kg cm per sq cm of new surface produced (based on air percolation) whereas the theoretical energy of this new surface, based on thermodynamic calculation by a number of investigators is 1 x 10'4 kg cm per sq cm or the work expended was 1000 times the new surface energy — an indicated crushing efficiency of 0.10 pct." It is frustrating to probe into comminution theory with the prospect that the energy one is measuring is 99.9 pct waste energy. Do the laws of comminution deal with energy consumed by mineral breakage or with waste heat energy? There seems to be something wrong. Solid State Theory may provide the answer. The following statement is particularly apt to the situation: "The fundamental fact about metals and indeed all materials, is that they are much weaker than they should be. By this, we mean that if the stress required to cause a given plane of atoms to slip past a neighboring plane is calculated from basic atomic and Solid State Theory, the resulting number is some 1000 times too large to be accounted for by errors in approximations or assumptions. We know now that this is due to dislocations, and we even have a fair understanding of the details of the process by which dislocations make a crystal weak. An intriguing possibility which suggests itself, results from the discovery of very minute metallic crystals which are apparently free of dislocations and which have a strength approaching the ideal value for a perfect crystal." Here we have an extraordinary reversal of the situation. The actual energy for breakage is only one-thousandth the theoretical instead of 1000 times as given by Taggart. But the theoretical energy presented by Solid State Theory is the binding energy between atoms (or ions) in a crystal lattice. This is the kind of energy envisaged by Kick's law. The surface energy or the other hand corresponds to Rittinger's law. Comparison of theoretical with actual, on the basis of surface or on the basis of Rittinger's law, seems to present an absurdity; yet Rittinger's law is confirmed by an impressive array of experimental evidence. Comparison of theoretical and actual on the basis of Solid State Theory or, in other words, on the basis of Kick's law seems reasonable; yet there is not a scrap of evidence to verify Kick's law. The situation appears paradoxical, but the developments in the next section of this paper show that the paradox is a hint to a strange turn of events. ENERGY-WEIGHT FRACTION FUNCTION charles3 has presented a final equation showing the relation of energy consumed in comminution to size of product n{-1) a-n + 1 E is energy, C is proportionality constant, a and n are constants and k is the coarsest size in the ground product (size modulus). In the course of study of a large amount of experimental evidence, Charles discovered that in the general case, a-n + 1 approximated zero. For some reason, a and n differed only by unity. But if a—n + 1 = 0 within experimental error, then it is obvious that Eq. 1 states that it requires an infinite amount of energy to grind any sample to any size. This is a case where nature gives an absurd answer to a man-made mathematical equation, hence something is wrong with the equation. An adjustment must be made to fit the equation with experience. TO reveal the nature of the adjustment, the differential equation preceding the second integration in Charles' group of equations is given When Charles integrated the quantity xa-n it was almost impossible for him to realize that he was dealing with a special case of integration and that

Jan 1, 1962

By W. H. Class

The embrittling effects of oxygen, ozone, nitrogen, air, and surface residues, on NaCl has been investigated. The embrittlement by ozone and oxygen was found to be associated with the formation of a NaClO3 surface compound. In these cases the initial crack that was responsible for fracture (in a bend test) always nucleated at the corners between the tension and side faces. The behavior of air was very erratic and on certain days did not produce enzbrittlement. During these periods, crystals that had become embrittled by the ozone treatment completely recovered their ductility after a short exposure to the ambient atmosphere, It was established many years ago1 that considerable ductility could be obtained in NaCl single-crystal specimens if the crystal surfaces were dissolved in water either during or immediately prior to the test. The original interpretation of this effect by Joffe attributed the enhanced ductility to the removal of surface microcracks by dissolution. Later investigations2'3 have suggested that the exclusion of air from the specimen surface is the criterion for extensive plastic flow prior to fracture. The air em-brittlement in this later work was attributed to the diffusion of gaseous atoms into the surface layers of the crystal, thereby impeding the movement of dislocations. This model satisfactorily accounts for the reembrittlement observed after further air exposure subsequent to the water dissolution treatment. However, the situation has recently become more complex by the observations in several laboratories4-t that under certain conditions air exposure does not impair the ductility of NaC1. It has also been recognized5 that improper drying operations after water dissolution can leave surface precipitates that lead to embrittlement. Cleavage defects on as-cleaved crystals can often be another source of embrittlement. In the present work the effect of the gaseous atmospheres nitrogen, argon, air, oxygen, and ozone, on the ductility of rock salt was studied extensively. The embrittlement resulting from oxygen and ozone exposures was found to be associated with the formation of a NaC1O3 surface film. It is suggested that certain atmospheres, one of which often can be ambient air, which inhibit the formation or favor the decomposition of this compound, can promote ductility. Thus one aspect of the Joffe effect is certainly related to the removal of surface compounds or complexes by water dissolution. The effect of surface precipitates that remain after drying operations and of cleavage defects were also studied. In neither of the latter cases was the embrittlement as severe as that found with a NaClO3 surface layer. PROCEDURE AND SPECIMEN PREPARATION The nature of the embrittlement produced by the agents mentioned above was studied by means of microscopy, mechanical testing, and X-ray diffraction. Specimens were cleaved from large crystals of optical quality sodium chloride obtained from the Harshaw Chemical Co., and, except for those tested in the as-cleaved condition, were given a 15- to 20-sec immersion in distilled water followed by a rinse in absolute methyl alcohol. The specimens were then blotted on a soft, absorbent paper, and dried by a few seconds exposure to a stream of warm, dry air. Such a procedure was found to give a control surface which was microscopically free of residues. (A few crystals were intentionally painted with a concentrated NaCl solution in order to investigate the effect of surface residues). All specimens were of 0.140 sq in. cross-section. Crystals prepared in the above manner were immediately placed in a gas train where they could be exposed to the desired gases for preselected periods of time. For the oxygen and nitrogen exposures, pure reagent-grade gases were employed. The ozone was provided in the form of an ozone-oxygen mixture (approximately 10 pct ozone) prepared by passing commercial grade oxygen over a strong ultraviolet light source. All gases were dried prior to their introduction into the train. Since argon was found to be completely inert in its behavior (i.e., residue-free specimens that were exposed to argon were not embrittled), it was periodically utilized to check the control specimen surfaces as well as the condition of the gas train used for aging the specimens. After exposure to the gaseous media in question, the crystals to be used for the measurement of the strain to fracture were transferred from the gas train to a protective oil bath (without further exposure to the atmosphere) where the tests were conducted in three-point bending. The apparatus was so adjusted that the load could be applied at a constant, continuous rate. Other Snecimens from the gas train were deformed

Jan 1, 1962

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,' it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.' An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100'~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962

By W. M. Merritts

A joint investigation by the Bureau of Mines and the Christopher Coal Co. at the Humphrey No. 7 mine, operating in the Pittsburgh coalbed in northern West Virginia, was undertaken to gain more insight concerning the hazardous emission of methane gas in mining, This report describes the equipment, procedure, and results. Horizontal bleeder holes drilled in the faces drained large quantities of methane, eliminating downtime of mining equipment. Also, larger quantities of methane were removed by forcing 14 to 25 g.p.m. water at 25 to 200 p.s.i. 5 pressure into the bleeder holes, In one infusion test a fluorescein dye was added to the infusion water; in later mining operations, the infusion water was traced for a distance of 1,500 feet. With vacuum pump applied to the horizontal hole the gas-flow rate increased, and the methane content decreased.

Jan 1, 1962

By Lindsay D. Norman

Eleven major pyrometallurgical processes and operations suggested for recovering manganese from domestic resources are described. These include seven pyrometallurgical processes that usually yield a ferroalloy or a product from which ferromanganese can be produced in one operation. The remaining four involve pyrometallurgical operations whose products require either an additional two-stage process to produce ferromanganese or chemical processing to recover a high-quality manganese oxide product.

Jan 1, 1962

By W. M. Houston

Pebble phosphate deposits of Florida have been established from south of Hardee County to north of the Georgia state line or a distance of over 200 miles and mining has been carried out in an ever-increasing scale since 1885. Deposits that can be mined on the economical standards of today, however, are confined in a roughly circular area about 30 miles in diameter, generally within Polk and Hillsborough Counties, in the central part of the State. The phosphate deposit, which is in the Bone Valley formation of the Pliocene age, is covered by Pleistocene terrace deposits of unconsolidated quartz sand. The matrix is composed of approximately 1/3 clay slimes, 1/3 silica sand and 1/3 phosphate pebbles. The phosphate occurs usually as rounded pebbles, ranging in size from about 1 inch down to approximately 400 mesh. The phosphate may vary from well- defined hard pebbles to soft weathered rock. The color and character of the phosphate will range from smooth buff pebbles to black and white or "salt and pepper rock." The screen size distribution varies considerably between locations and the recoverable phosphate varies may extend down to the 400 mesh size in some areas, while in others the phosphate may cut off sharply at about 35 mesh.

Jan 1, 1962

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined in part for the sgstem Gd-Fe. Seven intermetallic compounds have been found at compositions corresponding to the following Gd-Fe ratios; 2:3, 1.2, 1:3, 2:7, 1:4, 1:5, and 2:17. The GdFe, com-pound has a congruent melting point above 18000C, whereas all of the remaining compounds melt incongruently, A eutectic exists at 13 wt pct Fe at a temperature of 860°C. ALTHOUGH an increasing amount of information is becoming available on the metallurgy of pure rare earth metals, relatively few studies have been made on alloy systems of the rare earths with the transition metals; iron, nickel, and cobalt. Even less data are extant on gadolinium alloys although it could be expected that such alloys might possess interesting structural and magnetic properties. In this paper, we report investigation of the gadolinium-iron alloy system. Studies on systems containing nickel and cobalt will be presented in subsequent papers. Previous data on gadolinium-iron compounds have been reported by Endter and Klemm1 and Jep-son and Duwez.2 Both reports agree on the existence of the GdFe2 phase, which crystallizes with the C-15type structure (face-centered cubic). This is in accord with results of the present work. EXPERIMENTAL The gadolinium metal used was prepared by met-allothermic reduction of high purity gadolinium fluoride. A typical analysis of the metal thus produced indicated the principal impurities to be oxygen, 0.24 pct, and tantalum, 0.2 pct. The iron metal used for alloying was a reagent grade material. Alloys were prepared by arc melting mixtures of the respective metals. Appropriate quantities of the two component metals were carefully weighed, blended and compacted. The compacts were then melted in an arc furnace consisting of a water-cooled copper hearth plate and a water-cooled tungsten-tipped counter electrode contained in a brass vacuum chamber. The furnace was evacuated to an absolute pressure of less than 1 with the leak rate established as being less than 20 per min. The furnace was then back-filled to a pressure of 25 mm of Hg, with a 75 pct He-25 pct Ar mixture. Arc melting at 25 v and 300 amp was maintained for about 30 to 60 sec until the entire visible area of the sample became molten, by which time surface tension had drawn the molten metal pool into a large bead. After allowing the furnace to cool, the alloy button was inverted and the melting process repeated. A series of melts was made covering entire composition ranges from 100 pct Gd to 100 pct Fe. All samples were examined metallographically in the as-melted condition. As the phase diagram became rationalized, and differential thermal analysis had given indications of temperature arrests, annealing was carried out in vacuo or in argon. Generally, compositions containing more than about 60 pct Gd were heat treated at 750°C and alloys containing less than this quantity of gadolinium were annealed at 1000°C. Prolonged annealing times were of the order of 100 to 200 hr. Metallographic examination was repeated on the annealed materials. Although little material loss was noted during alloy preparation, chemical analyses were made on all specimens prepared. The following standard, analytical techniques were used. Samples were dissolved in hydrochloric acid; insoluble material was filtered off, ignited and fused with potassium pyro-sulfate. The cold melt was leached with dilute acid and the solution thus obtained added to the main sample solution. Gadolinium was always determined gravimetri-callv as oxide from oxalate ignition. Iron was removed from an aliquot sample by electrolysis on a mercury cathode at approximately six volts. Gadolinium in the iron-free electrolyte was then precipitated as oxalate which was subsequently ignited to oxide. Iron was determined volumetrically in an aliquot solution by reduction with stannous chloride fol-

Jan 1, 1962

By James R. Kerr

Although metallurgical benefits of processing metals in a vacuum or reduced atmosphere have been realized for a hundred years, the problem of creating a vacuum in the range from 10-0 to 10-4 mm. of mercury in a moderately sized furnace chamber has been difficult to solve. The demand for these and lower pressures, with the advent of World War II, for separating the fission-able uranium isotope from its stable twin by the electromagnetic process, gave impetus to developing pumps capable of delivering extremely low pressures. With the release of data by the Atomic Energy Commission on methods of securing high vacuum in large equipment, steel companies took the initiative, and the growth of the vacuum-melting industry was assured. Vacuum-induction melting of steel in the United States began on a small scale in early 1945 and in 10 years grew to 60,000 pounds per month or 720,000 pounds per year. The years following 1954 showed tremendous expansion, culminating in 1958 in a capacity of more than 36 million pounds.

Jan 1, 1962

By R. L. Lincoln

The effects of adding from 1 to 50 atomic percent (a/o) to vanadium were investigated by the Bureau of Mines. Properties studied included as-cast and annealed hardness, microstructure, fabricability at room temperature and elevated temperature, tensile strength, electrical resistivity, and oxidation resistance at 625° and 800° 2. Additions of small amounts of hafnium resulted in lessened as-cast hardness, decreased electrical resistivity, impaired roll- ability, increased oxidation resistance, and greater tensile strength. Larger amount of hafnium caused greater as-cast hardness, increased electrical resistivity, further impaired rollability, continued increase in oxidation resistance, and lessened tensile strength. INTRODUCTION The purpose of this study was to determine the effect of hafnium additions on the properties of vanadium and to learn if this binary alloy had any special or unusual properties. This investigation is a part of a larger research project in which new and expanded uses of vanadium are being sought. Domes tic vanadium is found frequently in combination with uranium, and because of the demand for uranium as a nuclear fuel, there now exists a surplus of vanadium-bearing minerals and vanadium pentoxide as a byproduct of uranium production. Primary principles of conservation demand that greater use be made of this readily available surplus; finding suitable metals to alloy with vanadium to enhance its properties is one way to increase its utilization. This report is the result of an investigation of the effects on the properties of vanadium when hafnium is added in amounts from 1 to 50 a/o.

Jan 1, 1962

By Alla D. Mah

The need for more and better basic thermodynamic data for the oxides of many of the rare metals is evident to anyone who attempts thermodynamic calculations involving these substances. In continuation of a Bureau of Mines program to meet this need, this paper reports new experimental values of the heats of formation at 298.15° K. of the hexagonal crystalline variety of germanium dioxide and germanium dioxide glass. The values were obtained by means of combustion calorimetry and sodium hydroxide-solution calorimetry. The calorimetric results also made possible the derivation of values for the heat and entropy of fusion of hexagonal germanium dioxide at its melting point. The newly measured data were combined with previously known entropy and high-temperature heat content values to obtain heats and free energies of formation of germanium dioxide (in the hexagonal crystalline, glassy, and liquid states) over the temperature range from 298.15° to 2,000° K.

Jan 1, 1962

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

By R. C. Bates

Uranium mine workers? daily exposure to radon daughters was estimated by two methods of sampling, detailed and spot-check. Both methods involve time- weighting measured exposure levels to arrive at an average exposure figure. Random sampling, or sampling without regard for the duration of exposure, has proved inadequate for estimating average exposure levels. During the first phase of the study, the breathing zones of eight workmen in three underground uranium mines were sampled for an entire shift; 20 to 36 radon-daughter samples were collected per man-shift, Analysis of these data indicated that a suitably accurate estimate of the full-shift exposure could be made by time weighting a considerable lesser number of representative radon-daughter samples. This analysis led to the spot-check method of estimating full-shift exposures to radon daughters. Additional detailed studies were made in seven mines to Learn more about the full-shift radon-daughter exposures and to test the spot-check method, In all, 617 radon-daughter samples were taken in 10 underground uranium mines during 26 man-shifts, and the spot-check method was tested 35 times.

Jan 1, 1962

By Robert K. Koch

Laboratory-scale studies on defluorination of natural and synthetic fluorspars by pyrohydrolysis at 1,500° C. were made to determine the feasibility of developing a process for producing hydrogen fluoride from siliceous fluorspars. It was found that the reaction (at 1,500° C.) is not promising for process development, even though a silica-free offgas can be generated. The primary difficulty is the low hydrogen fluoride content of the offgases; an HF content of 6 percent was the best achieved. Previous research by the Bureau of Mines has demonstrated that offgases averaging 27 percent hydrogen fluoride can be produced under carefully controlled conditions at 1,280° C. The lower temperature process is a better method for production of HF. However, charges in which the CaF to Si02 mole ratio varied from 0.4 to 2 could be processed with similar results. Also, combined alumina and ferric oxide contents up to 25 mole-percent did not noticeably alter the rate of defluorination. Therefore, virtually any natural siliceous fluorspar would respond in essentially the same manner when exposed to water vapor at 1,500° C.

Jan 1, 1962

By S. J. Aresco

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove grindability index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions 5/ issued by the Bureau of Mines; the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor and, if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous sampling of coal as delivered is a check on the practical results obtained in burning the coal.

Jan 1, 1962