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By B. K. Miller, R. S. Bradley

THE principal producing areas of fire clay in Missouri are: (I) the east central district, which includes Audrain, Callaway, Montgomery, Warren, and Boone Counties [ ] (Fig. I); (2) the St. Louis district, which includes St. Louis and St. Louis County; (3) the north central Ozark district, which includes Franklin, Gasconade, Osage, Maries, Phelps, and Crawford Counties. Most of the semiplastic[$] fire clay is found in Audrain, Callaway, Montgomery and St. Louis Counties, and in St. Louis. Flint fire clay is found in Callaway, Audrain, and Montgomery Counties and in most of the north central Ozark district. High-alumina diaspore clay is found only in the north central Ozark district, except a few deposits found in Montgomery County. This paper is concerned with the semiplastic fire clay that occurs in the east central Missouri district near Mexico, Audrain County, Missouri, which is mined by the open-pit method as practiced by the A. P. Green Fire Brick Co. About one-fourth of the semiplastic fire clay in that district is mined in shaft mines, and three-fourths in open pits.

Jan 1, 1941

By W. E. Horst

Flotation feed was hell constant for batch laboratory tests and continuous pilot and commercial plant tests on a spodumene ore to determine the relation.ship between flotation behavior and the size and type of flotation machine. Results. showed that additional retention time would be needed in the plant flotation circuit to duplicate laboratory or pilot plant performance when operating Dariables of the. plant flotation machines remained unchanged. During the past few years of operation at Kings Mountain, N. C., full-scale flotation has generally yielded poorer metallurgical results than those obtained in the laboratory or pilot plant. After 2 min in each size of Denver flotation machine in the spodumene rougher circuit, pilot recovery (41.7 pct) was almost three times that of the plant (13.6 pct) and about twice that of the laboratory (21.0 pct). Pilot and commercial plant data are based on continuous operation, and laboratory results on batch testing of rougher performance. The ore is a pegmatite containing spodumene, feldspar, quartz, mica, and amphibolite. Data were accumulated to evaluate the scale-up relationships between laboratory, pilot plant, and plant flotation cells. Flotation rate constants and dimensional analysis were used to define the relationship existing between flotation behavior and scale of operation. Measuring Flotation Rates: Efficiency of the rougher stage was measured by flotation rate, defined as the recovery that can be attained within a given time." • The problem of measuring flotation rates has been studied by many investigators, whose methods have varied. Published studies an flotation kinetics have been summarized recently by Gaudin.l When comparing flotation rates, it is more satisfactory to compare straight line relationships between recovery and flotation time than exponential curves resulting from plotting cumulative recovery vs cumulative flotation time. To convert the exponential curves into straight line relationships, rate equations were applied similar to those used in chemical kinetics to study the velocity of chemical reactions. Two rate equations have been used in this investigation to measure efficiency of the various cells: 1.5 order Rate Equation dR/dt=k (A-R)1.0 [Eq.1] Second Order Rate Equation dR ---- - K(A - R)2 [Eq. 2] dt Upon integration Eq. 1 becomes 1/(A-R)1/2=k/2 t+1/A1/2 [Eq. 3] and Eq 2 becomes: or fEq. 4] t/R=1/A2K+t/A [Eq. 4] where R = cumulative recovery [percent recovery of total value (spodumene) in flotation feed]. A = initial concentration, pct (100 pct of mineral to be separated). t = flotation time (minutes). k = flotation rate constant for 1.5 order rate equation [units: 1/(percent) 0.5 (min)1. K = flotation rate constant for second order rate equation [units: 1/(percent) (min) 1.

Jan 1, 1959

By CHARLES SIMENSTAD

COAL preparation, or coal washing, is not a new subject to the Pacific Northwest. Most of the coals mined in this state smaller than lump, and nearly all such sizes mined on the Pacific slope of the Cascade mountains, require washing before marketing. A large proportion is being put through some washing process, but coal washing in this state, has not reached the efficiency it is practicable to obtain. In fields where the coal, as mined, contains less impurities, where working conditions make it practicable to eliminate some of these impurities under- ground, or where a large proportion of the run-of-mine coal is lump, coal preparation does not present the problem it does in our local field. Here the coal is associated with considerable impurities and the slack, or steam sizes, aggregate about 80 per cent. of the output. Therefore, approximately 80 per cent. of the coal mined must be washed to become a valuable fuel. Washing then becomes a major operation, as hand picking of the 20 per cent. of lump is a standard and comparatively simple operation. Some coal beds here are so interstratified with bone, of a more or less massive nature, that hand picking of lump is not economically efficient. In such cases the coal must be crushed fine enough for it to be freed from the bone, so that the two may be separated. Coal cleaning in this field, therefore, must receive skilled attention to purify this fuel and raise its stand- ard. Without greater efficiency in cleaning, the importation of coal from outside the state will be even greater than in the past.

Jan 1, 1926

By G. B. Craig, G. L. Montgomery

A simple technique has been developed which reveals glide dislocations in zone-refined aluminum as etch pits. The technique has been tested quantitatively by making dislocation counts on aluminum single crystals deformed in pure bending. The method has the advantage of being insensitive to the orientation of the surface under examination. A number of etchants which will reveal dislocations in annealed aluminum have been reported.'-' These etchants apparently depend on decoration of the dislocations by an impurity (probably iron) and cannot, therefore, be used to reveal fresh glide dislocations. In addition, it is unlikely that screw dislocations will be etched because of their small attraction for impurity atoms. Amelinckx6 has reported that glide dislocations located along slip traces can be revealed by fluo-rated aqua regia. This work indicated that dislocations themselves, irrespective of decoration by impurity atoms, are responsible for the etch pits. However, as a result of additional etching experiments, Wyon and Marchin7 concluded that dislocations alone are not sufficient to explain the localization of etch pits on slip lines in aluminum using chemical etch-pitting techniques. In addition, their results show that glide dislocations are revealed only on surfaces approximately parallel to a (100) axis and that not all slip systems are attacked. These observations have been confirmed by the present authors. The technique described in this article is insensitive to the orientation of the surface, and reveals dislocations on all glide systems. Fig. 1 shows a deformed region in the neighborhood of a scratch. Dislocations can be seen along three slip traces. In the present work, single crystals of zone-refined aluminum are polished for from 2 to 5 min in a chemical polishing reagent held at 100°C, as described by Herenguel and second:' H2Sol 60 pct H3PO4 30 pct HNO3 10 pet The samples are then coated with a thin oxide film by annealing in air at 450°C for 1 hr and cooling in the furnace. After deformation, dislocation etch pits are developed by immersing the specimen in the same polishing solution which is now held at a temperature of 50°C. The formation of small hydrogen bubbles indicates that etching has occurred. The sample is immediately removed from the solution. Prolonged etching results in enlargement of the pits and, in regions of high dislocation density, the overlapping and loss of resolution of individual pits. It is the experience of the authors that contact with iron will ruinously contaminate the reagent. With careful etching, dislocations separated by half a micron can be resolved optically and the method has been shown to be sufficiently sensitive to reveal dislocations produced during the pre-easy glide region of deformation, Fig. 2. A few examples of glide-dislocation configurations, as revealed by this technique, are shown in Figs. 1 to 4.

Jan 1, 1964

Jan 1, 1893

By Francisco Cadena

The construction of Norris Dam, built by the Tennessee Valley Authority on the Clinch River, a tributary of the Tennessee River, involved the production of coarse and fine aggregate for approximately 1,000,000 cu. yd. of concrete. A hammer-mill plant for the manufacture of sand from quarried rock was indicated as the most economical method of providing this material. The abrasive character of the feed as compared to the average hammer-mill feed made it necessary to control operations rather closely, and this resulted in the accumulation of many data hearing on production and maintenance. This paper will deal only with three specific sets of data, accompanied by such general information as may be necessary to explain the conditions under which they were obtained and followed by discussions on the relation of silica content to hammer wear, comparative costs of slugger and stirrup hammers, and comparative costs of tool-steel and manganese-steel grate bars. Coarse Aggregate Aggregate for the concrete poured at Norris Dam came from a dolomite quarry within 2000 ft. of the west abutment of the dam. Geologically this rock is known as a Knox dolomite. A typical chemical analysis is given in Table 1. Table 1.—Typical Chemical Analysis Per Cent H2O, 110° F............................................. 0.02 lgnition loss.............................................. 43.56 MgO.................................................... 19.19 CaO ................................................... 29.07 Fe²O³.................................................... 0.39 Al2O³ .................................................. 1.94 SiO2..................................................... 5.75 SO2...................................................... Tr. Rock was carried by 12-yd, dump trucks to a 42-in. gyratory crusher set at 6 1/2in. The product of the primary crusher was taken by a belt conveyor to a double.-deck vibrating screen followed by a 5 1/2-ft. cone

Jan 1, 1938

By Francisco Cadena

The construction of Norris Dam, built by the Tennessee Valley Authority on the Clinch River, a tributary of the Tennessee River, involved the production of coarse and fine aggregate for approximately 1,000,000 cu. yd. of concrete. A hammer-mill plant for the manufacture of sand from quarried rock was indicated as the most economical method of providing this material. The abrasive character of the feed as compared to the average hammer-mill feed made it necessary to control operations rather closely, and this resulted in the accumulation of many data hearing on production and maintenance. This paper will deal only with three specific sets of data, accompanied by such general information as may be necessary to explain the conditions under which they were obtained and followed by discussions on the relation of silica content to hammer wear, comparative costs of slugger and stirrup hammers, and comparative costs of tool-steel and manganese-steel grate bars. Coarse Aggregate Aggregate for the concrete poured at Norris Dam came from a dolomite quarry within 2000 ft. of the west abutment of the dam. Geologically this rock is known as a Knox dolomite. A typical chemical analysis is given in Table 1. Table 1.—Typical Chemical Analysis Per Cent H2O, 110° F............................................. 0.02 lgnition loss.............................................. 43.56 MgO.................................................... 19.19 CaO ................................................... 29.07 Fe²O³.................................................... 0.39 Al2O³ .................................................. 1.94 SiO2..................................................... 5.75 SO2...................................................... Tr. Rock was carried by 12-yd, dump trucks to a 42-in. gyratory crusher set at 6 1/2in. The product of the primary crusher was taken by a belt conveyor to a double.-deck vibrating screen followed by a 5 1/2-ft. cone

Jan 1, 1938

By Carls Benedicks

It is well known by every one who has had to deal with boiler tubes that these are often seriously affected by a sort of corrosion, occurring as a local pitting, that frequently causes a perforation of the tube in a rather short time. The characteristic appearance of this corrosion is shown in Fig. 1. A very similar corrosion occurs in condenser tubes (Fig. 2).l A study of the microstructure or local chemical composition of the metal (iron 70:30 brass) fails to reveal any cause for this pitting. Of course one might possibly assume the starting point to be some oxide particle, causing an electrolytic local action, but this in no way explains the continued corrosion, progressing even when the assumed oxide particle must have disappeared. By the excellent work done by the Corrosion Research Committee of the Institute of Metals, and communicated, in October, 1923, to the Institution of Engineers and Shipbuilders in Newcastle-on-tyne, stress was laid on the faot that a content of entangled air has a very obnoxious effect. In the following correspondence, Sir George Goodwin stated that "engineers have, for a long time past, regarded air as the big enemy to be fought against in all questions of corrosion'72 and Kenneth Fraser pointed out that the most vital point is "the avoidance or removal of possibly the chief cause of present day corrosion, i. e. entrapped air and gases brought out of solution."3 In their reply, however, the authors state that they had "never for a moment believed that entangled air was responsible for the beginnings of corrosion, and express the opinion that the gradual liberation of air could not account for localized corro~ion."~ On consulting the many textbooks on corrosion, as that

Jan 1, 1925

By CARLE R. HAYWARDC

BEFORE discussing this subject it is necessary to define somewhat the meaning of the tern metallurgical.. When I was a student at M. I. T. ore-dressing was not thought of as metallurgy in any sense of the word, but it was considered as more closely allied to mining, enabling the miner to market an otherwise unmarketable product, or at least to market it to better advantage. Progress in ore-dressing has gradually allied it more closely with smelting, for at present the raw material received by the smelter is predominantly concentrates and smelting practice has been profoundly affected by the products of the concentrating mill. It is not surprising therefore that in many schools ore-dressing is frankly considered as metallurgy and although there may be some dissenting opinions it will be considered as such in this discussion. Twenty-five years ago at M. I. T. metallography was taught in a few optional lectures. This subject has developed rapidly and been expanded into the new and increasingly important field of physical metallurgy. To many metallurgists the -term metallurgy means only physical metallurgy. They know little or nothing about smelting and leaching and even less about ore-dressing. Having then broadened the scope of the term metal¬lurgy to cover ore-dressing, smelting, leaching and phys-

Jan 1, 1930

By D. H. Forbes, H. M. Manasevit, F. L. Morritz

Single-crystal thin films of molybdenum have been grown. by the pyrolytic decomposition of molybdenum hexafluoride in a hydrogen ambient on various insulating substrates at temperatures front 650° to 900° C. Single-crystal discs of various orientations of magnesium aluminate spinel, a aluminum oxide, magnesium oxide, and the natural facets of beryllium oxide were all observed to exert epitaxial control on the depositing film. Determinations of the crystallographic relationships existing between film and substrates have been made, using X-ray diffraction three-circle goniometry and Laue back-reflection techniques. Using these data, crystallographic overlays have been constructed which suggest a possible interfacial geometry on the basis of a match between metal deposit atoms and metal ion sites in the substrate. A continuing program has been in effect in the Auto-netics Laboratories over the past several years aimed at the development of electronic materials in new and useful forms using chemical vapor deposition techniques. During the course of these investigations, the epitaxy of silicon1"5 and tungstenep7 on single-crystal metal oxide insulators was studied extensively. The deposition of molybdenum is a logical extension of the tungsten work since the crystal structure is identical and the lattice dimensions differ by less than 1 pct. The pyrolytic decomposition of molybdenum hexafluoride in hydrogen was used to grow molybdenum films on the oxide substrates AlzOs, MgA1~04, MgO, and Be0 at from 650" to 900°C, depending on the substrate material. Under the experimental conditions to be described, monocrystalline films of controlled orientation were obtained. The materials investigated and their crystal structure are listed in Table I. EXPERIMENTAL The molybdenum depositions were effected by the hydrogen reduction of molybdenum hexafluoride (MoFe) in a flowing system of hydrogen at atmospheric pressure. The schematic of the apparatus is shown in Fig. 1. The hydrogen, purified by passage through a heated palladium thimble, was mixed with the vapor of the liquid MoFe maintained in a steel bottle at room temperature (25°C). The mixture was passed over the substrate, which was heated by rf induction of a sup-

Jan 1, 1969

By C. E. Lawall, C. T. Holland

When this study was started very little information was available regarding the physical characteristics of West Virginia coals. This was particularly true of friability and of crushing strengths of the coals. Some work had been done on specific gravity studies but the available information applied to only a few coals. In practically all coal-classification systems thus far proposed, the predominating factors of classifications are largely based on the chemical characteristics of the coal. Recently some investigators have pointed out that a classification based on chemical and physical properties of coal might serve to place coals in their proper group better than classification systems based on chemical properties alone. One of the aims of this study was to obtain some data on the physical properties of coal which might help to classify West Virginia coals. The Samples Fig. I shows where the coal samples were obtained and the approximate division line of the high and low-volatile coal fields of the state. The relative geological horizons of the coal beds tested are shown in Fig. 2. In securing samples of coal for friability and specific gravity tests, it was the aim always to obtain a representative sample of lump coal produced at a particular mine. The samples were obtained from the loading boom, the railroad car, or the mine cars. Wherever it was possible to secure samples from a loading boom they were taken from it by taking shovelfuls of coal from the loading boom every minute until about 200 lb. of coal was obtained. If there were no loading booms used at the mines sampled, the coal sample was taken from a loaded railroad car by systematically taking shovelfuls of coal at definite intervals over the whole top of the car until about 200 Ib. of coal was obtained.

Jan 1, 1932

By A. H. Geisler

INTRODUCTION THE correlation of property changes during precipitation with structure has progressed, sometimes rapidly but other times more slowly, since the fundamental discovery of Merica, Waltenberg and Scott.1 The predominent factor that hampered the progress has been limitations imposed by the various detection methods. Refinements in X ray diffraction techniques and in metallographic methods, which have been extended by the electron microscope, have contributed new information within the last few years. These permit an extension of the theory as proposed by Mehl and fetter in 1940.2 Now that a suffcient number of alloys has been investigated to establish a general mechanism of the precipitation process, a correlation of the facts into a generally applicable theory of age-hardening is both warranted and desirable. 'I he purpose of the paper is to provide an orderly correlation of the phenomenological facts of precipitation hardening. Speculation on mechanism of hardening will be confined to that consistent with existing theories of hardening. Age-hardening accompanies the formation of a new structure, the precipitate, as provided by an alloy system in which solid solubility decreases with decreasing temperature. Upon this premise alone all such systems would be expected to include age-hardenable alloys. Alas, this is not always the case. Few attempts have been made to explain the variable degree of age-hardening among different alloys or to explain the influence of small alloying additions upon the hardening. Dispersion hardening as originally postulated3 is not adequate.* Coherency hardening-the term that will be used to distinguish the properties of a two-phase mixture in the unique and unstable transition state at which the phases are strained into precise atomic registry (continuity or coherency) in planes

Jan 1, 1948

By Eleanor Haslem, Carl A. Zapffe

THE present investigation has three principal purposes: I. To develop a method for measuring hydrogen embrittlement that avoids certain errors complicating previously used methods. 2. To explore in a preliminary way some of the fundamental factors controlling embrittlement. 3. To apply the measurements specifically to stainless grades of steel, whose sensitivity or insensitivity to hydrogen embrittlement has never been clearly defined. SELECTING A TEST METHOD Hydrogen embrittlement is a condition of low ductility resulting from excessive absorption of hydrogen by the steel at some period in its history, and may be revealed by almost any test involving cold deformation. Tensile tests, impact tests, and bend tests are commonly used for detecting hydrogen embrittlement; although numerous other tests, such as cold-upsetting or extrusion, could be used. The simplicity of using a wire specimen for cathodic and acid pickling tests, and the especial adaptability of the bend test to wire specimens, led to selection of the bend test for the present research. Bend tests usually have been of three general types: (I) fatigue, (2) reversed bend, and (3) single bend. The first two types, though widely used, are inaccurate because their measurements are counteracted by an aging effect; and the third type has not been developed to its fullest utility. The effect of cold-working in removing hydrogen is well known. During a bend test hydrogen can be observed escaping from the convex side simply by coating the specimen with oil; and any technique employing flexing or reverse bending may therefore have its measurements masked because the mechanical action reduces the embrittlement during the test. This factor is so important that even elastic flexing of a hydrogen-charged wire specimen should be avoided before testing if accurate measurements are desired. DEVELOPING A MACHINE FOR MEASURING HYDROGEN EMBRITTLEMENT As for the single-bend test, its theory is good, and recovery caused by mechanical work is kept to a minimum. With a given degree of hydrogen embrittlement, a specimen will break at a given angle if the bending is applied unidirectionally and uniformly. The radius of the bend must be kept constant; and the rate of bending should be a constant, slow enough to allow reading of the breaking angle, and yet rapid enough to prevent significant recovery from the escape of hydrogen during bending. A simple apparatus (Fig. I) was constructed using a type H Foxboro drive unit A, which is a synchronous motor with a gear-reduction ratio of 600 to I. A cord, fixed at one end to a wooden pulley B on the drive shaft of the motor, follows the pe-

Jan 1, 1946

By S. Weissmann, P. R. Swann, D. F. Wriedt

The sizes and density of precipitates in an intemally oxidized 0.19 wt pct Al-Ag single crystal have been determined by low-angle X-ray scattering and by transmission electron microscopy . The correlation in particle sizes measured by the two techniques is reasonably good. For an oxidizing temperature of 800°C the particles were found to INTERNAL oxidation of dilute alloys of aluminum in silver produces an oxide which has an excess of oxygen compared to Al2O3.' It is believed that the excess oxygen is an indication of the small sizes of the oxide particles. Depending upon the particular model chosen for the oxide structure, the size of the o-A1 particles can be calculated as a function of the oxygen-to-aluminum ratio. These calculations pre- have diameters in the range 30 to 140A, with a mean size of about 50.4 as observed by electron microscopy. At lower oxidizing temperatures, less than 600°C, no clearly resolved particles are formed, and it is suspected that if A1-0 clusters exist they must be exceedingly small, i.e., 10A or less in diameter. dicto that the particles would vary in size from 15 to 100A. This range of sizes is amenable to detection by both small-angle X-ray scattering and transmission electron microscopy. This paper compares the cluster sizes in such internally oxidized A1-Ag alloys determined by transmission electron microscopy and small-angle X-ray scattering. SPECIMEN PREPARATION Single crystals were prepared from 99.9999 pct Ag, obtained from Cominco Products, and 99.99 pct Al, obtained from Aluminum Co. of America. All melting operations were carried out in graphite molds under flowing purified hydrogen in a horizontal zone refiner. The silver was first degassed,

Jan 1, 1964

By Edgar C. Bain

Of the important phenomenon of the hardening of steel, Professor Sauveurl says: It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say this of other problems. It seems likely that one of the new avenues of approach to many metallo-graphic problems is the study of crystal structure, or more accurately, the atomic arrangement, by means of the x-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of x-rays by Laue and the Braggs2 and later by HullI3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the x-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 1, 1923

By Edgar C. Bain

Of the important phenomenon of the hardening of steel, Professor Sauveurl says: It would seem as if the methods used to date for the elucidation of this complex problem have yielded all they are capable of yielding and that further straining of these methods will only serve to confuse the issue, the point having been reached when this juggling, no matter how skilfully done, with allotropy, solid solutions, and strains is causing weariness without advancing the solution of the problem. The tendency of late has been to abandon the safer road of experimental facts and to enter the maze of excessive speculations, in which there is great danger of some becoming hopelessly lost. The conclusion seems warranted that new avenues of approach must be found if we are to obtain a correct answer to this apparent enigma. With some degree of fitness we may say this of other problems. It seems likely that one of the new avenues of approach to many metallo-graphic problems is the study of crystal structure, or more accurately, the atomic arrangement, by means of the x-ray spectrometer. The crystal structure of some materials has been carefully worked out by the mineralogist, but his methods are, in general, unsuited to commercial metals and a method that yields even better information is at hand as the result of work on the diffraction of x-rays by Laue and the Braggs2 and later by HullI3 St. John, and others. It should be understood that the contour of free crystals, which is the subject of measurements by the crystallographer, is the result of the atomic structure and, in general, bears a simple and obvious relation to it. The use of the x-ray spectrometer4 has been described frequently, so the procedure will not be given here.

Jan 1, 1923

By Eugene Coste

ALTHOUGH some of the observers who first paid especial attention to the occurrences of oil and gas in the strata (such as Hunt in 1859, Andrews in 1861, Winchell in 1865, Mendelejeff in 1876, Höfer in 1876, Minshall in 1881, and I. C. White in 1883) seem to have been impressed with the fact that oil and gas deposits were connected with the disturbances in the rocks caused by their upheaval,1 yet, with the exception of Mendelejeff, and possibly Andrews, these observers do not appear to have understood what is really the one essential factor in the occurrence of oil and gas in the strata: viz., the faulting, uplifting, fracturing, fissuring, and jointing always accompanying even slight rock disturbances, and in certain districts (petroliferous provinces)2 allowing solfataric hydrocarbon emanations to force their way up from the interior and to reach and impregnate the porous portions of sediments subjected to the disturbances. Instead of this simple explanation to account for the observed connection between petroleum deposits and rock disturbances, most of the observers mentioned above, and many others who have followed them on the name lines since, have entirely reversed the problem. To them, instead of the dissemination of gases from fissures into the sediments, it presented the accumulation and concentration, according to anticlinal or other geologic structures, of oil and gas originally present throughout the whole mass of the strata where they were produced by the decomposition or distillation of organic remains. Whether this important problem involves accumulation from sources within the oil-bearing strata themselves, or infiltration and dissemination from outside sources, may be easily determined if all preconceived ideas are put aside and the established facts only are considered.

Jan 9, 1914

By A. W. Sommer, H. H. Kellogg

It is shown that SO3-O2 mixtures react with sphalerite at an appreciable rate ill the temperature range of 361° to 527°C to fornz ZnSO4. The rate of reaction follows a parabolle lax. Oxygen, or O2-SO2 mixtures, have a negligible effect on sphalcrite in the same temperatuee range. PRACTICAL roasting of sphalerite is usually performed at 800°C or higher. The calcine is composed of zinc oxide unless the roaster atmosphere contains relatively large amounts of SO2 and the temperature is held to 800oC or lower, in which case zinc sul-fate may also form. Ong, Wadsworth, and assell' have made a careful kinetic study of sphalerite oxidation under these "normal conditions" and have concluded that the rate of the reaction is controlled by the decomposition of an activated complex adsorbed on the sphalerite surface. They found the rate of oxidation to be small at 700°C. Extrapolation of their data to 400°C would indicate an almost negligible rate at this temperature. In our work sphalerite was reacted with air, mixtures of SO2, O2, and N2, and mixtures of SO3, O2, and N2 in the temperature range 361o to 527OC. Negligible rates of oxidation were found, except for the gas mixtures containing SOs. With this latter gas, the oxidation of finely divided sphalerite was fairly rapid and zinc sulfate was the product. Based on the limited evidence available, the rate of sphalerite oxidation by SO3 is postulated to be controlled by gaseous diffusion through pores or cracks in the zinc-sulfate coating. This evidence for the direct reaction of sphalerite and SO, at low temperature may prove of importance to the understanding of zinc-sulfate formation in the dust-collecting equipment usually associated with zinc roasters. The roaster gas carries off fine dust, much of which may be unreacted sphalerite. The temperature in dust-collecting equipment drops from the roaster temperature (about 800°C) through the range of temperature we studied, to ambient temperature. Such dusts are known to contain far larger amounts of zinc sulfate than the primary calcine. It has been assumed in the past that this sulfate is formed by reaction of ZnO dust with SO3 (or SO, plus 0,) in the partly cooled gases. Our work shows that an alternative possibility exists—the direct reaction of SO3 with ZnS dust. EXPERIMENTAL Reaction rates for sphalerite at 350° to 600°C are relatively small so that it was necessary to use finely divided material with a relatively large surface area in order to obtain measureable amounts of reaction. In the preliminary experiments, pure mineral sphalerite, ground to pass a 325-mesh sieve, and chemically precipitated ZnS (in the form of an impalpable powder) were used. In the quantitative rate experiments the ground mineral sphalerite was processed in an Infrasizer to obtain a product with particle size between 9 and 18 µ. The analysis of this material was 66.7 pct Zn, 0.09 pct Fe, and 32.7 pct S (theoretical sphalerite is 67.1 pct Zn, 32.9 pct S). The sized powder was carefully mixed and divided into l-g samples. The apparatus used for the quantitative rate measurements is shown in Fig. 1. For the preliminary experiments the following change was made: The external catalyst furnace (B, C)* was not used. *Letters refer to Fig._______1 .___- Rather, when catalysis of the SO2 + O2 reaction was desired, the glass beads in basket M were replaced by vanadium-oxide pellets. Procedure—A l-g sample of ZnS was placed on a shallow stainless-steel tray, I, and spread evenly to a depth of about 1mm. The tray was placed in the reaction assembly and the assembly inserted in the cold furnace. The furnace tube was flushed with dry argon and then heated to the desired reaction temperature. The temperature was controlled to ±0.5oC. Gas mixtures (O2 + N2 or O2 + SO2) were prepared from tank gases by means of a mixing device identical to that employed by Darken and Gurry.2 The total flow rate of gas was 205 ml per min to point A of Fig. 1. The accuracy of the individual and

Jan 1, 1960

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965

By Dr. Hans Von Höfer

APART from the hypothesis of a .cosmic origin (which failed of acceptance because it was not adequately supported by facts), the only important controversy concerning the origin of petroleum has been, for a long time, between the advocates of inorganic and of organic origin respectively. Each of these theories has had a long history of development, and is still being perfected, under the influence of two causes: (1) the increasingly extensive and thorough study of the oil-fields (of which new examples are periodically discovered and opened); and (2) the progress of synthetic experiments devoted to this question. Moreover, the advance in our physical and chemical knowledge of the properties of this peculiar natural product has necessarily modified all criticism of conflicting views. I. THE HYPOTHESIS OF INORGANIC ORIGIN That the notion of an inorganic origin of petroleum, first set forth by Berthelot in 1866, and afterward ingeniously developed and formulated by Mendelejeff, should thus have proceeded chiefly from chemists, is quite natural; for the question was one of possible chemical processes in the earth's interior, and of imagined chemical reactions to be, verified by experiment. Hypotheses of this kind were suggested by many chemists, of whom two, P. Sabatier and J. H. Senderens, may be specially named by reason of their highly interesting chemical experiments. Among geologists, Mendelejeff's hypothesis was received at first with much interest and favor; for it rested on the assumption of a central terrestrial mass of iron carbide, and the geologists had good reasons for adopting that assumption. Yet comparatively few of them attempted to furnish geological proofs of the hypothesis: the majority either silently believed in it, or for one or another reason rejected it altogether.

Jan 5, 1914