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By Leo Brewer, Gerd M. Rosenblatt

Thermodynamic calculations predict the species vaporizing from metal-oxide mixtures when reliable free energy functions, enthalpies of formation, and dissociation energies are available for the possible gaseous and condensed oxide components. Calculations of the oxygen to metal ratio in the vapor phase compared with the oxygen to metal ratio in a liquid metal saturated with oxide impurity are presented The possibility of purifying metals contaminated with oxide by vacuum melting or by distillation is discussed. Kinetic considerations affecting rates are neglected. IN recent years extensive information has been obtained on the thermodynamic stability of gaseous oxides of metals due to a variety of new types of measurement. Perhaps the greatest amount of information has come from the application of mass spec-trometry to the study of high-temperature vapors.' In many instances oxides of quite unusual oxidation states are found to be important in the high-temperature vapors. At low temperatures the standard free energy change for a reaction as given by the equation ?F° = ?H° - T?S° is determined primarily by the AH" value. However, at higher temperatures where the value of T in the T?S° term is large, the entropy term becomes equal to or greater than the AH term. At low temperatures only reactions for which AH is negative or only slightly endothermic are of importance. This restricts the main equilibrium species largely to those with completed octets or those with the principle oxidation number of the element. At

Jan 1, 1962

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is neccssary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important cornponents of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transFormation are dealt with in a highly detailed and descriptive manner in. the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilib-rium conditions of thermal treatment. The Guilletl diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts: At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase's in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. Reference may be made at this point to the efforts of Marsh5 to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encountered in traversing the nickel-steel nickel-cast-iron range under what might be called ordinary departures from equilibrium. ExperimentaT. Conditions Since the intent has been to establish structures developed under arbitrary conditions, experimental details have perhaps more than usual importance. Three of these conditions should particularly be noticed: (I) the material was cast and not subjected

Jan 1, 1942

By Carl O. Thieme

INDUSTRIAL specialization has rapidly created a demand for new and better alloys. A more thorough understanding of the requirements of specific industries and the discovery of processes by which it has been made possible to utilize certain metallic elements in larger quantities, together with greater purity in most virgin metals, has resulted in a great increase in the number and variety of alloys. This increase in the number of elements entering into non-ferrous alloy manufacture has increased the contamination in secondary metals, as received by the smelter. In order to successfully refine scrap of a much more complex nature it has been necessary for the smelter to install new equipment and to constantly search for new methods of refining as well as to improve the methods already in use. In some instances it is largely responsible for specialization in the secondary metal industry. It is usually necessary to remove the contaminating impurities in scrap or eliminate to a degree not objectionable, no matter how introduced. In order to know what metals or elements are of an objectionable nature, the smelter must make a study of the effect of single elements and combinations of elements on many of the physical and mechanical properties, such as strength, ductility, color, hardness, casting soundness, etc. The smelter of secondary metals must be able to utilize scrap materials of all kinds, for, sooner or later, most fabricated metal parts and the waste products formed during the process of manufacture find their way to the smelter. In addition, the smelter, in contracting for salvaged material from the producer, gets some undesirable and unusual materials. The value of secondary metals and the importance of their recovery has increased in recent years and it is no longer sufficient to recover the base metal only, such as copper from copper-bearing material, but it is essential that other elements present be recovered and converted into useful form. This paper will deal not with the smelting and refining or separation of impurities from secondary metals but an attempt will be made to show the increased value of metal scrap when properly segregated and in a less contaminated condition. There are five principal reasons for contamination in secondary metals: New and unusual alloys, productive methods,

Jan 1, 1928

By Carl O. Theime

Industrial specialization has rapidly created a demand for new and better alloys. A more thorough understanding of the requirements of specific industries and the discovery of processes by which it has been made possible to utilize certain metallic elements in larger quantities, together with greater purity in most virgin metals, has resulted in a great increase in the number and variety of alloys. This increase in the number of elements entering into non-ferrous alloy manufacture has increased the contamination in secondary metals, as received by the smelter. In order to successfully refine scrap of a much more complex nature it has been necessary for the smelter to install new equipment and to constantly search for new methods of refining as well as to improve the methods already in use. In some instances it is largely responsible for specialization in the secondary metal industry. It is usually necessary to remove the contaminating impurities in scrap or eliminate to a degree not objectionable, no matter how introduced. In order to know what metals or elements are of an objectionable nature, the smelter must make a study of the effect of single elements and combinations of elements on many of the physical and mechanical properties, such as strength, ductility, color, hardness, casting soundness, etc. The smelter of secondary mctals must be able to utilize scrap materials of all kinds, for, sooner or later, most fabricated metal parts and the waste products formed during the process of manufacture find their way to the smelter. In addition, the smelter, in contracting for salvaged material from the producer, gets some undesirable and unusual materials. The value of secondary metals and the importance of their recovery has increased in recent years and it is no longer sufficient to recover the base metal only, such as copper from copper-bearing material, but it is essential that other elements present be recovered and converted into useful form. This paper will deal not with the smelting and refining or separation of impurities from secondary metals but an attempt will be made to show the increased value of metal scrap when properly segregated and in a less contanlinated condition. There are five principal reasons for contamination in secondary metals: New and unusual alloys, productive methods,

By Wallace E. Pratt

IRon-oRe deposits in the Philippine Islands became the subject of official record as early as 1664. Undoubtedly iron ore was known and recognized by the Filipinos long before the earliest Spanish records. It is even possible that the Filipino practice of smelting iron ore is, like the native copper smelting, older than the Spanish conquest of the islands. The first records have to do with the magnetite-hematite ores near the towns of Santa Inez and Bosoboso in Rizal Province, from 15 to 20 miles east of Manila. The magnetite-hematite ores of Bulacan were exploited in 1783. Similar ores near the town of Mambulao in Camarines Province yielded a number of specimens to be exhibited in Spain in 1834. With the exception, then, of the lateritic iron ores on the eastern coast of northern Surigao, the true nature of which was not recognized until 1914, the important iron-ore deposits of the Philippines had all been discovered before the islands came under the dominion of the United States. Indeed, in the Spanish documents relating to the history of iron mining are statements which, if their accuracy be not questioned, leave us in the Philippines today with much less iron ore than the Spaniards found. To quote, for example, a report submitted to the Superior Government in Spain in 1835 by one of its emissaries, Don Lorenzo Calvo: "The Philippine Islands, most excellent Sir, possess iron and exhibit it in nearly every known mineralogical combination, and in such abundance that the cordillera of the island of Luzon, from Montufar Point in San Bernardino Straits to Cape Bojeador, is composed of no other mineral than iron, its ranges, of the third order, being in content and structure totally iron of the best quality, the more valuable in that its combinations are such as to facilitate its fusion and to render its redaction to metal simple." Today, however, it is recognized that the iron-ore deposits in the Eastern Cordillera of Luzon constitute, not a continuous belt, but a series of widely separated deposits, including a half dozen orebodies within a distance of 10 miles in Bulacan Province, a single outcrop at Santa Inez, Rizal Province, farther south, and three deposits around

Jan 1, 1916

By H. F. Easter

The lead department of the El Paso Smelting Works at El Paso, Tex., is operated strictly on a custom basis. The ores treated are drawn from the surrounding territory, comprising New Mexico, Arizona, western Texas, and northern Mexico. Ores received from the last-named section originally amounted to a very large tonnage, but. of recent years have dwindled into comparative insignificance so far as this plant is concerned. This has been due partly to the establishment of a lead-smelting plant at Chihuahua, which is much closer than El Paso to most of the important mines, and partly to the recent revolutionary troubles in Mexico. There are no mines of either lcad or copper in the immediate vicinity of El Paso. In general, it may be said that the lead-ore supply of recent years has been uncertain and precarious, with a general tendency toward an excess of silica and a shortage of iron. This latter requirement has been met in large part by the use in El Paso lead furnaces of considerable amounts of roasted leady copper matte from the Chihuahua smeltery and of converter slag from the El Paso converters. These two materials, coupled with complex lead-copper ores from Bisbee, Ariz., have introduced into the lead-smelting operations a most unusual amount of copper, which has had an important bearing upon the smelting practice of the plant. his matter will be discussed later. The ore, loaded in either box cars or gondolas, enters the storage yard on four tracks elevated about 8 ft. above the ground. As all unloading is done by hand, unloading platforms at the height of the car floor parallel the tracks on each side to afford a runway for wheelbarrows. At frequent intervals these lengthwise platforms are joined together by others running crosswise to facilitate the distribution of the ores evenly over the beds, which are located below and between the tracks. At present much of the bedding space formerly used for lead ores is given over to the copper department, but 20 bins of various sizes are retained for the use of the lead furnaces and the Huntington & Heberlein roasting plant. The largest of these holds about 1,000 tons, while the smallest holds not over

Jan 1, 1916

By J. B. Bassett, E. S. Rowland

The experimental work reported herein firas inspired by the publication of a paper by Grange and stewart, in which it was suggested that at low chromium contents the effect of this element on the Ma point was greater than at higher chromium contents, It was argued that, if a small increase of chromium in solution in austenite caused a sharp lowering of the M, point, it might lead to an explanation of occasional unsolved stress cracking of SAE 52100 during heat treatment. Commercial hardening is carried out at temperatures of incomplete solution, leaving carbides available to enrich the austenite during any inadvertent increase in temperature, such enrichment of the austenite in chromium content would lower the M, point nearer room temperature where cracking is more likely to occur. According, it was decided to investigate the effect of chromium, in quantities between o and 2 pet, on the M, point of commercial steels. Fig I summarizes the data available on chromium steels. For purposes of comparison, the M, temperature values were corrected by means of the Grange and Stewart formulas to (I) Hypoeutectoid compositions: 0.50 pct carbon and 0.80 pct manganese (z) Hsereutectoid compos-sition': 1." pet carbon and O.35 pct manganese. Only the steels having compositions reasonably close to these corrected values were included, because large adjustments inevitably introduce increased error such as are experienced in using the formula. The straight lines of Fig I were drawn by the authors. These data obviously do not settle the question Of the effect Of chromium On the Md Oint, particularly at low chromium contents. While it is fairly well established that chromium causes the M, to be lowered when present in quantities of I pet Or more, Grange and Stewart1 have suggested that in small amounts (less than 1 pet) it is more effective in lowering the Ma point, while Klier and Troiano2 have suggested that in small amounts it is less effective in lowering the Ma point. Payson and Savage3 concur with Klier and Troiano and further suggest that the effect is not linear at these concentrations. Rose and Fischer4 report that small amounts of chromium actually raise the Ma point of a 0.20 carbon steel. Material Two series of 35 Ib induction heats were melted for this work, the analyses of which are given in Table I. One series was aimed at 0.50 pct carbon and 0.80 pct manganese with chromium additions in 0,25 pet increments from o to 1.5 pct with a single heat at 2.0 pct Cr. This series was considered necessary because the commercial heat treatment of SAE 52100 does not generally introduce more than about 0.60 pct carbon in solution in the austenite. The high

Jan 1, 1949

By J. B. Bassett, E. S. Rowland

INTRODUCTION THE experimental work reported herein was inspired by the publication of a paper by Grange and Stewart,1 in which it was suggested that at low chromium contents the effect of this element on the [M,] point was greater than at higher chromium contents. It was argued that, if a small increase of chromium in solution in austenite caused a sharp lowering of the [M,] point, it might lead to an explanation of occasional unsolved stress cracking of SAE 52100 during heat treatment. Commercial hardening is carried out at temperatures of incomplete solution, leaving carbides available to enrich the austenite during any inadvertent increase in temperature. Such enrichment of the austenite in chromium content would lower the [ M,] point nearer room temperature where cracking is more likely to occur. Accordingly, it was decided to investigate the effect of chromium, in quantities between o and 2 pct, on the[ M,] point of commercial steels. Fig I summarizes the data available on chromium steels. For purposes of comparison, the [M, ] temperature values were corrected by means of the Grange and Stewart formula§ to (I) Hypoeutectoid compositions: 0.50 pct carbon and 0.80 pct manganese (2) Hypereutectoid compositions: 1.00 pct carbon and 0.35 pct manganese. Only the steels having compositions reasonably close to these corrected values were included, because large adjustments inevitably introduce increased errors such as are experienced in using the formula. The straight lines of Fig I were drawn by the authors. These data obviously do not settle the question of the effect of chromium on the [M,] point, particularly at low chromium contents. While it is fairly well established that chromium causes the [M,] to be lowered when present in quantities of I pct or more, Grange and Stewart1 have suggested that in small amounts (less than I. pct) it is more effective in lowering the[ M,] point, while Klier and Troiano2 have suggested that in small amounts it is less effective in lowering the []M,] point. Payson and Savage3 concur with Klier and Troiano and further suggest that the effect is not linear at these concentrations. Rose and Fischer4 report that small amounts of chromium actually raise the-[M,] point of a 0.20 carbon steel. MATERIAL Two series of 35 lb induction heats were melted for this work, the analyses of which are given in Table I. One series was aimed at 0.50 pct carbon and 0.80 pct manganese with chromium additions in 0.25 pct increments from o to 1.5 pct with a single heat at 2.0 pct Cr. This series was considered necessary because the commercial heat treatment of SAE 52100 does not generally introduce more than about 0.60 pct carbon in solution in the austenite. The high

Jan 1, 1948

By Calvin Pierson, R. S. Dean, E. P. Barrett

Wrought iron and steel have been prepared from limonite, hematite, and magnetite ores by gaseous reduction, compacting and squeezing the resulting product at high temperature and finally melting the wrought iron so formed. The structure, analyses, mechanical and magnetic properties of the products are given. It is found that the structure of iron ores is best studied by subjecting them to gaseous reduction and using metallographic technique on the resulting sponge iron. In this way the cell structure of iron ore is clearly shown. The wrought iron made by heating compacted sponge iron to 1450" C., and forging, shows a cell structure inherited from the ore. This cell structure is further preserved in melting and casting the wrought iron. The probable relation of the properties of the materials to this inherited cell structure is discussed.

Jan 1, 1935

By Calvin Pierson, R. S. Dean, E. P. Barrett

Wrought iron and steel have been prepared from limonite, hematite, and magnetite ores by gaseous reduction, compacting and squeezing the resulting product at high temperature and finally melting the wrought iron so formed. The structure, analyses, mechanical and magnetic properties of the products are given. It is found that the structure of iron ores is best studied by subjecting them to gaseous reduction and using metallographic technique on the resulting sponge iron. In this way the cell structure of iron ore is clearly shown. The wrought iron made by heating compacted sponge iron to 1450" C., and forging, shows a cell structure inherited from the ore. This cell structure is further preserved in melting and casting the wrought iron. The probable relation of the properties of the materials to this inherited cell structure is discussed.

Jan 1, 1935

By S. G., Lasky

IT seems to be in the nature of concepts that they have many meanings, and that the meaning best reflecting the primary interests of a person tends to be accepted by him as the normal meaning of the concept. The concept of ore reserves is no exception, for there is no unanimity of meaning among the several groups of us who are interested in ore reserves, nor even among the individuals of a single group. The groups most interested in ore reserves would seem to include at least the mining industry, perhaps State taxing agencies, and the Federal Government in all its diversified activities, and I would include also the citizenry at large or at least that part of it that consciously thinks about problems-of national welfare. To each of these, and to different individuals within them, the term reserves represents something different, and the farther away the individual or group gets from physical contact with the ore, the more abstract does his or its concept become. It is something different to the policy maker from what it is to the fact-finder or to the miner.

Jan 1, 1945

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

Mills Day left a journal of his travel to Ohio and return by way of Pittsburgh in 1810. He left this comment about western Pennsylvania: "June 19. As I proceeded toward Pittsburg, (From Washington and Canonsburg) the country grew more populous. The hills appeared to consist of strata of freestone, iron, coal, and slate. June 20. Its (Pittsburg's) water communication with a vast extent of country and the immense beds of coal in its immediate vicinity render it a place peculiarly adapted to manufactures. Coal may be obtained of a good quality, ready delivered at 5 cents a bushel."1 Until within a year or so of this period, coal was used for domestic purposes, brick-making, by blacksmiths, etc.; now the industry entered a period of rapid growth caused by the introduction of the steam engine. As manufacturing was increasing due to the settlement of the western country, the additional facilities created by mechanical power were welcome. Apparently the first engine was installed in Pittsburgh, in a steam grist mill, in 1808; it is described in the Navigator of 1811: "The water of the boilers are heated by large fires made of stone coal, which is introduced at one end into a grated fire place as long as the cylinders themselves; the quantity of coal consumed daily by these boilers is said to be about twenty bushels, which cost one dollar." Later it mentions the effect of burning coal:

Jan 1, 1942

By Andre Hubaux

In the writer's opinion, more stress should be put on field and microscope observations, as J. L. Gillson does. His discovery of relics of big labradorite feldspars from the Marcy anorthosite in all the other rocks is proof enough that previous field observations have been inadequate. The writer's field experience with anorthositic massifs is limited to the Egersund-Sogndal district in southern Norway; however, this is a very large and well exposed area. It seems to have so many points in common with the Adirondack region that a detailed comparison should be beneficial. This comparison was not possible 20 years ago, owing to the scarcity of geological data, at least for Norway. Both regions are now far better known-the Norway district because of the work of Professors Bugge and Barth33-35 and especially because of the extensive field and microscopic research of P. Michot,36-46 who introduced me in the field to the problems of that region.

Jan 3, 1958

By R. E. Whippo, B. L. Murowchick

The commercially exploited sedimentary apatites exhibit a number of variable lattice substitutions which affect their chemical composition. Carbonate is a major diluent of phosphorus values in sedimentary apatites. Substantial amounts of water as hydroxyl, hydronium, and tetrahedral hydroxyl ions substitute for fluorine and oxygen, calcium, and phosphate, respectively. Calcium is also replaced by several other divalent and monovalent cations. The structural formula demonstrates the substitutions in the lattice of the sedimentary apatites studied in view of the crystal-chemical relationships which have been postulated for the isomorphous apatite series. The lattice constant a. varies from 9.29 to 9.40 A for the apatites studied. Quantitative relationships between this constant and lattice substitution are complicated by the interaction of multiple substitutions whose influence is non-additive. The mineral apatite, the principal raw material source of phosphorus for agricultural and industrial applications, offers a wide area for investigation. Considerable research effort has been expended in the study of apatite crystal-chemistry by medical, biological, and earth scientists. Few of these studies deal directly with the sedimentary apatites from the major occurrences which are widely exploited for commercial uses. It is the purpose here to present chemical analyses of several sedimentary apatites and discuss their chemical composition in relation to the structural and crystalchemical principles which have been postulated for the apatite isomorphous series. THE STRUCTURE OF FLUORAPATITE The atomic structure of fluorapatite was described, independently, by Ngray-Szabd and Mehmel in 1930 and has been accepted as presented, with only minor changes,4 since that time. The hexaogonal unit cell with dimensions of a = 9.37 0.01 A and c = 6.88 0.01 A contains two molecules of the composition "There are six (PO4) groups in the cell, four calcium ions on the trigonal axes, surrounded prismati-cally by six oxygen ions and six calcium ions surrounded by an irregular polyhedron of a fluorine and five oxygens. Fluorines are at the comers of the reflexion planes, touching three calcium ions each".l7

Jan 1, 1968

By K. L. Meissner

IT is well known that the so-called pure aluminum contains noticeable amounts of impurities, chiefly iron and silicon, and many investigators have studied the forms in which these impurities exist. Hanson and Archbutt1 state that iron exists in aluminum as FeAl3 and silicon as elementary Si. The solubility of FeAl3 in solid aluminum is practically zero, or at, least so small that the smallest trace of this compound is always visible as a separate constituent. Under the microscope an untrained eye can hardly distinguish, without etching, the two constituents FeAl3 and Si, but they can be differentiated by suitable etching reagents. Anderson2 also found the same results. At the same time, Merica, Waltenberg, and Freeman3 found a constituent of unknown composition. They found a small thermal effect, at 610° C., on the cooling curves of aluminum with small amounts of iron and silicon. The intensity of this effect increased with increasing silicon content, until an effect occured at 576° C. due to the eutectic between aluminum and silicon. The authors ascribed the effect at 610° C. to a compound, which they call "X constituent." It was thought to be a ternary compound containing iron and silicon and could be observed under the microscope as dark particles. Dix4 has published unetched photomicrographs of an aluminum with 0.51 per cent. iron, 0.99 per cent. silicon, and 0.32 per cent. copper that shows three constituents: the dark Si (black in the figure), the lighter FeAl3, which appears in half tone and crystallizes in needles, and a constituent of the same color as FeAl3 but of different crystal form, often resembling Chinese script. This last constituent, Dix thought, is a compound of Fe and Si; not the compound FeSi but a compound containing a relatively small amount of silicon. Therefore an alloy of aluminum, iron, and silicon (the copper should not be regarded in the following considerations) must contain the following four constituents: Al, FeAl3,

Jan 1, 1926

By P. Lees, N. Parkinson, K. Hartley, D. M. Donaldson

The reprocessing of advanced fuels such as carbides, oxides, and cermets, containing up to 30pct pu has been studied. Dissolution of uranium carbides in nitric acid produces appreciable quantities of mellitic acid which has undesirable effects in subsequent stages of the process. Mixed oxides containing up to about 40 pct Pu in solid solution with UO, are soluble in nitric acid and a leaching type process in nitric acid for a stainless steel/UO,. PuO, fuel containing 30 pct Pu appears to be feasible. It offers considerable economic advantages THE reprocessing of the U-Cr alloy core of the Dounreay Fast Reactor was described by Buck and others at the Second Geneva conference.' This paper described the flowsheet and plant for processing a relatively simple fuel of good dissolution charac- over total dissolution routes. A new oxidation-sub -limation process is described for metallic fuels containing up to 12 pct Mo. New data is presented on the solvent extraction of uranium and plutonium nitrates into tributyl phosphate -odorless kerosene and of the influence of radiolytically produced acid phosphates on this part of the process. It is concluded that there are no insuperable difficulties which will prevent the satisfactory reprocessing of high burn-up plutonium fuels by a solvent extraction route. teristics and of low-plutonium content after irradiation. However, it has been clear for some time that more satisfactory operation of the reactor can be obtained by the use of a core with better irradiation performance than U-Cr alloy and a U-Mo alloy will be used for the next charge. Recent modifications to the core mean that it is now possible to carry out irradiations of fuel element subassemblies similar to those which might be used in a fast power reactor and trials with plutonium-bearing fuel elements will be made in the relatively near future. These changes have meant that a considerable amount of reprocessing development work has had to be carried out for

Jan 1, 1963

By E. J. Roberts

Prior to 1916, thickening was an art, and any accurate decision as to what size of machine to install to handle a given tonnage of a specific ore must have been one of those intuitive conclusions, based on both intimate and extensive acquaintance with thick-ners and ore pulps. Then in 1916 "knowledge of acquaintance," became "knowledge about" with the publication of the Coe and Clevenger paper.' The unit operation of thickening had graduated to the status of an engineering science. The fundamental similitude relationships for the two major phases of the operation were defined so clearly that batch tests on models as small as liter cylinders could serve to specify protypes as large as 325 ft in diameter. It is quite apparent from reading the literature that Coe and Clevenger's contribution is not generally appreciated. In so far as the basic engineering relationships are concerned, the only real advance which has occurred in the 30 odd years which have elapsed since the Coe and Clevenger paper is the recognition of the effect of the rakes on the thickening process. Bull and Darby2 noted this in 1926, and the extensive use of the "gluten type" thickener, in which the effect is magni-fied, bears witness to its importance. Comings3 further verified this effect of the rakes. As a matter of fact, a number of papers show an apparent regression from the Coe paper in that the area determinations are made on the basis of a single test from One concentration of solids. Coe and Clevenger amply demonstrated that this is unsafe, since the controlling zone may be one other than that of the feed dilution. Comings3 neatly demonstrated this without apparently realizing it. Of course there have been significant advances in the application of the operation to industry. Open tray thickeners were introduced to save area; balanced tray thickeners, washing thickeners, and multifeed clarifiers were developed with all of their special hydraulic and mechanical problems. Combinations of all kinds have been introduced, such as combination agitators and thickeners, combination flocculators and clarifiers, combination thickeners and filters. With the establishment of the operation on a firm engineering foundation, installation was facilitated and expansion proceeded. There are still problems, of course, functional as well as mechanical. Sometimes the moisture in the underflow obtained in practice is not as low as is expected on the basis of the test data. Sometimes the underflow is so "thick " that its discharge and subsequent handling requires special attention. Island formation plagues some operators. The use of the thickener as a surge basin and blending tank in the cement industry poses unusual problems. Design of rakes and the drive mechanism must be continually im-proved. Corrosion problems must he overcome. Power requirements for raking the settled solids occasionally is the controlling factor as it was in the case of the all American Canal desilting installation. Other similitude relationships and design problems come into the picture when we enter the field of clarification or nonline settlement. We have an energy dissipation problem in introducing the feed and any models must satisfy the Froude model relationships. Autoflocculation requires detention which involves the same similitude laws that we encounter in the compression zone. Approach to an Exact Science The next step beyond having control of the similitude relationships is to understand the why of these relationships right back up the line to first principles. The ultimate might be that, if given the mineralogical composition of the solids and their size distribution together with an analysis of the suspending liquid, we could calculate the entire thickening behavior of the system. Then we could say we had reduced the operation to an exact science. True it might be more trouble getting this basic analytical data than to make our empirical determinations for area and volume, and we would need an ENIAC to calculate the results, but that does not detract from the desirability of such understanding. Considerable work has been done by the chemical engineers with this end in view. Comings,3 Egolf,4 Work,5 Kam-mermeyer,6 Steinour,7 and others have studied the problem. The writer has no final answer to the thickening story but would like to propose a picture of the mechanics of the two phases of thickening which has been found useful in understanding the subject and which leads to some convenient relationship in treating the compression step and arriving at the compression depth.

Jan 1, 1950

By Colin C. Harris, Nathaniel Arbiter

Flotation kinetics is the study of the variation in amount of froth overflow product with flotation time, and the quantitative identification of all rate con- trolling variables. With such variables maintained constant, the algebraic relationship between the proportion of mineral floated and flotation time is a flotation rate equation. This contains the constant values of all the rate determining variables implicit in one or more rate constants which must be evaluated from experimental data. The form or forms of the rate equation can either be deduced from assumptions or facts established about the mechanism of the process, or, more commonly, determined empirically or by analogy with similar rate process. (See pages 215 to 226 and 221 to 227.) The earliest contributions on flotation kinetics came in the mid- ~hirties,3,27,31 with interest increasing in recent years. The broad goal of these studies is the reduction of the total variability of a flotation system to equations among the individual variables, or among a lesser number of dimensionless groups.43 Although the goal is at present far from realization, its attainment will yield many practical advantages. The quantitative under- standing of the process should lead to improvements both in metallurgical results and flotation cell design. It should lead also to reliable methods for scaling-up* of laboratory and pilot plant results to full size operation without the need for expensive and time-consuming mill tests on commercial machines. Finally, this type of quantitative information will assist the automation of flotation cells and circuits as well as control by computers. Replacing present methods of control based on post-mortem assays and trial and error manipulation of reagents and cell variables by control through exact process analysis should yield higher levels of grade and recovery through reduction of the large variability of present-day results. CHEMICAL ENGINEERING ANALOGIES: Industrial flotation always involves flow of pulp through a series of stirred tanks. It thus bears formal analogy to many chemical engineering processes, the kinetics of which in flow systems has been studied for many de- cades.38,39,73,83 It will be useful to review these studies before considering flotation kinetics. Batch and continuous treatment are classified in Fig. 1. Batch operation in the true sense is unknown in flotation where concentrate is always removed

Jan 1, 1962