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By N. P. Goss

Asterism appearing in X-ray Laue diagrams is an extremely sensitive index of changes in the internal structures of individual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.l-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not conclusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made between mosaic and distorted grain structures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example: has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-l4 to 10-l5 c.c., or 10-15 cm. in size. These crystallites, or blocks, appear to survive the most drastic cold-working, for it has been shown, and more elaborately by Wood's recent work," that cold-working cannot reduce the size of these crystallites smaller than of the order 10-5 cm. The interesting correlation brought out by the experiments of Goetz and Wood is that the block size after severe cold-working is of the same order of magnitude as the groups that formed in the metal just before crystallizing from the molten state. The work of Ewald and Rennenger17 and the now classical experiments of Darwin and James12,13 all strongly suggest the existence of a periodic structure of crystal. lites smaller than the grain itself. Related to this effect is the appearance of veinlike markings in the microstructures. Ammer-man and Kornfeld,16 in their experiments, did not observe any evidence of veining in specimens of alpha iron annealed below A3 and believed that veining was not due to impurities in the iron, as Northcott16 suggested; veining was observed by them only in specimens annealed above A3. Hanemann,16 Schrader and Tangerding found that annealing in hydrogen did not diminish veining and so it could not be caused by oxides. They concluded that veining was due to a slight difference in the orientation of ferrite lattice blocks. This viewpoint is well supported by the evidence presented here.

Jan 1, 1941

By N. P. Goss

Asterism appearing in X-ray Laue diagrams is an extremely sensitive index of changes in the internal structures of individual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.l-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not conclusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made between mosaic and distorted grain structures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example: has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-l4 to 10-l5 c.c., or 10-15 cm. in size. These crystallites, or blocks, appear to survive the most drastic cold-working, for it has been shown, and more elaborately by Wood's recent work," that cold-working cannot reduce the size of these crystallites smaller than of the order 10-5 cm. The interesting correlation brought out by the experiments of Goetz and Wood is that the block size after severe cold-working is of the same order of magnitude as the groups that formed in the metal just before crystallizing from the molten state. The work of Ewald and Rennenger17 and the now classical experiments of Darwin and James12,13 all strongly suggest the existence of a periodic structure of crystal. lites smaller than the grain itself. Related to this effect is the appearance of veinlike markings in the microstructures. Ammer-man and Kornfeld,16 in their experiments, did not observe any evidence of veining in specimens of alpha iron annealed below A3 and believed that veining was not due to impurities in the iron, as Northcott16 suggested; veining was observed by them only in specimens annealed above A3. Hanemann,16 Schrader and Tangerding found that annealing in hydrogen did not diminish veining and so it could not be caused by oxides. They concluded that veining was due to a slight difference in the orientation of ferrite lattice blocks. This viewpoint is well supported by the evidence presented here.

Jan 1, 1941

By Herbert H. Kellogg

DEPOSITS of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (-325-mesh) sand assaying 95.5 per cent Si02, and a very fine (-3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. EXPERIMENTAL PROCEDURE The Sample.-The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.-By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fraction was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper.

Jan 1, 1945

The Pinto Valley, Arizona, plant of Cities Service Company is one of the newest copper producers in the United States, having started production in 1975. It is located a few miles west of Miami, Arizona, on the site of the Castle Dome Mine, a World War II operation which was shut down and its mill later moved and renamed the Copper Cities plant. The Pinto Valley concentrator uses six 18 ft (5. 5 m) diameter by 21 ft (6.4 m) long, 4000 hp, single-stage ball mills, taking crushed ore from four 7 ft (2. 13 m) standard and eight 7 ft shorthead crushers. It has a design capacity of 40,000 stpd but has higher tonnage capability for an expanded concentrator. The copper porphyry-ore is mined by two 15 yd and one 20 yd shovels (11.5 and 15.3 cu m) and is transported to the primary crusher by 150-ton trucks. The dump pocket is relatively shallow (14 ft or 4. 27 m deep); and because of the width necessary for the 150-ton trucks, it was designed to use the ore itself instead of manganese steel as an abrasion- resistant lining, although a heavy steel cap protects the dump pocket top edge. The pocket has a capacity of 300 tons of ore. Water sprays under the dumping positions direct a fog toward the truck being dumped for excellent dust control. Breaking of oversize is done by a hydraulic impact breaker mounted on a hydraulically operated articulated arm situated at the side of the dump pocket. Again because of the shallow pocket, no splitter is used to protect the spider of the 60 in. by 89 in. Traylor gyratory crusher, which is equipped with a hydroset mechanism. Crushed ore at 8 in. (203 mm) drops into the 360 st surge chamber lined with AR plate and then is fed directly to the 60 in. (1.52 m) stock- pile conveyor by an 84 in. by 20 ft (2. 13 m by 6.1 m) four-speed apron feeder at a rate of up to 4000 stph. Early in 1977, Cities Service will replace the four -speed electric drive with a hydraulic pump and motor with infinitely variable speed. They are also studying the replacement of the apron feeder with an 8 ft wide (2.44 m) belt feeder similar to those at Similkameen and Palabora. Peak crushing capacity would then be increased to 5000 stph. The AR plate in the crushed ore pocket was installed in large, rectangular sheets which required much less embedded metal to hold it in place than would the more conventional, smaller arid square pieces of cast manganese steel. For duty in the crushed ore pocket, where wear is not severe, the AR plate is a satisfactory material. The new Palabora Figure-8 crusher also uses this design.

Jan 1, 1978

By F. N. Rhines, W. S. Pellini

In many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummerl have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium of experimentation. New values obtained in this way are believcd to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by X. S. Dean2 and by E. E. Schumacher and F. C. Nix. Their points are represented in Fig. I. In their work the solidus was not located at antimony collcentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228OC.; J. E. Stead,7 24g°C.; Campbell,8 228°C.; W. Gontermann,9 245' to 252°C.; R. Loebe,lo 245°C.; E. Heyn and 0. Bauer,ll 245°C.; H. Endo,12 250°C.; R. S. Dean,= 247' to 258°C.; E. Abel, O. Redlich, and J. Adier,13 245°C.; W. Broniewski and L. Sliwowski,14 250' to 252°C.; H. Seltz and B. De Witt,4 25o°C. A temperature of 247°C. appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 247°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1943

By W. S. Pellini, F. N. Rhines

In many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummerl have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium of experimentation. New values obtained in this way are believcd to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by X. S. Dean2 and by E. E. Schumacher and F. C. Nix. Their points are represented in Fig. I. In their work the solidus was not located at antimony collcentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228OC.; J. E. Stead,7 24g°C.; Campbell,8 228°C.; W. Gontermann,9 245' to 252°C.; R. Loebe,lo 245°C.; E. Heyn and 0. Bauer,ll 245°C.; H. Endo,12 250°C.; R. S. Dean,= 247' to 258°C.; E. Abel, O. Redlich, and J. Adier,13 245°C.; W. Broniewski and L. Sliwowski,14 250' to 252°C.; H. Seltz and B. De Witt,4 25o°C. A temperature of 247°C. appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 247°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1943

By Thomas A. Read

The internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of ioo when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose—that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals mill be presented. Experimental Procedure The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrcment A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders M in. in diameter and I 1/2 to 21/2 in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is 1/4 in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Thomas A. Read

The internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of ioo when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose—that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals mill be presented. Experimental Procedure The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrcment A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders M in. in diameter and I 1/2 to 21/2 in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is 1/4 in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Harold Margolin

The Ti-Al system certainly merits the investigative attention it has been receiving and this latest contribution by Blackburn is therefore to be welcomed. The titanium-rich end of the phase diagram shown here, as well as the diagram by crossley,17 Clark et a1.,18 and Tsujimoto and Adachi,29 reveal no other intermediate phase than Ti3A1, although a previous work by Ence and Margolin20 had reported an additional intermediate phase. Since then, Buerger Precession pictures of single crystals of 10.5, 11.5, and 12.5 wt pct A1 were made at New York university21 and the extinctions were found to be typical of a D6h a Ti structure. Some superlat-tice spots and/or streaks suggesting the presence of an Mg3Cd structure, i.e., Ti3Al, were also found. Since these specimens had been quenched from the y region20 and had revealed a Ti, it was concludedz1 that y does not exist and the structures interpreted as m + y could not be so considered. The absence of normal two-phase behavior in these structures had been indicated in the paper. Accordingly, the two-phase region y + 6 becomes a + Ti3Al and there is some agreement between the results of Blackburn and of Ence and Margolin20 as to both shape and existence above 900°C of an a + Ti3Al field. Crossley 17 proposed that Ti3Al is a line compound which decomposes congruently at 900°C. It is difficult to discount entirely the fact that clear two-phase structures, varying in amount with position in the two-phase field, could be detected above 900°C by Ence and Margolin.20 Precipitation during quenching could not have been so regular and the twin-phase syndrome17 does not apply. The heat treatment and quenching technique was essentially the same as was used by Crossley, whereas Blackburn, who used a rapid quenching procedure, also showed a two-phase a + Ti3A1 field above 900°C. If the two-phase field exists above 900° C, it is easy to picture a two-phase field which could account for the data of Crossley below 900°C without invoking a line compound existence of Ti3A1. All that would be necessary would be an 0 + Ti3Al/Ti3Al boundary which curved sharply to higher aluminum contents below 900° C. It is clear that the controversy must be solved by techniques which obtain data at elevated temperatures without quenching. It is conceivable that the difference in width of the a + Ti3N fields reported by Blackburn and by Ence and Margolin is due to the longer annealing times used by the latter investigators. The criterion for establishment of equilibrium in our work20 was the

Jan 1, 1969

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947

By Ronald C. Koo

THE effect of grain size on the mechanical properties of the bcc metals has been a subject of intensive theoretical and experimental study.'-l5 Quantitative relationships have been established experimentally between yield stress and grain size and between the ductile-brittle transition temperature and grain size in a number of metals.6"15 Much significance has therefore been attached theoretically to the grain size dependence. In all these experiments, different grain sizes were always achieved by annealing specimens at various temperatures. The implicit assumption was that any change in the dislocation substructure or in the distribution of impurities which might occur simultaneously with the production of various grain sizes had only a negligible effect on the mechanical properties. The validity of this assumption, however, is questionable. transformation in iron-nickel alloys is actually an extraneous phenomenon due to inadvertent compositional changes in the martensite if the heating rate is not sufficiently rapid. This complication can be avoided by up-quenching for the reversal treatment,5 and then the stabilization does not appear. Clearly, the lattice imperfections and strengthening produced by the reverse transformation are not responsible for the marked stabilization which has been observed by other investigators in these alloys. Data will be presented in this note to show that, at least in recrystallized tungsten of commercial purity, the difference in the ductile-brittle transition temperature of specimens annealed at various temperatures is more a result of a variation in the distribution of impurities rather than of the difference in grain size produced by the anneal. Ductile-brittle transition temperatures in tension were determined on powder-metallurgy tungsten specimens recrystallized at various temperatures. Tensile specimens having a gage length of 1.50 in. and gage diam of 0.18 in. were recrystallized at 1450°, 2000°, 2350°, 2550°, 2750°, or 2800" for 30 min in a vacuum furnace at a pressure of 1 x 10"5 mm of Hg and then tested at a constant extension rate of 8 x 10 per sec in an argon atmosphere from 100" to 800". Typical quantitative analyses of impurities are given in the Table. These results show that, within the precision of the analyses, see Table, annealing did not result in any detectable change in the impurity contents of the specimens, nor was there any detectable difference in purity between specimens having large differences in grain size annealed at the same temperatures . The results of the tensile tests yielded three distinct ductile-brittle transition curves approximately 225' apart. As shown in Fig. 1, data of specimens annealed at 1450°C and those of specimens annealed at 2000°C (O) fell on Curve A. Data of specimens annealed at 2350" and 2550°C fell on Curve B, and those of specimens annealed at 2750" and 2800°C fell on Curve C. The decrease in ductility with increase in annealing temperature became so pronounced that one third of the specimens annealed at 2750" and two thirds of the specimens

Jan 1, 1963

By M. J. Stewart, F. Weinberg

PREVIOUS investigations into convective flow in molten metals have examined systems in which the length-to-height ratio of the enclosure is large, usually using long graphite boats.''2 In normal castings this ratio is generally small and it is not possible to extrapolate the results of previous work to casting configurations. The present investigation was undertaken to examine liquid flow in systems of low length to height ratio. The apparatus used for the experiments is shown in Fig. 1. The molten zone of tin is contained in an aluminum mold of inside dimensions 6.4 by 6.4 by 0.31 cm. A heating block containing a resistance coil is attached to one end of the mold and a cooling block is attached to the other end. These are used to produce a wide range of temperature differences across the mold. The mold is contained in a stainless steel tank which is heated from the outside by resistance heaters to give the required operating temperature during the experiment. Temperature measurements in the molten tin are made with an iron-constantan thermocouple PT equal to 5 atm. The phase diagram derived by us was the same as that found by Krivsky and Schuhmann, except for a similar discrepancy in one boundary line representing the gas composition in equilibrium with SO a. The vapor pressures of the pure components can be neglected at 1700°K, 1 atm and 2500°K, 5 atm. There-fore, in these cases PT is essentially the total pres-sure in the system. This is valid for all the diagrams presented by Krivsky and Schuhmann except for the one at 2500°K and 0.01 atm, where the vapor pressure of silicon is comparable to PT.6 This work was supported in part by the American Iron and Steel Institute. 'C. E. Wicks and F. E. Block: Thermodynamic Properties of 65 Elements, U S. Bur Mines, Bull. No. 605, 1963. R. P. Elliott: Constitution of Binary Alloys, 1st supplementary, McGraw-Hill Book Co., New York, 1965. 3W. A. Krivsky and R. Schuhmann, Jr.: Trans. TMS-AIME, 1961, vol. 221, pp. 898-904. 4M. F. Ancey-Moret, M. Olette, and F. D. Richardson: Mem. Sci. Rev. Met., 1964, vol. 61, pp. 169-76. 5J . F. Elliott and M. Gleiser: Thermochemistry for Steelmaking, vol. 1. Addison-Wesley, Reading, Mass. 1960. 6 J.Drowart, G. De Maria, and M. G. Ingraham: J. Chem. Phys., 1958, vol. 29, p. 1015. probe of 0.4 mm diam inserted into the open top of the mold. Radioactive sn113, in the form of a small sphere, was gently lowered into the molten tin at point A in Fig. 1 THERMOCOUPLE> WATER ARGON END HEATER QUENCH ARGON Fig. 1—Apparatus for detecting liquid flow. Point A indicates position the tracer was introduced.

Jan 1, 1970

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947

By G. T. Higgins

PREVIOUS workers1,2 have found evidence of exaggerated grain growth or secondary recrystallization on annealing sponge zirconium at temperatures high in the a, phase field, but no details of the orientation relationship between the secondary grains and "as-recrystallized" matrix were reported. In other hexagonal metals, namely dilute Mg-A13 and Cd-zn4 alloys, secondary recrystallization has been observed in which the secondary grains are related to the primary recrystallized structure by rotations about the c axis. These rotations are thus comparable with the rotations about the (111) axis observed in the secondary recrystallization of fcc metals. In the current work secondary recrystallization has been observed on annealing iodide zirconium at 800°C and the associated changes in crystallographic texture have been examined. The material employed was arc-melted iodide zirconium of the following composition: Impurity O H Fe Hf Pb I Ni C1 A1 ppm by wt 130 5 230 98 23 28 200 39 30 This was received as 0.25-in. plate, and, prior to the annealing studies, was cold-rolled to 0.040 in. Specimens 1 in. sq were chemically polished and annealed for various times at 800°C in a vacuum better than 5x 10-6 Torr. For metallographic examination specimens were first chemically polished and then anodized8 to enhance contrast between the grains when examined under polarized light. Changes in crystallographic orientation associated with the development of secondary grains were followed by (1011) and (0002) pole-figure determinations using a conventional Schulz goniometer in reflection. Filtered Cr Ka radiation was employed and great care was taken to avoid spurious re- sults due to the close proximity of the Bragg angles for the (1011) and (0002) reflections. Figs. 1 and 2 illustrate the change in grain structure on annealing at 800°C. After 24 hr the structure has ceased to be equiaxed due to the development of certain grains in preference to others. It is notable that the secondary grains do not grow to the extent observed in sponge zirconium.1,2 This appears to be due in part to the fact that normal grain growth is inhibited in the less pure sponge zirconium, with the result that the driving force for secondary recrystallization remains high, while at the same time the number of grains able to develop in the presence of the impurities is also smaller. As a consequence, in sponge zirconium those grains that do develop preferentially are able to grow into the fine -grained matrix without impingement, while in iodide zirconium the preferential growth of many grains leads to early impingement. The pole figures determined for specimens annealed for 5 min and 24 hr at 800°C are illustrated respectively in Figs. 3 and 4. These indicate that the dominant feature of the initial recrystallized texture consists of basal planes at an angle of 321/2 deg to the sheet surface, with a (1120) axis lying parallel to the

Jan 1, 1967

By W. S. Pellini, F. N. Rhines

IN many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummer1 have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium 0f experimentation. New values obtained in this way are believed to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by R. S. Dean2 and by E. E. Schumacher and F. C. Nix.3 Their points are represented in Fig. I. In their work the solidus was not located at antimony concentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228°C.; J. E. Stead,7 247°C.; Campbell,8 228°C.; W. Gontermann,9 245° to 252°C.; R. Loebe,10 245°C.; E. Heyn and 0. Bauer,11 245°C.; H. Endo,12 250°C.; R. S. Dean,2 249° to 258°C.; E. Abel, 0. Redlich, and J. Adler,13 245°C.; W. Broniewski and L. Sliwowski,14 250° to 252°C.; H. Seltz and B. De Witt,4 250°C. A temperature of 249°C- appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 249°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1942

By J. B. Clemmer, F. D. DeVaney, H. A. Doerner

PRODUCTION of magnesium metal in the United States during the past decade has increased from less than 6oo,ooo lb. in 1928 to more than 4,800,000 lb. in 1938.1 The growing industry has stimulated interest in methods of production and in sources of raw material. All of the present domestic production is from brines. However, the availability of large tonnages of magnesite in the state of Washington, together with the possibility of cheap power, have created interest in the utilization of magnesite for the production of magnesium metal as well as for other purposes. Magnesite, the carbonate of magnesium (MgCO3), usually is associated with limestone (CaCO3) and dolomite (MgCO3CaCO3). It occurs in crystalline and microcrystalline (sometimes termed amorphous) forms.2 The more common crystalline mineral is found in various shades of white, gray, yellow and brown, the colors being due to impurities, chiefly iron. Magnesite has a hardness of 3.5 to 4.5 and a specific gravity of 3.0 to 3.1. It forms rhombohedral crystals in the hexagonal system, having a vitreous, pearly luster. The quarries and mines of the Northwest Magnesite Co. near Chewelah, Wash., are large producers of magnesite for refractories. The deposits are extensive, some veins being hundreds of feet wide. The boundaries of the veins are indefinite, and the magnesite is interfingered with dolomite. Calcite, talc, serpentine, quartz and shale are disseminated through the deposits. The quality of the ore cannot be determined by appearance or by simple tests; chemical analysis is required. These features make it difficult to determine the boundaries or total quantity of workable ore.3 Only the higher-grade ores are mined, and a considerable proportion of the magnesite content is discarded by hand-sorting and log-washing methods. After calcining, the sorted product meets the specifications for usual refractory material, as it contains approximately 81 per cent MgO, 7 per cent Si02, 6 per cent CaO and 6 per cent Fe203 + A1203. A sample of the reject material had the following analysis after calcining: 65.4 per cent MgO, 6.3 CaO, 21.1 Si02 and 6.5 R203. The percentage reported as R203 includes compounds whose chlorides are acid-soluble but give precipitates in ammoniacal solution that are ignited and weighed. The more common constituents are Fe203, A1203 and Ti02. The sorted magnesite product is not the best grade, even for refractory purposes, and leaves much to be desired for a reduction process. The rejected material contains a large proportion of magnesite. It is apparent that an effective concentration method would yield a higher recovery and a better product. In general, the refractory grade is not suitably pure for other uses. Recent developments in the production of

Jan 1, 1940

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine ( — 325-mesh) sand assaying 95.5 per cent SiO2, and a very fine (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotalion Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine frac- . tion was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1948

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine ( — 325-mesh) sand assaying 95.5 per cent SiO2, and a very fine (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotalion Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine frac- . tion was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1948

By D. H. Baldwin, R. E. Reed-Hill

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By Cuppam Dasarathy

THE object of this note is to report briefly certain results of investigations on the Fe-In phase diagram. BISRA-high purity H-iron and 99.9 pct pure indium were used to prepare the alloys. The experimental techniques consisted of thermal analysis, optical metallography, and X-ray diffraction. A phase diagram based on the present results as well as those reported earlier by the author' is shown in Fig. 1. It is seen that the liquidus points fall on a smooth line which meets the monotectic isotherm at 1470°C. The liquidus extends up to 3.4 at. pct In. The phase boundary separating the two liquidus L1 and L2 is shown dotted. The experimental solidus meets the monotectic isotherm at -0.9 at. pct In. The 6/6 + L2 boundary drops steeply to the 6 + La/y + L2 boundary at -1350°C. In this region, it is impossible to detect satisfactory thermal arrests because of the steep phase boundary. The present diagram shows that indium lowers the temperature of the d/y transforma-tion and raises the temperature of the y/a transfor-mation. The y +d region is found to be very narrow. Indium gives rise to a restricted y field when alloyed with iron. The width of this field is between 0.4 and 0.5 at. pct In. Details of the alloys containing 40 and 50 at. pct In have already been reported by the author' and the transformation temperatures of these alloys are included in Fig. 1. It appeared from optical metallography and X-ray diffraction that the room temperature solubility of indium in a iron is less than 0.28 at. pct since alloys of 0.28 at. pct In and above, slow cooled to room temperature, contained dark etching second phase particles situated both in the matrix and grain boundaries of the a-grains, see Figs. 2 and 3. These particles were identified to be unalloyed indium by X-ray diffraction. The lattice parameter of the a phase reached a maximum of 2.8672A at the indium level of -0.28 at. pct. The present diagram, Fig. 1, is in substantial agreement with that of Stadelmaier and Fiedler' except for certain differences in detail. For example, they found the monotectic composition and temperature to be 7.0 at. pct In and 1443oC, respectively, while the present work indicates them to be 3.4 at. pct In and 1470°C. The 6 + L2/y + L2 transformation is indicated in the present work to occur at -1350°C, whereas Stadelmaier and Fiedler find this to occur at -1320°C. They also claim that the width of the y field is 0.2 at. pct In while the present work shows the width to be between 0.4 and 0.5 at. pct In. 1) Indium, when alloyed with iron, gives rise to a restricted y field, the width being >0.5 at. pct In.

Jan 1, 1970