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By C. L. Mantell

When considered from the viewpoint of world annual output, tin is one of the rarest metals. Its annual production is exceeded by that of iron, copper, lead, zinc. aluminum, magnesium; probably by that of the ferroalloys of manganese, chromium, and silicon, and possibly by the world production of sodium; while it exceeds only the output of such common metals as nickel, antimony, mercury, tungsten, molybdenum, silver, gold and the precious metals. Cassiterite, or tinstone, until the second World War was the only mineral that was an important source of tin. This mineral is frequently called "tin ore." The use of the term should be restricted to the ore containing the mineral, and not, in addition, to the concentrates of the mineral obtained from the ore or from stanniferous alluvial deposits. There is a general misuse of the term "tin ore" in the Malay Peninsula and adjacent localities, particularly where most of the mineral is obtained from secondary stanniferous deposits. The term "cassit-erite" is exclusively used in mineralogical, geological, and other scientific writings; it is unfortunate that it is not mole frequently used when referring to the occurrence of the mineral on an economic scale. Ores "Tinstone" js a very convenient old English term deserving a more frequent use. Tinstone is a dioxide of tin, or stannic oxide. When chemically Pure, as in the very rare transparent variety, it has a metallic content of 78.6 per cent tin. Frequently, however, the crystals and grains contain appreciable amounts of impurities, chiefly iron and tantalum. The impurities here referred to are those actually in the mineral itself. Tinstone usually has a deep brown or black color with an adamantine luster. Several other colored varieties are known, among them red ruby tin, yellow rosin tin, and yellow wax tin. the names jn each case being descriptive of the mineral's appearance. Ainalite is a variety of cassiterite con-taining almost g per cent of tantalum pentoxide. Sparable tin, tooth tin, and needle tin, as a result of their acute dite-tragonal pyramidal crystalline form, re-ceive their names from their crystallo-graphic appearance. Wood tin is a compact variety of cassiterite composed of radiating fibers resembling dry wood. Toad's-eye tin is a similar variety on a smaller scale in which the fibers appear to resemble the eye of a toad. Stream tin is water-worn tin-stone. Float tin is sometimes employed to describe the cassiterite occurring in soil derived from the weathered surface of a mineralized area. Stannite is an ore of tin of lesser impor-tance than cassiterite. It is a sulphide of tin, copper, and iron, sometimes known as tin pyrites or bell-metal ore. Its chemical com-position is sometimes expressed by the for-mula Cu,S.FeS.SnSz with zinc usually present in varying quantities. The tin con-tent varies from 22 to 27 per cent and there is about 29 per cent of copper, 13 per cent of iron, and 30 Per cent of sulphur.

Jan 1, 1944

By N. A. Zeigler

GRaphitization phenomena occurring in solid cast iron have principally been studied from the angle of the reactions taking place during annealing of white castings in the manufacturing of malleable iron. The selected bibliography at the end of this paper presents the high spots of the published information in this field. Graph-itization of gray iron upon reheating has received much less attention, primarily because only on rare occasions is this material subjected to any kind of industrial heat-treating. Moreovcr, articles made from gray iron are seldom used commercially at temperatures when any graphitization can take place. When used in such conditions, it is assumed that the articles can be replaced at frequent intervals, which can be afforded because of the low cost of gray iron. However, there is at least one commercial process in which articles made from gray iron, during their manufacturing processing, are subjectcd to rather high temperatures; that is, manufacturing of cast-iron enamelware, which is glazed at about 1600° to 1700°F. (870' to 930°C.) From practical experience, it has been found that one of the convenient and economical compositions of gray iron suitable for enameling is, in round figures, as follows: Si, 2.50 per cent; Mn, 0.35; S, 0.07; P, 0.80; T.C., 3.35; C.C., 0.70. Since this iron usually is cast into thin-walled sections, the percentage of com- bined carbon in it is relatively high. Upon heating in the enameling furnaces, this combined carbon graphitizes, which causes permanent dimensional changes of the articles. Obviously, from practical considerations, it is desirable to maintain these dimensional changes as constant as possible. In the course of experimentation with this iron, two series of experimental heats were prepared in which the manganese to sulphur ratio of the standard cupola metal was offset by ladle additions of: (I) progressively larger amounts of sulphur, and (2) progressively larger amounts of manganese. Each one of these ladle charges was cast into experimental plates 8 by 4 in. and about 5/16 in. thick. All told, 13 ladle charges were thus treated. All of them are listed in Table I, together with their chemical analyses. It may be noted that the manganese to sulphur ratio in these samples ranges between 1.2 and 30.2. Every one of these compositions was subjected to thermal allalysis, using an automatic, self-recording differential dila-tometer. The specimens used in this instrument are 50 mm. long and 4 mm. in diameter. During the dilatometer cycle they are kept under a vacuum of about 3 microns. Each one of them was subjected to a thermal cycle by heating it to I830°F. (1000°C.) in 3 hr. and cooling to room temperaturc in 5 hr. Figs. I, 2 and 3 present three automatically recorded dilatometer curves for irons: Serial No. I (normal composition), Serial No. 6 (high sulphur), and Serial No. 13 (high manganese). All three of these figures are

Jan 1, 1945

By Arthur Lubinski, K. A. Blenkarn

It is explained why the bottom portion of freely suspended tubing in a pumping well buckles and straightens in succession during the pumping cycle. Field evidence of resulting rod-on-tubing wear, excessive polished rod load, and excessive horsepower are given. The possibility that buckling hastens pump wear is strongly suggested. Means for either prevention of buckling or for mini-mizing its effects are explained, their relative merits compared, and field results of their use given. These means are: tension anchors, tail pipe, sucker rod guides, and corrosion inhibitors. Charts and formulas for best use of tension anchors, tail pipe, and guides are given. Use of tension anchors, or compression anchors with a heavy tail pipe, prevents both buckling and breathing, thus improving volumetric efficiency. Without tail pipe, buckling above compression anchors precludes such improvement. INTRODUCTION It is well known that a column must be subjected to some compression in order to buckle; and also that a structural member does not buckle if subjected to a tension. When consideration is given to a tubular column, the question may be asked, "How is the buckling phenomenon affected by inside or outside pressure?' At first, it seemingly should not be affected. However, this is not so. In order to arrive at a correct deduction one should first understand the basic reasons for buckling of a column under loading*. Then he should add to the effect of that loading the effect of pressure. Following this procedure, one may discover quite unexpected phenomena. In some cases, when subjected to more pressure inside than outside, a pipe may buckle under tension. In other cases, a pipe may remain straight, although subjected to a very large compression. In 1950 and 1951 it was explained why the bottom portion of a string of pipe freely suspended in a well does not buckle even when subjected to a large compression due to buoy- ancy.2,3 It was shown that the com-monly used concept of a neutral point, as being a point in the string with neither compression nor tension, is inadequate, and a more relevant definition of the neutral point was introduced. The findings were also generalized to cases of different pressures inside and outside a pipe.3a Later, in a further generalization, allowance was made for variations of stress and pressure with depth.' The findings were applied to the new technique of hydrostatic high pressure testing of lengths of pipe in the mill.5 In 1952 it was observed that previous theoretical findings apply to tubing in pumping wells. The lower part of freely suspended tubing buckles during the upstroke portion of the pumping cycle. Later, it was ascertained that this phenomenon is responsible for wear and malfunctioning of the equipment. Various remedial measures were devised and successful field trials conducted. Only brief mentions on the subject have been published.6,7 In this paper, the phenomenon of tubing buckling is explained, field

Jan 1, 1958

By D. F. Gibbons

THIS investigation was undertaken in order to gain further information on the mechanism of plastic deformation of iron at temperatures between room temperature and 77.2°K, and also to contribute to our understanding of the low temperature brittleness phenomenon that occurs in both the tensile and impact tests. It was decided to study as pure an iron as possible and to use the tensile test in order to simplify the problem as much as possible. Two series of iron were used throughout the investigation: iron A, obtained from the National Research Corp. and supplied as gas-free, high purity iron; and iron B, obtained from Fast' and produced by melting iron under purified hydrogen. Typical analyses of samples of both irons, after fabrication, are given in Table I. The main difference in composition of these irons is in their nickel and oxygen contents. Nickel has a very large solid solubility in iron. However, oxygen has an extremely small solid solubility. An attempt was made to reduce the oxygen content still further by remelting under purified hydrogen. This was successful in reducing the oxygen content to -0.0006 pct. However, no results on tests of this iron are included, since difficulty was encountered in fabricating the ingot. Wire specimens 1 mm in diameter were used for the investigation. The wires were produced from the ingots, as supplied, by cold rolling and swaging, with intermediate vacuum anneals at 700°C. Care was taken to reduce preferred orientation in the wires to a minimum by keeping the percentage of reduction in area between anneals of 30 to 40 pct. X-ray transmission photographs showed no indication of preferred orientation. The final grain size of iron A was 20 to 24 grains per linear mm and of iron B, 16 to 18 grains per linear mm. All specimens were tested in the decarburized and denitrided condition unless otherwise stated. The procedure was to pass hydrogen, saturated with water vapor at 26oC, over the specimens at 730°C for 2 hr. The specimens were quenched in iced water and then annealed in a vacuum of - 5x10-6 mm Hg for one day at 560°C to remove hydrogen. Higher temperatures were used for the vacuum anneal but this temperature was found to be quite satisfactory in removing hydrogen. The specimens were slow-cooled after the vacuum anneal. Where it is stated that the specimens were carburized, the specimens were given an identical decarburizing treatment and then carburized by passing hydrogen, saturated with pure n-heptane vapor at 0°C, over the specimens at 730°C. The specimens were then homogenized at 730°C for 2 hr in dry hydrogen. After the carburizing treatment the specimens were given the same vacuum anneal as for the decarburized specimens. The carbon content was determined from the maximum value of the internal friction carbon peak.2 Apparatus Fig. 1 shows a diagram of the tensile apparatus, with half the cooling coil removed. The cooling coil enabled temperatures from 200" to 77.2oK to be obtained. The apparatus was designed to fit a standard Tinius Olsen Universal tensile machine. The apparatus consisted of the rigid plate A which carried two carefully machined hooks H. These hooks attached the plate firmly to the moving crosshead of the tensile machine. The lower grip B was rigidly suspended from the plate A by three stainless steel rods. The upper grip C was joined to the upper grip of the tensile machine by the stainless steel rod E. The lower part of the apparatus was surrounded by a Dewar vessel, which was made a sliding fit inside the brass collar D. The specimen was held in a clamp which fitted into the grip, forming a ball and socket joint (see inset a). This was to attain as nearly pure

Jan 1, 1954

By Bernard S. Borie

THE U-A1 binary system has been studied by Kaufmann and Gordon.' They have shown that three intermetallic compounds occur in the system: UAl², UAl², and a third compound tentatively identified as UA15. UA1³ is simple cubic, a, = 4.26A. Its unit cell contains one formula weight, and it is iso-morphous with AuCu³. UA1² is face-centered cubic, a, = 7.72A, with eight formula weights per unit cell. Rundle and Wilson have shown that it is iso-morphous with Cu²Mg.² A Debye-Scherrer pattern of the Al-rich compound indicated a more complex structure than either UA1² or UA1³. The following is a report of an investigation of the crystal structure of this compound and a determination of its stoi-chiometric formula. A melt of uranium (99.9 pct pure) and aluminum (99.9 pct pure) was prepared which contained about 25 pct U by weight. It was cooled from 950" to 650°C at a rate of 500" per hr and then taken from the furnace and air cooled. An X-ray diffraction pattern of the ingot showed only lines of aluminum and the Al-rich compound. Filings from the ingot were reacted with a solution of sodium hydroxide, producing a fine black powder, the diffraction pattern of which showed no traces of aluminum. A comparison of the Debye-Scherrer pattern of our sample with the data published by Kaufmann and Gordon1 showed that it is identical with the Al-rich phase which they reported. Single crystals were obtained by cooling the melt more slowly (about 50°C per hr). After reaction with sodium hydroxide, the crystals appeared as small black needles attached to the ingot surface. Cell Size, Space Group, and Uranium Positions A series of Weissenberg photographs for rotation about two of the crystallographic axes, taken with copper radiation filtered through nickel foil, revealed an orthorhombic cell of dimensions: a = 4.41 ± 0.02A b = 6.27 ± 0.02A c = 13.71 ± 0.03A Reflections of the type hkl were observed only if: h + k + I = 2n, of the type hkO only if: h = 2n and k = 2n, of the type h01 only if: h + 1 = 2n, and of the type Okl only if: k + 1=2n. Hence, the cell is body-centered with an 001 glide plane. The evidence for the existence of the glide plane is the observed extinction of 23 possible re- flections of the type hkO with at least one index odd. There are only two space groups consistent with these data: C"" — I2ma and D28 2h — Imma.³ he possible sets of atomic positions for these space groups are: 12ma: (0 0 0; ½ ½ ½) + 4: (a) x 0 %; x % % (b) x ¼ z; x ¾ Z 8: (c) x y z; x y z; x, ½ + y, Z x, M - y, z Imma: (0 0 0; ½ ½ ½) + 4: (a) 0 0 0; 0 ½ 0 (b) 0 0 ½; 0 ½ ½ (c) ¼ ¼ ¼; ¾ ¼ ¼ (d) ¼ ¾ ¾ ; ¾ ¾ % (e) 0 ¾ Z; 0 ¾ z 8: (f) x 0 0; x 0 0; x 1/2 0; x ½ 0 (g) ¼ Y ¼; ¾ Y ¾; ¾ y ¼; 1 y ¼ (h) 0 y z; 0; ;; 0, ½ + y, z; 0, l/2 - Y, Z (i) x 1/4 z; x ¾ z; ¼ z; x ¾ z 16: (j) xy z; x y z; x y z; x y z; x, ½ + y, Z; x,½ - y, z; x, ½ - y, z; 11 1, + y,Z Though density measurements on different samples were found to vary somewhat, they were all within the range 5.7 * 0.3 g per cu cm. If it is assumed that the unit cell contains four formula weights of UAl,, it is 6.5 g per cu cm. If there were as many as eight uranium atoms per unit cell, the

Jan 1, 1952

By M. J. Sinnott

WITH the advent of nodular iron as an engineering material, considerable interest has been shown in developing this material for various applications. Generally the strength, hardness, or ductility are the more common properties used for design purposes but occasionally applications involving a knowledge of the thermal conductivity of the material is required. A search of the literature showed, rather surprisingly, that relatively little work has been done on this property for all types of cast iron. Insufficient data are available on thermal and electrical conductivities to develop the Weidemann-Franz ratio, or the Lorentz relationship, for estimation purposes. There are no data on nodular irons and the published data on malleable irons are quite sketchy. For these reasons the conductivity of the group of nodular irons listed in Table I were measured. Irons I to IV were made in such a fashion as to maintain the carbon and alloy content essentially the same while varying the silicon content. Test specimens were cut from the mid-section of 4-in. keel castings. Iron V is a commercial casting of nodular iron. The test specimen of this iron was cut from the center of a large cast billet 3x10x26 in. All alloys were tested in the as-cast condition. A microstructural examination showed that each iron had spheroidal graphite but the size and distribution varied with the silicon content of the iron. The spheroid size decreased while the number of graphite nodules increased as the silicon content of the iron was increased. The matrix structures of each iron consisted of pearlite and ferrite with the proportions varying from predominantly pearlite in the low-silicon iron to mostly ferrite in the high-silicon iron. The commercial heat, iron V, was predominantly pearlite probably because of its higher manganese and phosphorus content. Two methods for measuring the thermal conductivity were used. The first was a modification of the techniques described by Powell and Hickman and Van Dusen and Shelton,² the second method was a simpler technique described by Jakob and Hawkins." Since the agreement of both methods as tested on two sets of duplicate samples was excellent, the simpler experimental technique was used. The results of the measurements are given in Table II along with a summary of the microstructural constituents. These conductivity data indicate that as the percentage of silicon increases there is a corresponding decrease in the thermal conductivity even though the structure is changing from pearlitic to ferritic. Such a change in microstructure is usually accompanied by an increase in conductivity. A third factor involved in the behavior of these irons is the size and distribution of the graphite nodules. The relative amounts of graphite do not change greatly but the size and distribution do. Generally graphite improves the conductivity but in the present case such an effect is probably masked by the alloying effect from the silicon and its dispersion through the matrix. The thermal conductivity of the nodular irons studied is less than that of regular foundry irons by some 10 to 30 pct and is less than that of regular malleable irons.' The cause of the decreased conductivity is probably the more highly alloyed fer-rites obtained in these irons and the changed mode of distribution of the graphite as compared to the regular foundry irons. References R. W. Powell and M. J. Hickman: Journal Iron and Steel Inst. (1946) 154, No. 2, p. 99. 'M. S. Van Dusen and S. M. Shelton: U. S. Bur. Standards Journal of Research, RP668 (1934) 12, p. 429. ³M. Jakob and G. A. Hawkins: Elements of Heat Transfer and Insulation. 2nd Ed. (1950) New York. John Wiley and Sons. ' J. W. Donaldson: Journal Iron and Steel Inst. (1933) 128, No. 2, p. 255.

Jan 1, 1954

By L. H. Schwartz, S. K. Lahiri, M. E. Fine, D. Chandra

WHILE the yield stress of solution treated Fe-Cu alloys increases rapidly with aging, a precipitate has only been directly observed in overaged samples.'-" This precipitate is essentially pure fcc copper, the E phase. Hornbogen2 suggested that the initial hardening is due to clustering of copper atoms in a bcc iron matrix. Hornbogen was not able to obtain direct confirmation for such bcc clusters by either X-ray diffraction or electron microscopy; however, he did observe analogous clustering in Fe-Au alloys7 where the scattering factor difference between iron and gold is more favorable than that for iron and copper. Fujii, Nemoto, Suto, and Monma4 recently observed diffuse electron diffraction scattering in a 2.5 pct Cu alloy aged at 500°C: for 30 hr. They suggested that part of the diffuse SCattering was due to a modulated structure of 26 to 42 wavelength parallel to the (110) matrix plane. This disappeared with further aging. However, 30 hr at 500°C is well beyond the peak strengthening in this alloy which occurred at less than I hr at 500oc.4 By transmission electron microscopy they could not distinguish between quenched samples and samples aged to maximum strength. The purpose of the present investigation was to try to obtain further confirming evidence for a precipitation stage preceding the formation of the fcc E phase. Change in Young's modulus was selected for study be- EXPERIMENTAL PROCEDURE The Fe-1.67 at. pct Cu alloy was supplied by the U.S. Steel Corporation in the form of a hot forged rectangular bar. The carbon and nitrogen contents of this alloy were 70 ppm and less than 10 ppm, respectively. The samples for Young's modulus measurements were made by cold swaging to & in. diam and cutting to 2 in. lengths. Tensile test samples 1 in. long were prepared by cold rolling to a thickness of 0.012 in. and then machining to gage dimensions of 0.5 by 0.012 in. For Mijssbauer studies, foils 1 mil thick were prepared by cold rolling. During fabrication the alloy was given intermediate anneals at 845OC followed by quenching. The specimens after preparation were solution treated at 1000°C (y field) or 845°C (a field) for 1 to 2 and 5 to 6 hr, respectively, in a dynamic vacuum of about 2 x lom6 torr. The tensile and modulus specimens were drop-quenched into iced brine through an aluminum foil which vacuum-sealed the bottom of the furnace tube. The MOssbauer foils were drop-quenched into helium gas cooled by passing through N2 (liq) in a copper coil. The grain diameter of the modulus and tensile specimens was between 0.025 and 0.035 mm. The samples were aged from 400" to 500°C in a dynamic vacuum of 2 x 10-6 torr and cooled by pulling into a water-cooled portion of the vacuum system. The dynamic Young's modulus was measured at room temperature using electrostatic excitation and detection of longitudinal vibrations.' Neglecting any length change during the aging, (this is expected to be comparatively small), the fractional change of Young's modulus (?Et)/Eav, is equal to twice the fractional change of the resonant frequency (?ft)/fav . ?ft =ft —fo where fo and ft are the resonant frequencies of a specimen before aging and after aging to time t. The measured f's, approximately 51,000 cps, were corrected to 25°C for any variation in the ambient temperature. The tensile tests reported were carried out at room temperature in an Instron with a 1000 lb full scale load cell. The flow stress reported herein corresponds to a strain of 0.002. The Massbauer spectra were taken in a constant acceleration model AM-1 NSEC spectrometer. The

Jan 1, 1970

By A. E. Zawadzki

A progress report is presented on the development of a process for the removal of sulfur dioxide from flue gases. Catalytic oxidation of the sulfur dioxide in flue gases, with the production of recoverable sulfuric acid, has been demonstrated to be technically feasible. Problems associated with the process are discussed. The need for an inexpensive and efficient process for controlling sulfur dioxide emissions from utility plant stacks has been accentuated by the ever-increasing public demand for elimination of all man-made air pollutants. I would like to describe the results of an investigation of the development of such a process; more important, I would like to present a discussion of the problems associated with the process which remain to be solved. The research work on the BCR catalytic gas phase oxidation process has been jointly sponsored by the Association of Edison Illuminating Cos., Edison Electric Inst. and Bituminous Coal Research, Inc., since 1958. However, work on SO2-pollution abatement was initiated by BCR in 1953. Tieman and Clymer,1 working with ozone and simulated flue gases, evaluated a gas phase oxidation process for removing SO2 from flue gases. Their experimental data indicated that the use of ozone to oxidize SO2 in flue gas concentrations, with subsequent recovery of H2SO4, did not appear to be economical due to the large ratio of ozone to sulfuric acid produced (2.6 to 1). The cost of the ozone would be 6 to 10 times the cost of sulfuric acid produced. As a result of the ozone study, work on a catalytic oxidation process was developed. The following reactions are the basis for the catalytic oxidation process Reaction [I] normally occurs in the combustion of sulfur-bearing fuels. At the high temperature found in the combustion chamber, 95% to 99% of the sulfur in the fuel is oxidized to SO2 and 1% to 5% is oxidized to SO3. The concentration of SO2 in the combustion gases depends on the combustion efficiency and the quantity of excess air used. A commonly used rule of thumb is 0.1 percent by volume SO2 in the flue gas for each 1% sulfur in the fuel. Reaction [2] proceeds at a wide range of temperatures. The rate of the reaction is rapid above l,000°F; however, the equilibrium conversion drops rapidly above this temperature. 2 Reaction [3] occurs rapidly to completion at temperatures below 400°F; above this temperature some SO3 exists in equilibrium with H2SO4. Complete dissociation of H2SO4 occurs above 650°F.3 The simplicity of the proposed process provided added incentive to the development and evaluation of the various component unit operations. The advantages of the process were considered to be as follows: 1) no raw materials were required, 2) the unit operations were not radically new; and 3) a salable product, sulfuric acid, would be produced. The successful development of the process was contingent upon the solution of several major problems: 1) The development of a catalyst which would provide high catalytic activity at reasonable conditions of gas flow and temperature without causing an unacceptable increase in pressure drop. 2) The development of a high temperature dust collection system to provide clean flue gases to the catalytic reactor. 3) The complete recovery of the sulfuric acid produced in the process; the effluent gas must contain less than 20 ppm by volume of sulfuric acid. As of this date, the complete solution to these problems has not been achieved. EXPERIMENTAL Catalyst Development: The use of platinum and vanadium catalysts for the production of sulfuric acid by the treatment of dry gases containing 5% to 20% by volume sulfur dioxide has been known for many years. The application of the basic idea of catalytic oxidation of sulfur dioxide in flue gas concentrations was

Jan 1, 1965

By J. L. Brimhall, R. A. Huggins, M. J. Klein

IN a recent paper1 it was shown that small additions of magnesium, copper, and oxygen decrease the stacking fault probability in plastically deformed silver. Correlation of :X-ray data with measurements of the twinning frequency and metallographic observation of slip lines indicated that this effect may be due to an increase in the relative stacking fault energy. It is the purpose of the present note to report experiments on these alloys of known stacking fault probability that relate to the stacking fault contribution to electron scattering in silver. There has been a considerable amount of disagreement in the literature concerning the contribution of dislocations to electrical resistivity in metals. Calculations relating to the scattering of conduction electrons by the dislocation core, its strain fields, and related effects have been made by several authors.2-5 In addition, experimental work on Cu,3,6-10 Ni,11 and Ni-Co alloys1:! has shown that dislocations in those materials exert an anomalously large effect on resistivity, this effect being related to the presence of extended dislocations. The problem of the scattering due to the stacking fault region between partial dislocations has been treated theoretically using several different procedures.13-'0 The results of these calculations show a wide range of predicted values, from rather large to completely negligible, due to the models and the approximations involved. Almost all of this work has been applied to the specific problem of scattering in copper. The more complete theoretical treatments depend rather critically. on the shape of the Fermi surfaces and the effective mass parameters. The scattering from stacking faults might therefore be expected to vary significantly from one metal to another. Unfortunately, sufficiently accurate information is not available .which would allow one to have any confidence in a theoretical prediction of the scattering in the case of silver. Resistivity measurements were made on small wire specimens of vacuum melted high purity silver and several dilute alloys. These measurements were made at approximately 20°C, with great care being given to temperature measurement and corrections. At such temperatures phonon scattering is significantly greater than imperfection scattering. However, the experimental technique was such that measurements on similarly treated samples were reproducible to better than 2.4 X 10-9 ohm-cm, which was satisfactory for this work. Values of the stacking fault probability and the increase in resistivity after severe plastic deformation are given in Table I. The increases in resistivity resulting from plastic deformation agree quite well with previous work on silver.14,21-26 In addition, it has been previously found that interetitials and vacancies in silver anneal out well below room temperature, so that the residual imperfection scattering in these experiments could be expected to be primarily associated with dislocations;. It is seen from the data in Table I that large changes in stacking fault probability are accompanied by differences in resistivity due to imperfection scattering of only a few percent. If the scattering of conduction electrons by extended dislocations is primarily due to the area of the stacking fault region independent of the stacking fault energy, and not the core and strain fields associated with partial dislocations, the resistivity increase should be proportional to the product of the dislocation density and the stacking fault width, as is the stacking fault probability. Therefore, the imperfection scattering caused by plastic deformation of the alloys should be considerably smaller than that found in the pure silver. Since this was not observed, these results sugegest the possibility that stacking faults do not themselves contribute appreciably to the electrical resistivity of silver deformed at room temperature. An alternative explanation of these observations is that the scattering by the stacking fault is roughly proportional to the stacking fault energy, rather than being determined by the total area of such faults. Sufficient evidence is not yet available to separate these two possibilities. This work was supported by the Office of Naval Research.

Jan 1, 1962

By C. Kremer Bain

DURING the past several years of diamond drilling in Washington County, Mo., the St. Joseph Lead Co. has discovered a concentration of commercial lead-zinc ore at four different points within an area of 36 square miles. The largest and to date the most promising group of these orebodies is located in the Indian Creek area. It was considered to be of sufficient value to warrant development. The Indian Creek area is in the center of the northern half of Washington County, 11 miles northwest of Potosi, Mo., the county seat. The location is readily accessible from Potosi by car or truck over the all-weather Missouri State Highway No. 114. The topography is one of rolling relief, varying from an elevation of 700 ft above sea level on Mineral Fork and Indian Creek to a maximum of 1176 ft at High Point Tower. It is divided in equal halves between the drainage to Mineral Fork and to Indian Creek. The shaft site at 1060 elevation is on the divide between the two drainage areas. The Indian Creek side is rough and heavily wooded, with only a few cultivated clearings. The slopes to Mineral Fork are more gentle and rounded, with much of the area cleared for farm land. Most of the surface is covered with Potosi and Eminence formations, which show little evidence of any structure. Ore structure was worked out by extensive diamond core drilling, with holes varying in depth from about 700 to 1300 ft. As of Oct. 1, 1950, 218 prospect holes had been drilled within the 36-square mile area. The ore is disseminated galena with considerable accompanying sphalerite in the Bonne Terre forma-tion in the shape of irregular blanket-type deposits. The main controlling structural feature of the outlined mineral zone is a buried pre-Cambrian rhy-olite-porphyry ridge extending partly through the Bonne Terre formation, which laps against the por phyry and also covers it. The mineralized zone parallels and forms an irregular halo around the porphyry ridge and is concentrated in the Bonne Terre formation where the La Motte sandstone is cut out by the porphyry ridge. This is a very common mineral occurrence in the southeastern Missouri lead belt district. The La Motte sandstone, which normally underlies the Bonne Terre formation, is thus cut out entirely. In this area the Bonne Terre is usually about 275 to 320 ft thick, the La Motte varying in thickness from zero up to 400 ft. Commercial concentrations of ore are indicated at several places, the most notable being at the shaft site where an orebody at least 4000 ft long with widths of 500 to 600 ft has been outlined. The total thickness of mineralized rock reaches 150 ft in some holes, although total ore thickness runs from 8 ft to about 60 ft, often in more than one layer. Preliminary Planning Ore reserves as outlined lend themselves to open-stope mining with trackless haulage and mobile loading machines and drilling equipment. This type of equipment has proved to be very efficient during recent years in the company's lead belt operations. After a study of bids for shaft sinking and an estimation of comparative costs, it was decided that the shaft would be sunk by St. Joseph Lead Co. personnel using company equipment. Since the plant site is about 26 miles from the company's nearest lead belt operations, it was necessary to plan a complete surface plant, including mill, shops, office, change room, and warehousing facilities. Immediately following the filing of an application for a certificate of necessity, a headframe was selected for which detailed drawings were already available. The order was placed for fabrication so that it could be delivered and erected in time to serve for sinking the shaft. This eliminated the expense of a temporary headframe. Drilling was started on two churn drill holes near shaft location, and two 1000-gpm deep well pumps

Jan 1, 1954

By H. M. Otte, A. G. Crocker

SLIP, twinning, stacking faults, and precipitates on well-defined planes in a crystal produce traces that are visible on either a polished or an etched surface. The purpose of this note is to establish the usefulness and limitations of the information obtained from such traces when determining the orientation of single crystals or grains in a polycrystal. Attention will be confined specifically to traces produced by octahedral planes in cubic crystals, though most of the remarks can be taken as more generally valid. The problem of determining the crystal orientation is completely solved in principle' and in particular for the special case under consideration.1'2 Tables are available3 in which the orientations can simply be looked up when given the two or three angles between the traces. Thus a quick and simple method is available for obtaining the orientation of a crystal from surface traces. In this note two examples will be given from recently published papers and will show the use of the method with the aid of the Tables, as well as some of the precautions that should be taken in the procedure. As part of an analysis of X-ray Kossel lines, Peters and Ogilvie 4 determined from them the crystallographic orientation of the specimen. They chose a Cu-5.10 wt pct Si alloy that had been partly transformed from the a (fee) phase to the k (hcp) phase. The latter formed as very straight platelets along the octahedral planes of the a phase, and a photograph (Fig. 7 of Ref. 4) was reproduced in the paper4 of the region for which the orientation had been determined from the Kossel lines. Apart from a very small area (about 0.15 mm diam) near the top center of the photograph, the region shown was clearly all of one orientation. Traces in four different directions were readily identified. Starting with the smallest angle and proceeding counterclockwise, the angles between the traces were measured to be 27° 43', 55° 16', 64 3 43 1, and32"26'. These add up to 1802 08 1, indicating a cumulative error of 8'. The correct values should, of course, be taken from the original glass plates, or at least from prints on distortion-free paper, so the precision of the quoted values is actually greater than their accuracy. The solutions can be looked up in the Tables3 in four ways, depending on how the angles are paired, tion for the minutes of arc is required and the solution obtained will be identical for all the four pairs if the values of the angles are not in error. In a practical situation, such as this one, there are several sources of error, so that the four solutions obtained will all be slightly different. An arithmetic average of the four solutions is mathematically incorrect, but may, in special cases, give an answer close to the correct one. A rigorous procedure for refining the orientation has been described by Mackenzie;5 he gives a least-squares method that can be applied, if necessary, to this type of problem. The orientation thus determined can be compared with the one from the Kosel lines and discrepancies larger than the experimental error assigned to nonor thogonality of the X-ray or electron beam to the specimen. Here the example will only be used to illustrate the general procedure for making a very rapid rough check. From measurements on the stereographic projection, Fig. 9 of the paper,4 we can determine that the surface normal is approximately (0.434, 0.704, 0.562). From the Tables3 we find, using 28°, 55" as a good approximation to the first pair (27°43', 55°16'), that the surface normal is (0.453, 0.678, 0.579).* These two values are within 2 deg of each

Jan 1, 1967

By R. J. Grace

Primarily, this report presents the results of direct efficiency tests which were conducted on the 200-hp Coal-Pak, hot water generator, No. 3 unit, at the Otterbein College heating plant in Westerville, Ohio. Also included is a comparison of fuel consumption of the old plant with that of the new plant, a comparison of efficiencies obtained by the indirect method on a 300-hp Coal-Pak, and the cost of gas vs coal to show the savings effected by the latter. Tests were conducted with ten different bituminous coals selected by Mr. S. A. Frye, business manager at Otterbein College. The coals, of ten different suppliers, from four different states and eight different seams, represented competitive products economically available to the heating plant. The tests were conducted by the usual plant personnel which consisted of the plant superintendent and two assistants. No outside supervision of any kind was given during the tests. The tests were made from Dec. 13, 1960, through Mar. 4, 1961. During this period, 300.03 tons of coal were burned in the No. 3 unit. This tonnage represented 25.5 pct of the total coal requirements for the 1960-61 season. Operation during the period was typical for the comfort heat load which the plant supplies. Of the 78.12 operating days, the boiler was on bank or holdfire 14.31 days, or 18.32 pct of the time. The length of individual bank periods varied from 2 hr to three days. Run periods varied from about 2 hr to 7.26 days. DESCRIPTION OF PLANT AND HEATING EQUIPMENT The new Otterbein College heating plant, completed in the summer of 1957, is located in a 50x50 ft boiler room on the lower level of a combination maintenance building and heating plant. The building is situated away from the main college complex on a hillside, which allows for on-grade delivery of coal to the three bunkers. The bunkers are located directly above and connected with the individual stoker hoppers. Fig. 1 shows an in-plant view of the Coal-Pak installations. The No. 3, hot water, unit is at the extreme right. The heating plant consists of three 200-hp Coal-Paks. Unit No. 1 is operated at 4 psi and carries the steam heating load of 14,000 sq ft EDR (steam) installed in two buildings. Provision has been made to convert these buildings to hot water heating at some future date. Since the unit under maximum load conditions operates only at about 50 pct steaming capacity, a heat exchanger was installed to convert steam to hot water. Thus, during light loads in mild weather the unit can be employed more efficiently to supply both steam and hot water and eliminate the need for operating either of the two hot water units. Units No. 2 and No. 3 serve a hot water heating circuit for a large group of 21 buildings of the College. These boilers deliver hot water at temperatures up to 200°F to the various buildings through distribution lines in tunnels. The present calculated maximum heat loss for the College is 15.195 million Btu per hr. The Coal-Paks have individual design capacities of 6.700 million Btu per hr. Table I lists the design date for the Coal-Paks. The No. 3 unit was chosen as the test unit, primarily because of its bunker location at the far end of the delivery ramp. Because of this location any excess coal above bunker capacity could be conveniently stored and isolated from the adjoining bunkers. Each bunker has a capacity of 30 to 35 tons of coal. The No. 2 and No. 3 hot water generators are equipped with automatic controls which maintain the

Jan 1, 1962

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),' while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).' These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969

By G. R. Love, M. L. Picklesirner

THE use of color adds a new beauty, power, and versatility to metallography. This has been amply demonstrated in a number of public exhibits and on the walls of corporate, government, and university metallographic laboratories around the world. Indeed, in a number of cases, the color not only is of esthetic value but is scientifically essential to the competent examination of particular samples and systems. Optical strain analysis,' determination of true grain size in U-A1 alloys: phase identification in Nb-base alloys,3 analysis of transformation rates in heat-treated Nb-Zr alloys,4 measurement of solidification segregation in cast Nb-Zr alloys,' study of the intermediate phases in Nb/Sn diffusion couples,6 investigation of the oxidation kinetics at various surface orientations in single crystals,7'8 and a number of other research efforts9'10 would have been vastly more difficult without the extra clarity and distinction introduced by color—either the colors resulting from particular polarized light techniques or the interference colors obtained by oxidation. It is unfortunate that the beauty of colored micro-structures cannot be shared more widely, but the economics of publishing a technical magazine apparently prohibits color plates except under extraordinary circumstances. It is doubly unfortunate that no convenient, general method exists for communicating the information available in colored microstructures to the scientific community. True, in some instances the color changes observed are dramatic enough that direct black and white photography is adequate. In photoelastic stress analysis, several orders of interference fringes may be produced and it is frequently desirable to suppress the color effects (use monochromatic light) to simplify interpretation. On the other hand, relatively minute color variations may be readily detectable by eye, be of considerable assistance in interpreting a structure, and yet be enormously difficult to reduce to an unambiguous black and white print. In order to illustrate a possible compromise or solution to the above problems, we wish to show three black and white photographs of the same region of an Nb/Sn diffusion couple whose interpretation depends heavily upon use of color techniques. These micro-structures were obtained from a section through a rod consisting of commercial-purity niobium tubing filled with 99.995 pct Sn (melt-filled in 10"6 Torr vacuum). The composite rod, measuring 500 mm long, was bent into a hairpin shape and inserted into water-cooled copper grips in a vacuum high-temperature furnace. The rod was outgassed for 2 hr at a furnace temperature of 800°C and was further heated by self-resistance using a 2.2-kva ac power supply. The rod was raised to 1910°C over a 4+-hr period, held for 15 min, slow-cooled to 1500°C over a -hr period, and free-cooled to room temperature (all temperatures were measured with W5Re/W26Re thermocouple). Throughout the heat treatment the ambient pressure was kept below 8 x lo-' Torr. Metallographic preparation of the sample was completely conventional except that it was necessary to extend the grinding steps to remove damage in the brittle NbsSn phase introduced by sectioning. No satisfactory chemical or electrochemical etch has been found for these diffusion couples; of those which have been tried, any that attack the niobium-rich phases at all attack the tin-rich phases disastrously. However, the final polishing steps did produce a slight relief effect and this, coupled with anodizing, yielded excellent clarity in the microstructures for direct observation. The anodizing voltage was chosen to give maximum change in color per unit change in composition. In this case, indeed normally, this maximum sensitivity occurred in the blue-to-red color range. The pure niobium tube wall anodized to a relatively bright blue

Jan 1, 1967

By E. A. Hopkin

Laboratory tests conducted by the author. together with actual field experience in Canada. have indicated the magnitudc of some of the factors affecting ability of drilling mud to clean the hole. A correlation was observed between funnel viscosity and particle slip velocity. A relationship was also observed between the Bingham yield value of the mud and the particle .slip velocity. Laburatury tests indicated little change in slip velocity with funnel viscosities up to ahout 80 sec/qt or to yield values of aboul 15 lb/100 .sq ft. The lip velocity of the partic1e.s. studied vuried from 160 ft/min with water to neerly zero for high mud viscositie. lncreasing the mud density, creating laminar annular mud flow or rotating the drill pipe Mlay also improve the carrying capacity of mud. Field tests indicated that during fast upper-hole drilling, the rate of cutting removal must he sufficien to maintain the concentration of cuttings in the annulus at less than 5 percent by volume to prevernt balled-up drill collars and .stuck drill pipe. INTRODUCTION In the Mid-Continent area, hole cleaning during rotary drilling normally involves the use of low-density drilling muds with funnel viscosities varying from 26 to 80 sec/qt. However, frequently it is necessary to raise the mud viscosity in excess of 200 sec/qt to clean the hole. In addition, field experience has indicated that during very fast upper-hole drilling, annular mud velocities considerably in excess of the maximum slip velocity of the cuttings (normally considered to be 120 to 150 ft/min) are necessary to prevent balling the bit and drill collars. In view of these variations in mud properties and circulation rates necessary to clean the wellbore, a study of factors affecting hole cleaning and the relative magnitude of each was undertaken. The study was also prompted by the knowledge that a drilling mud with properties close to those of water would drill at rates several times that of a viscous mud. The carrying capacity of these near-water muds was not clearly understood, however, and many drillers were reluctant to use them. DISCUSSION EFFECT OF MUD PROPERTIES ON DRILLING RATE The effect of mud properties on drilling rate has been studied by a number of investigators. 1t is clear from their work that mud properties close to those of water will significantly improve drilling rate and bit life. If the water-type mud will also effectively clean the hole and cause no logging or formation impairment problems, the choice of an appropriate drilling fluid is clear—use water. Often, however, a water-type drilling fluid is not capable of effectively cleaning the hole. THEORY OF PARTICLE SETTLING The forces acting on a particle that is allowed to settle through a fluid quickly reach equilibrium, and the particle settles at some constant velocity referred to as the slip velocity. The slip velocity of any particle depends upon a number of factors such as density and viscosity of the fluid, the volume, specific gravity, shape and roughness of the particle, and upon the shape and area of the projected face of the particle at right angles to the direction of relative fluid solid movement. Brown' expressed this relationship for spheres in Newtonian fluids in the following equation. where v, = slip velocity D, — diameter of sphere p, = density of spheye p, = density of liquid /a = friction factor g = constant. The friction factor f, varies as the size, shape, surface roughness and slip velocity of the body, and as the density and viscosity of the fluid varies. WaddelV ound experimentally that where dynamic similarity exists. f, was a function of the particle Reynolds number (NRe) of the sphere (Fig. 1). Fig. 1 shows that f, for spheres varies from over 10 for low NKe numbers to 0.44 for N,,. over 600.

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By R. W. Armstrong, D. H. Feisel

Self-diffusion in pure crystalline solids has been described through extension of the Cohen and Tum-hull volume -fluctuation model originally proposed for diffusion in simple liquids. It is shown, for a number of crystalline solids, that the self-diffusion coefficient, D, obeys the relationship where a is the lattice spacing, v the Debye frequency, Z' the lattice-volume fluctuation per atom required for a diffusion jump, and (?V/Vo) the relative increase in the lattice volume resulting from thermal expansion between O°K and the temperature under consideration. The calculated value of Z' is dependent upon the difiusion mechanism and the lattice geometry. ThE need for an increased understanding of mass-transport processes in crystalline solids has resulted in much research to determine rates of self-diffusion.' For several metals (e.g., copper, silver, and iron), the experimental values of the self-diffusion coefficient, D, have been determined over a large interval of temperature and the accuracy of D has been investigated through repeated experiments. Also, a number of empirical and theoretical diffusion studies have established a rational basis for understanding the D values for the different elements.2"6 The empirical diffusion analysis by Sherby and simnad6 supplied the main stimulus for the present study. Sherby and Simnad, reviewing the self-diffusion data for a substantial number of pure crystalline solids, suggested that sufficient data were available to establish with some certainty the apparent intrinsic material properties which influence D. Without explicit regard for any mechanism of diffusion, these investigators obtained an empirical relationship for D which correlated the self- diffusion coefficient for each element with the melting temperature, crystal structure, and valence of the particular element. Their analysis is only unsatisfactory in that the effect on D of crystal structure is not very clear and the valence to be assigned to an element is not always straightforward. The present study is an attempt, from a very different viewpoint from that of Sherby and Simnad, to establish a basis for understanding the self-diffusion coefficients for crystalline solids. This analysis was undertaken for the purpose of developing a general expression for D which would explicitly depend on the mechanism of diffusion. The main result of the study is that diffusion in crystalline solids may be described in terms of a volume-fluctuation model which was originally proposed by Cohen and Turnbull7 to describe diffusion in simple liquids. The model appears to be useful for predicting self-diffusion coefficients in crystals. The following sections describe the volume-fluctuation model for diffusion, the application of this model to crystals, and the resultant agreement with experimental data. 1) THE VOLUME-FLUCTUATION MODEL FOR DIFFUSION Cohen and Turnbull7'8 developed their model for liquid self-diffusivity for the purpose of describing certain properties of liquids, glasses, and the liquid-glass transition. A hard-sphere model for the liquid structure is used. In this model, the size of a spherical molecule or atom is fixed for all temperatures by the interatomic spacing at the absolute zero of temperature. At any temperature above O°K, the atom is viewed as being contained within a larger spherical cage defined by the interatomic spacing of the atoms at that temperature. A random distribution of varying cage sizes is assumed to exist in the liquid. An individual diffusion jump occurs when the free volume of an atom (the volume of the cage containing the atom minus the volume of the atom) is large enough for the atom to jump out of its cage. With this physical picture of diffusion in liquids, Cohen and Turnbull derive the following equation for self-diffusivity: D=Doe-yv*/vf [1] where Do is the product of three factors which are the diffusion-path geometry, the diffusion-jump distance, and the velocity of the diffusing atom, v*

Jan 1, 1964

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper .to, discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in. brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: 1-gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2-liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3-glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4-crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that carried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant, contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.1 At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1-aqueous solution, a much more expansible liquid, and a gas; 2-aqueous solution, salt crystals, and a gas; and 3-the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20° and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.2-6 Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid. carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.7,8 Hartley (1876, 1877),9,10 Hawes (1881),11 Wright (1881),12 Johnsen (1920),13 and Holden (1925)14

Jan 1, 1952

By C. O. Lee, R. H. Feierabend, Z. W. Bartlett

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953

By C. O. Lee, Z. W. Bartlett, R. H. Feierabend

DESPITE the fact that American brimstone production has increased 2 times since the prewar period 1935-1939, the demand for sulphur exceeds the supply. To alleviate this situation efforts are being made to increase the production of sulphur and bring the shortage to an end. The most important developments are being undertaken on the Gulf Coast. One new brimstone mine has been put into operation and three others are being developed. These projects are expected to account for a large part of the additional sulphur production now anticipated for the free world.'.' Except for a small amount of byproduct sulphur from sour natural gas and refinery gases, American brimstone is produced by the same process devised by Frasch 60 years ago, consisting essentially of the injection of superheated water at about 325°F into sulphur-bearing formations through wells which are drilled from the surface by standard oilfield methods. Sulphur deposits vary in depth from a few hundred feet to 2500 ft from the surface; in a typical deposit the sulphur occurs as crystalline aggregates in porous limestone and gypsum in concentrations varying from 5 to 40 pct, the thickness of the formation ranging from a few feet to several hundred.3 The deposits are usually surrounded by formations impermeable to the flow of hot water, the top and sides being enclosed by impermeable sediments and the bottom by dense impermeable anhydrite. As the hot water leaves the well bore, it percolates through the formation and transmits its heat to the rock and sulphur. When the sulphur reaches 240°F it melts, separates from the rock, and flows through the hot channels downward to the bottom of the well. Here it is freed from incoming water and from formation water, which saturates the porous rock, by gravity separation, liquid sulphur being 1.8 times as heavy as water. It then is pumped to the surface in a relatively pure state, 99.5 pct or better. Chief contaminants are organic impurities, such as petroleum residues, which are soluble in sulphur and tend to discolor it.' Sixteen deposits of commercial magnitude have been discovered in the Gulf Coast area. Five of these deposits have been depleted and abandoned with production totalling more than 26,886,000 tons. Eight properties are operating and have produced 65,875,-000 tons to Jan. 1, 1952, for a total Frasch-type production of 92,761,000 tons. Three new deposits are under development. Aforementioned deposits are listed in Table I. Each of these deposits has been found in the cap-rock overlying shallow intrusive salt plugs or domes and buried in several hundred to as much as 2500 ft of sediments. All salt domes do .not contain sulphur; only 16 sulphur deposits have been found in a total of 231 salt domes which are known to exist in the Gulf Coastal states of Texas, Louisiana, Mississippi, and Alabama. Ten of the salt domes lie in the Gulf of Mexico offshore from the Texas and Louisiana coasts. Additional offshore domes may be found, but their value as a sulphur potential is questionable owing to the great hazard and high cost that can be visualized at these exposed locations where depths of water reach 50 ft. Marsh operations of Freeport Sulphur Co. are in the southeast section of Louisiana. In general, the country is low, flat, relatively uninhabited marshland broken by many shallow lakes and bayous which extend for irregular distances inland. Geologically, the coastal area is of sedimentary origin, having been built up gradually under the sea by deposition of material carried down by large streams to their deltas. Offshore bars were formed enclosing

Jan 1, 1953