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By J. J. Jonas, J. L. Uvira

Equipment was constructed which permitted the hot compression of 99.8 pct Armco iron and 2.8 pct Si steel at constant true strain rates of 0.05 to 1 per sec over the temperature range 600" to 1000°C. A maximum true strain of 1.9 could be attained, followed by immediate quenching or by isothermal annealing. True stress-true strain curves were obtained, and the steady-state flout stress, a, strain rate, i, and temperature, T, were found to fit the following expression: The constants A, a, n', and AH were determined for the two ,materials. The activation energies obtained for Arrnco iron and silicon steel are 66 and 80 kcal per mole, respectively, and approximate those for seu- diffusion and for creep. This indicates that hot compression is a diffusion-controlled thermally activated process. THE hot compression of iron and steel is usually carried out in the austenite temperature range,1"7 as this is the one of greatest interest with respect to industrial hot working. However, a disadvantage of testing in the austenite range is that the hot-worked structure is destroyed by the phase transformations taking place during cooling. The present study was therefore carried out in the ferritic temperature range, and the hot-worked substructures were preserved by rapid quenching after deformation. The substructural results will be described in a separate paper, and the present communication is restricted to the strain rate/stress/temperature relationship observed during hot working. The results of hot-compression testing are usually given in the form of true stress/true strain curves, with a different curve for each temperature/strain rate ~ornbination.',~,~ Sometimes simple algebraic equations are fitted to the curves, so that certain extrapolations or interpolations can be performed.1'2'5 These equations are, however, devoid of mechanistic interpretations. The present study was undertaken to show that hot compression can be described by an equation of the type used in creep studies. That is, it will be shown that the temperature dependence of the strain rate in hot working is well-represented by an Arrhenius term, with an activation energy similar to that for creep. Also it will be seen that the stress dependence of the strain rate is similar to that for creep EXPERIMENTAL METHOD AND MATERIALS The investigation was carried out with the following three ferrous materials: 1) Armco iron; 2) Armco iron with 0.26 pct Mn; 3) 2.8 pct Si steel. The first two materials were utilized for investigations performed in the temperature range 600" to 800°C; the last one was used for tests at temperatures from 600" to 1000°C. The materials were of commercial purity,* as shown in Table I. Cylinders of five different sizes were prepared by strain annealing. The resulting mean grain diameter was 3 mm in the 1-in. Armco iron and 2 mm in the other sizes and grades. Different ratios of diameter/height were used to enable the determination of the coefficient of friction. The specimen faces were provided with concentric grooves, which acted as lubricant holders during compression, as recommended by English and ~ackofen' and others.2'9 Powdered glass lubricants were applied to the samples before hot compression to decrease friction and barreling, following the practice of previous investigator~.~~~~~~~~ Different mixtures of glass powder were used for each temperature, after the determination of suitable compositions by experiment.'' Equipment for Hot Compression. Hot-compression tests were carried out on an adapted 150-ton vertical hydraulic extrusion press and also on a modified high-temperature creep machine. The modified extrusion press was used for temperatures up to 800°C. The following items were added to the press: a) a high-temperature furnace with built-in upper and lower platens; and b) a transmission assembly, which permitted the attainment of logarithmically decreasing crosshead speeds. These accessories are described in detail in Ref. 11.

Jan 1, 1969

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 L. Leibowitz, M. G. Chasanov, L. W. Mishler

A drop calorimeter system is described for use in measuring enthalpies to 3600°K. Data are presented for tungsten between 2800" and 3600°K. The enthalpy of tungsten in cal per mole between 2000° and 3600°K can be represented by the equation HºT- Hº298 = - 1.7622 X 103 + 5.7772T + 8.9861 where T is in degrees Kelvin. A tabulation of com -puted values is presented for heat capacity, entropy, and free energy function. A drop calorimeter has been constructed to carry out enthalpy measurements at temperatures to 3600°K. Samples are heated by induction1 and dropped into a commercial adiabatic calorimeter, modified for this purpose. The experimental temperature is limited by the melting point of container materials and compatibility of the container and its contents. Several high-temperature drop calorimeters have been described in the literature1-5 but none has been used at temperatures as high as those in the present work; our measurements of the enthalpy of tungsten range from 2800" to 3600°K. DESCRIPTION OF EQUIPMENT An overall schematic view of the equipment is shown in Fig. 1. Power for the induction coil is supplied by a 25-kw 250 kHz Ther-Monic generator coupled to an iron core RF transformer. The Sample capsule is suspended in the work coil by 10-mil diam tungsten wires which are wrapped around a horizontal 5-mil diam tungsten wire. The horizontal suspension wire is clamped between two massive copper electrodes which are fixed in an x-y motion device that allows adjustment of the position of the heated capsule from outside the vacuum chamber. The copper electrodes are connected by flexible copper straps to a 1250-joule (5 kv, 100 pfarad) condenser bank. When it is desired to release the capsule, the condensers are discharged through the horizontal suspension wire causing it to vaporize rapidly. Very reliable and precise release of the capsule is achieved in this manner. Experiments have shown that no heat correction is required for this discharge energy. As part of the temperature measuring system, two prism holders have been incorporated in the apparatus. The upper prism holder is in the main vacuum chamber itself, whereas the lower one is in a side arm attached to the drop tube below the gate valve. The upper prism is mounted on a rotary vacuum feed-through, and may be moved under a protective shield when not in use. This prevents deposition of vapors on the prism surfaces when temperature measurements are not being made. Similarly, the lower prism is mounted on a push-pull vacuum feed-through, and when not in use may be pulled into its side tube. The prism mountings are fitted with guides and stops so that they may be moved precisely into the desired position. The aim throughout is to minimize the time the prisms are exposed to vapors from the hot samples. At the high temperatures reported in this paper, only the lower prism was used. The upper prism holder in these cases was fitted with an additional radiation shield. By using a prism and viewport, the lower surface of the samples can be observed by an optical pyrometer. The measurements discussed in this paper were obtained with a Leeds and Northrup 8622-C-S series manual pyrometer which is estimated to be accurate to 0.5 pct. Pyrometer calibrations and prism and window corrections were carried out in the conventional manner6 using tungsten strip lamps calibrated by the National Physical Laboratory, Teddington, England. Prism corrections were rechecked after each use. All work to date has been done in vacuum, and no measurable change has been observed in the prism correction below -2300°K for the upper prism and below -2800°K for the lower one. The total time of exposure of the prisms is about 50 sec per run. At high temperature, the final temperature reading is corrected by using the final A value for the prism; see Ref. 6 for details of this procedure. The calorimeter is a modified Parr Instrument Co. (Moline, lll.), Series 1230 adiabatic calorimeter with automatic jacket control. Other authors5 have used a similar calorimeter with good results. The calorimeter jacket cover and calorimeter cover are attached to the drop tube which contains a radiation shield. This shield is a gold-plated copper disc which can be operated manually from outside the calorimeter. The receiver is attached below the radiation shield and is lined with tungsten. In a typical experiment, the calorimeter and its jacket water temperatures were adjusted to 0.000°K temperature difference. The sample was allowed to equilibrate in the furnace at the desired temperature for about 20 min. The initial calorimeter temperature was then recorded, the sample dropped, and appropriate shutters closed. After about 3 min, the drop tube and receiver were filled with helium to 60 torr. The final calorimeter temperature was recorded after it had remained constant over a 5-min period. The equilibration time in the calorimeter was about 25 min. Thermistor probes are used to operate a hot and cold water supply system to maintain the jacket temperature equal to the calorimeter temperature. For actual measurements of the calorimeter temperatures, a quartz thermometer was used (Hewlett Packard Dymec Thermometer, Model #2801A). This thermome-

Jan 1, 1970

By Gordon E. Agar

Several correlations have been proposed to relate energy consumption and size reduction in comminution, and although these are arrived at from different starting points, it is postulated that they are all statements of the same basic concept. To test this postulate, the dry ball mill grindability of langbeinite was determined, and the results were analyzed according to the various methods. An examination ' of the energy-particle size relationships proposed in the recent past revealed that they had much in common. In fact, the conclusion was tentatively drawn that these expressions were essentially the same, even though they were arrived at from quite different basic premises. The equations attributed to Charles2 and Holmes3 were shown to re- duce to the same single equation, W - A K-3, and the simulated continuous test used by Maxson et al.4 was shown to give the best experimental value of the required empirical parameter, ß. Furthermore, the size distribution parameter a in the Schuhmann equation, y - (x/K)2, was shown to be equal to ß in many cases. The kinetic approach used by Arbiter and Bhrany5 should give the same results as the Maxson test procedure; however, the batch operation used by Arbiter and Bhrany could not produce data that would be as precise as the simulated continuous technique. To test the validity of these conclusions, the simulated continuous method was used to obtain data on the dry grinding of langbeinite. The results are discussed in terms of the various equations and approaches. APPARATUS AND MATERIAL A ball mill with internal dimensions of 17.5 cm (6 7/8 in.) in length by 19.4 cm (7 5/8 in.) in diam was loaded to 50% of its volume with balls 3.2 cm in

Jan 1, 1969

[Year of Election . 1944 .WALTER HULL ALDRIDGE New York. N. Y 1944 . SELWPN GWILLYM BLAYLOCK Trail. B.C.. Canada]

Jan 1, 1946

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

P. H. ARGALL, Magdalena, N. Mex. (written discussion *).-The Chilean mill has generally been considered a fine-crushing machine and as such has had many advocates; it has also. had quite a number of denouncers; hence, the action of the Portland engineers in using the Chilean mill for the preparatory work usually accomplished in, rolls or rock breakers and adding a ball mill to do the fine grinding is novel, though of doubtful utility in the long run, even though a fair efficiency is obtained for the combination machines, as measured by Chilean mill practice. In order to follow the development of Chilean mill practice on Cripple Creek ores, I might say that two 6-ft., Chilean mills were placed in operation in Stratton's Independence mill in April, 1908, treating ore crushed by rolls to pass Y4 in. screen aperture. Screening was, however, found to be an unnecessary refinement, as was also the use of plows in the mills; both screening and plowing were abandoned before the Portland engineers finished the experiments in stamp milling upon which they were then engaged. Two additional 6-ft. Chilean mills were added in the spring of 1911, three of them giving the required 10,000 tons per month capacity, one being always in reserve. The Portland company began using Chilean mills in June, 1910, at its Victor mill, and the same company purchased the Stratton's Independence mill in June, 1915, and remodeled it; it is now known as the Independence mill. A description of Stratton's Independence milling practice, is given in the November, 191.1, issue of Mining Majazine (London). These Chilean mills were used as fine grinders and that they accomplished their purpose is shown by the screen analyses, in which 62 per cent. of the pulp passed 150-mesh screens. To make coarse crushers of these Chilean mills, the Portland engineers have increased the speed, substituted steel in various parts for cast iron, provided new and enlarged thrust bearings to take care of the centrifugal force incident to higher speed, and have, thereby, greatly increased the cost of the machines. They have also reduced the width of the tires and dies from 8 in., as used in the original mill, to 7 in., a reduction of 12 ½ per cent. in the crushing surfaces, to say nothing of the loss of abrasion or attrition incident to the larger surface. At the same time, they have apparently increased the weight of the rollers by using tires 5 7/8 in. thick as against tires varying between 3 and 4 in. on the original mills, thereby increasing

Jan 4, 1920

By H. C. Gatos, Ahmed Azzam

A UTORADIOGRAPHY would appear to be sim-A pler and less time-consuming for diffusion studies than any of the radioactive tracer techniques commonly employed, namely, the sectioning, surface increase, and surface decrease techniques.' Accord- ingly, it was felt worthwhile to investigate the applicability of autoradiography to self-diffusion measurements, and gold was chosen for this purpose. The radioactive isotope Au'!'' was used, as obtained from the Brookhaven National Laboratory. Its radiation consists of p (0.97 mev) and y (0.41 mev) rays, and it has a half-life of 2.69 days. No-Screen X-ray film was found suitable for these experiments: the film has the desired high speed for recording P rays and yet is practically insensitive to y rays. On the other hand, due to the high atomic weight of gold, this metal is a strong absorber for p rays. The

Jan 1, 1953

By J. C. Bierlein, R. A. Dodd

Endurance strengths at 10' cycles, fatigue-hardening rates, and endurance strength/0.2 pct proof stress ratios have been determined jbr a range of Cu(Ni), Cu(Si), and S.R.0. Cu(Au) solid solutions. Some douht is cast on simple cross slip models of fatigue hardening in view of opposite composition dependencies of hardening displayed by Cu(Si) and Cu(Au). The temperature dependencies of hardening also are the opposite of predictions made on the basis of a cross slip model. A correlation apparently exists between the fatigue strength/0.2 Pc~ proof s1.re.s~ ratios and rates of fatigue hardening. An increase in PS/PS due to alloying or temperature change is accompanied by a decrease in hardening rate, and vice versa. In recent years there has been much interest in the determination of the dislocation structure of fatigued metals and alloys. The accumulated evidence, e.g., Refs. 1 to 5, suggests that the structure may be dependent on the stacking fault energy, 7, of the fatigued metal in the same way that fatigue hardening rates have also been shown to apparently depend on u .6' 7 The above research followed the various earlier theories relating crack nucleation to ease of cross slip, e.g., Refs. 8 to 131 so "ggesting that y may indeed be the parameter of principal significance in all facets of the fatigue process. However, comparatively little attention has been paid to correlating engineering fatigue data with observations of the above type. Certainly, it would be useful if potential engineering fatigue performance could be assessed from a knowledge of easily determined alloy properties, and the present research originated from this standpoint. TO investigate the widest Possible range of 7 would require the use of two solvent bases, e.g., aluminum and copper, but a reasonable coverage can be provided by copper-based solutions alone. Therefore, it was decided to work with Cu(Ni) and Cu(Si) solid solutions, the approximate stackillg fault energies of which are given in Table I. The y range extends from low, Cu(7.5 at- Pet Si), to moderately high in Cu(2-5 at. ~ct ~i) and two of the Cu(Ni) alloys. The values listed in Table I should be regarded as qualitative only, being derived as follows. Dillamore and smallman14 quote a value of 85 i 30 erg.cm-2 for the stacking fault energy of pure copper, based on an earlier value due to Howie and swannl5 corrected by Brown's formula.'' Since the ratios (alloy)h(pure copper) have been reported17,18 for Cu(Ni) alloys containing up to 30 pct Ni, approximate ) values for these alloys can be computed, and a rough estimate of 7 for Cu(50 at. pct Ni) obtained by extrapolation. The relatively low y value obtained in this way for Cu(50 at. pct Ni) coincides with the observation of Nakajima19 that the stacking fault probability is a maximum at this composition. Likewise, the y values for the three ~u(~i) alloys are estimates based on values given by Swann and Nuttingo corrected on the basis Of Brown's estimate that the true 7 values are probably 2.3 times greater than those originally computed. In addition to the above alloys it was decided to investigate short-range ordered (s.R.O.) CU(AU) alloys containing up to 25 at. pct Au. This last alloy has been shown to have a well-defined planar arrangement of dislocations when deformed,21,22 probably due to cross slip being restricted by the S.R.O. Engineering fatigue data was to be represented by the determination of endurance strengths, and these were to be correlated with fatigue hardening and mechanical property data. EXPERIMENTAL I, order to study the desired properties and property changes, the following alloys were prepared: Cu(2.5 at. pct Si), Cu(5.0 at. pct Si), Cu(7.5 at. pct Si), Cu(5.0 at. pct Ni), Cu(25.0 at. pct Nil, Cu(50.0 at. pct Ni), Cu(5.0 at. pct AU), Cu(15.0 at. pct AU), Cu(25.0 at. pct AU). The copper and gold were zone-refined, while the silicon was semiconductor grade. The nickel was of 99.95 p,t. purity.* All alloys were induction-melted in a *Kindly supplied by the International Nickel co. helium atmosphere, appropriate precautions being taken to avoid segregation in the Cu-Au series. Rod stock was obtained by rolling and swag,ng. A few Bridgman single crystals were grown for fatigue-hardening studies, but most material was machined into polycrystalline fatigue speciments of the design shown in Fig. 1, and into polycrystalline tensile and fatigue-hardening specimens of simple cylindrical design. All specimens except Cu(Au) were annealed; the latter were quenched from above T, to produce short-range order. A few of the quenched alloys were examined for long-range order by step-scanning over

Jan 1, 1969

By Irving Cadoff, Jack Medoff

THE linear thermal expansions of oriented single crystals of zinc were measured in the range from 20" to 416°C using a Leitz HTV optical lever differential dilatometer. The single crystals, supplied by Dr. J. J. Gilman, General Electric Research Laboratory, Schenectady, N.Y., were prepared from 99.999 pct-purity zinc, and were in the form of rods approximately 2 in. long by 0.15 in. in diameter having the following orientations: x = 1.5, 12, 20, 30, 37.5, 49, 60, 73, and 82 deg where x is the angle between the specimen axis and the (0001) plane of the crystal. From the family of expansion vs temperature curves, the instantaneous expansion coefficients were calculated at 100°C intervals, and Fig. 1 shows a plot of these derived coefficients for each orientation. Coefficients were obtained from the raw data using the chord-slope method. The curves in Fig. 1 indicate a positive temperature coefficient for low x, a negative temperature coefficient for high X, and an expansion coefficient invariant with temperature, amounting to about 43 x 106, for a crystal orientation of approximately 52 deg. From the available data, it is possible to arrive at the values for the axial thermal-expansion coef- ficients a, and a, by extrapolating the curve of the expansion coefficient vs orientation to zero and 90 deg orientations. More precise values for a, and a, are obtained if the instantaneous coefficients are plotted against the square of the cosine of the orientation angle, as shown in Fig. 2. The extrapolated terminal points of the best straight line through the data points of such a plot define the axial coefficients at that temperature. The theoretical justification for the linearity of this curve comes from inspection of a rearranged form of the general anisotropic equation for expansion: ax=a, + (a, -a,)cosZx [1I in which a, is the expansion coefficient in the "c" or [0001] direction and a, the expansion coefficient in the "a" or [ll50] direction. From Fig. 2, the axial coefficients at 100°C, for example, were found to be a, = 13.9 x 10'6 and a, = 62.4 x 10"6 per "C. In the same way, the coefficients were determined for 20", 200°, 300°, and 400°C. This data is summarized in Fig. 3. It is of interest to observe the common intersection of the curves in Fig. 3, which seems to bear out the earlier observation, from Fig. 1, of a

Jan 1, 1964

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 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

By N. O. Gray, John Henderson

Hydrogen-reduction data for naturally occurring single crystals and Prepared polycrystals of dense hematite have been presented. Results cover the temperature range 400o to 1000oC, for particles from ten sources, ranging in size from 0.07 to 10 mm and in shape from spheres to cylinders, cubes, and thin slabs. A consistent pattern of behavior has been demonstrated for single crystals and the reduction mechanism shown to be temperature-dependent. Below 579oC reduction is a simple topochemical process but at higher temperatuves it is complex and occurs in two distinct stages. Prepared particles from these laboratories behave in a similar manner to the single crystals. Data from two investigators showing topochernical reduction of Prepared particles above 575°C are inconsistent with that for other dense hematites. It is concluded that topochenzical reaction should not be used as a model for generalized rate expressions for dense hematites. SINCE 1958, McKewan1-6 has brought to prominence a simple concept of dense hematite reduction. This model is that oxygen is lost from a hematite particle undergoing reduction only from an oxide-iron interface that recedes in such a way that the oxide remaining retains the original shape of the particle, i.e., reduction occurs topochemically. An adjunct to this concept is that any intermediate oxides in the transition from hematite to iron only form thin layers so that oxygen cannot be lost from the particle without movement of the oxide-iron interface. Further, the rate of oxygen loss from the particle is said to be proportional to the area of the receding interface so that the iron layer grows linearly with time and the over-all reduction process can be described by the equation where ro and do are the initial particle radius and density, respectively, R is the fraction of the original oxygen lost, i.e., the fractional reduction, at time t, and K is the rate constant. The idea of an underlying simplicity in hematite reduction is attractive because it gives a tractable basis from which general theories of hematite reduction can be developed and it has received wide support,7-14 based mainly on the large amount of data13 that can be fitted to Eq. [I]. However, despite the fact that this equation has been derived for dense materials, the bulk of the data that have been used to test it13 have been for materials of only about 90 pct of theoretical density (5.26 g cm-3) or less, so that its generality for dense hematites has not been demonstrated. In any case, as will be seen, adherence of reduction data to Eq. [1] does not necessarily imply that reaction occurs topochemically. In this work only data for hematites approaching theoretical density are considered and it will be shown that in only one study besides McKewan's is topochemical behavior observed over the whole range of temperature investigated. For the majority of materials a linear rate of interface advance is observed to complete reduction only when wustite is not a stable intermediate phase in the transition of hematite to iron, i.e., at temperatures below about 575°C. Above this temperature, reduction is an exceedingly complex series of reactions that takes place in two distinct stages and it is only in the first stage that reaction in any way resembles a topochemical process. This means then that, far from representing general behavior as has commonly been supposed, topochemical reaction for dense hematites is only a particular behavior that may be observed under some circumstances. EXPERIMENTAL Hydrogen-reduction data have been collected and cross-checked in these laboratories by three techniques, weight loss, collection of water evolved in the reduction reactions, and direct metallographic examination. Details of these techniques are discussed elsewhere," where it is shown that results obtained by the three methods are in close agreement. The weight-loss method, by which most of the results were obtained, consisted of hanging the sample in a platinum mesh basket from an Ainsworth Model AV-AU-1 vacuum recording balance inside a vertical l 1/4-in.-ID alumina tube furnace. Dry deoxidized hydrogen was flowed downwards through the tube at 2 to 4 liters min-1 (stp). Single crystals from two sources and artificial oxides from three sources have been examined. The single crystals were from hematite deposits at Yampi Sound, Western Australia, and Brazil, the latter being obtained from Gregory, Bottley and Co., London, U.K. The "Yampi Blue" crystals were hand-picked from washed, magnetically concentrated, sized fractions, -200 mesh BSS (mean diameter ca 0.07 mm) and —36 + 44 mesh BSS (mean diameter ca 0.4 mm) while 10-mm cubes were cut from the Brazilian crystals with a diamond saw. The starting materials for the prepared particles were hematites designated, respectively, "Specpure Iron Oxide", Laboratory No. S639 from Johnson Matthey & Co. Ltd., London, U.K., "Calcined Ferric Oxide" from B.D.H. Laboratory Chemicals Division, Poole, U.K., and "Pigment Grade Oxide", EPR-50, from C. K. Williams & Co., Easton, Pa., U.S.A. Approximately spherical particles were prepared from the artificial oxides by rolling the material, moistened if necessary, in a glass jar, and cylindrical compacts approximately 10 mm in diam and of approximately equal height were pressed in a steel die at 200 psi. These spheres and cylinders were subsequently fired in oxygen for 20 to 100 hr at 1370°C. The

Jan 1, 1967

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

DESPITE the fact that American brimstone production has increased 2 ½ 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.1,2 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.4 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 caprock 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, 1952

By G. H. Kesler, C. E. Dryden, J. H. Oxley

Rates of heat- and mass-transfer from rods to recirculating air were determined within a one-quarter-scale model of a metals deposition bulb. The dependence of local and averaged rates of transfer upon outlet geometry, number of rods, position upon a rod, and airflow rate was established for flow patterns created by radial and tangential air inlets. The results are given a qualitative interpretation in terms of rates and distribution of metal deposition in a prototype deposition bulb. IT is well known that a number of metals can be prepared from volatile compounds containing them by causing dissociation of their compounds to occur at heated surfaces. Examples of such metals include silicon, titanium, zirconium, and aluminum, which can be prepared from their halides. While the ability to prepare high-purity metals by this technique is of importance in itself, the rate of deposition of metal also is important in considering the commercial potential of such a process. If the over-all process of deposition is broken down into separate steps of transport of materials to and from the heated deposition surface and establishment of chemical equilibrium at the surface, as was described in a recent paper,1 then since surface temperatures are usually high and surface equilibrium is attained very rapidly, the rate-controlling step can be considered as either that of transport of reactants to the surface or of transport of products other than deposited metal away from the surface. These two transport steps are related through the reaction stoichiometry. It can be shown1 that the rate and distribution of metal in such a transport-controlled process are determined by the over-all and local mass-transfer coefficients in conjunction with the equilibrium conversions at the hot surfaces. The rate relationship is: w = [KA(y a-y s)] B.E where the bracketed group is the rate of arrival of the reactant at the surface of area A as determined by the mole fraction driving force (y a - y s) and the convective transport constant K. The factor B is the weight fraction of metal in the reactant, and E is the equilibrium fractional conversion to metal. Numerical values of y, and y, are fixed by the vapor composition and the equilibrium compositim of reactant at the surface; and E can be determined by thermodynamic calculations or by experiment. However, values for the convective coefficient K are available generally only for systems of simple geometry, such as cross-flow past a rod or sphere or parallel flow past a flat plate or through a tube. Often it is necessary to work with systems of more complex geometry and in which the vapor flow may not be uniform or exactly parallel or perpendicular to the surface. It is possible, of course, to establish working correlations for these more complex systems by direct experiment; but the experiments usually are costly in both time and money. To circumvent this objection and to aid in arriving at an understanding of the relationships and interactions of the process variables, it is helpful to construct a model of the flow system in which air, water, or other convenient fluids can be substituted for the process vapors and with which mass-transfer measurements or analogous he at-transfer measurements can be made upon a simulated deposition surface. By this means, a large number of measurements can be made in a reasonable time, and the correlation of these results can be applied to the prototype system. Examples of the application of these techniques are to be found in the literature (e.g., Ref. 2). It is the purpose of this paper to illustrate these techniques by description of a model study which was done at Battelle Memorial Institute. The work to be described was of a preliminary nature; the investigation subsequently was extended to develop quantitative relationships among the significant dimensionless transport, geometric, and flow parameters. This more detailed study will be the subject of a future paper.

Jan 1, 1962

By Keats, J. L.

IN THE literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical charac- teristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete as data possible on all the factors that affect the elimination of metalloids were obtained.

Jan 1, 1957

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

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 H. R. Deeth, C. J. Koenig

About ten years ago nepheline syenite was introduced to the ceramic industry and the material has now found application in the various branches of the industry, namely, as a vitrifying agent in white-wares and as a source of alumina and alkalies in glasses, glazes, and porcelain enamels. Spencel described the early mining and processing developments regarding this material. Since the time of his article many research papers have appeared relating to the usage of nepheline syenite but little has been published relative to subsequent mining and processing methods. A complete indexed review of the literature was issued recently by Ohio State University.2 Since "Lakefield" nepheline syenite from Blue Mountain, Ontario (Fig I); is the only commercial ceramic-grade nepheline syenite now being marketed on this continent, discussion is limited to this operation carried on by American Nepheline Limited, Lakefield, Ont., and its subsidiary in the United States, American Nepheline Cory. at Rochester, N. Y. The Deposit Blue Mountain is a long ridge rising to an elevation of about 350 ft at its highest point above the surrounding country and extending for about six miles in a northeasterly direction across Methuen township, Peterborough County. The rock of the Blue Mountain central alkaline intrusive is fine grained, light colored and of even granitic texture. The solidified mass consists predominately of the minerals albite, nepheline and microcline in order of abundance. The average mineralogical composition for the deposit obtained by a study of 112 samples taken regularly over the whole formation is as follows:3 Volumetric Mineral Per Cent Albite.................... 54 Microcline................ 20 Nepheline................ 22 Muscovite................ 2 Mafics.................... 2 (Biotite, hastingsite, magnetite) Total................... loo The mineral nepheline (or nephelite) belongs to the feldspathoid group but is lower in silica content than are the feldspars. It is a silicate of soda, potash, and alumina (NaKAl2O32SiO2). Its presence with albite (Na2oA12O3 6SiO2) and microcline (K2O A12O3 6SiO2) gives the Blue Mountain deposit an alkali content of 15 pct and an alumina content of approximately 24 pct. While this huge alkaline mass is somewhat variable mineralogically, it has a uniform chemical composition. When the iron, mostly in the form of magnetite, is removed during processing, a remarkably uniform finished product is obtained. Geological surveying has disclosed many million tons of nepheline syenite in the Blue Mountain deposit. Diamond drilling in the area where mining is now being carried out indicates a block of about one million tons.

Jan 1, 1949