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By Gerhard Bockstiegel

Kuczynski's formula has been derived for the case of nonspherical particles. TWO formulae of Kuczynski's type have been derived, one describing the increase in tensile strength, the other describing the progress of shrinkage of a powder compact. It has been strength,shown that the exponents of all three formulae each contain two magnitudes of different physical characters, viz, the geometrical factor a and the kinetic factor ß. The interrelationships between the three exponents are stated. SOME years ago Kuczynski1 experimentally showed that the radius, x, of the area of contact between very small spherical metal particles and a metallic block is related to the time of sintering, t, by the following equation x = constant tk [11 where k has the value 1/5 or 1/7. Assuming that the metal particles were perfect spheres and the metallic block was perfectly flat, he derived the foregoing equation from theoretical considerations of the process of material transport in metals, and he showed that exponent k is different for different mechanisms of transport, e.g., k = 1/2 for viscous flow (according to Frenkel2), k = 1/3 for evaporation and condensation, k = 1/5 for volume diffusion, and k = 1/7 for surface diffusion. From this Kuczynski concluded that the mechanism of transport was either volume diffusion or surface diffusion, depending on whether the value of k, as found in his experiments, was 1/5 or 1/7. Subsequently. Cabrera8 corrected Kuczynski's calculations with regard to surface diffusion, showing that the theoretical value of exponent k is 1/5 for both volume and surface diffusion. He supposed that the different experimental values of k were due to slight differences in the shape of the metal particles. An exponential relationship similar to the aforementioned was found by Okamura, Masuda, and Kikuta,4 Masuda and Kikuta, and Takasaki8 when studying the rate of shrinkage on powder compacts during sintering. The authors measured the shrinkage by means of the fraction w = Vp — V./Vp — V,,,, where V,, is the volume of the green compact, V, is the volume of the sintered compact, and V,,, is the volume of the compact in its densest state. This fraction, w, they found, is related to the time of sintering, t, by the equation w == constant tm. [21 Further, Bockstiegel, Masing, and Zapf7 observed that the tensile strength, s, of sintering iron powder compacts can also be related to the time of sintering, t, by an equation of the foregoing type, i.e., s = constant tn. [3] For exponent n the values 0.28 (S=2/7) and 0.35 ( 2/5) were obtained, and the authors pointed out that there might exist a simple interrelation between exponent n as found in their experiments and exponent k in Kuczynski's equation. The authors supposed that 2k = n, since the strength of adhesion between a metal sphere and a block (as in Kuczyn-ski's experiments) must approximately be proportional to their contact area, p. x2. Theoretical Considerations This paper is an attempt to correlate the fundamental experiments of Kuczynski's type with the results obtained with powder compacts as represented by Egs. 2 and 3. In particular, the paper is to show how the rate of sintering is influenced by the geometry of the sintering particles and by the type of material transport. As the geometry of particles conglomerating in a powder compact is very complex, some simplifying assumption has to be made, of course, in order to adapt the problem to mathematical treatment. In the following paragraph a suitable simplification is introduced, and Kuczynski's formula is derived for the case of nonsphcrical particles. Relation Between Area of Contact and Sintering Time—As the face of contact between two particles in a sintering powder compact is not necessarily a circle (as in the case of spheres sintering to a block), Kuczynski's formula is modified as follows: Let the perimeter of the face of contact be described by means of polar coordinates R, 4, as shown in Fig. la, so the area of contact, f, is determined by f= 1/2 . S112p[R(Æ) ]2 dÆ [4] Then, let the two particles be intersected by a plane perpendicular to area f. The intersection is shown in Fig. lb. According to the nomenclature in this figure, the distance, h, between the surfaces of the two particles is a function of T and Æ: h = h(r,Æ). For the particular case of spherical particles, as in Kuczynski's theory, this function becomes: h = constant r2. It shall be assumed here that in the close neighborhood of their

Jan 1, 1957

By Ford R. Bryan, Edward F. Runge

BECAUSE of the need for ductile heat resistant alloys of non-strategic composition, there has been metallurgical development of Fe-A1 alloys possessing improved ductility and hot strength, together with high oxidation resistance. Iron and alu- minum form solid solutions up to approximately 35 pct Al. Alloys in the 8 to 12 pct A1 range are characterized by excellent oxidation resistance, high electrical resistivity' and, when appropriately alloyed, have creep rupture strength equivalent to that of the austenitic stainless steels.' At higher aluminum levels, the magnetic properties are of considerable interest. Nachman and Buehler" have recently reported on the desirable magnetic characteristics of the 16 pct alloy.

Jan 1, 1957

By M. T. Simnad, G. Derge, Ling Yang

A method is described for using radioactive tracer for the direct determination of ionic mobility in a molten electrolyte. The ionic mobility of Fe" in silica-saturated iron silicate is found to be 0.0009 (*0.0002) cm2 sec ' volt L at 1250°C. eLECTROCHEMICAL studies', ' of molten iron eE oxide and iron silicates have shown some ionic conductivity at all compositions. The current efficiency in electrolysis increases with the concentration of silica to a maximum of 90 pct at about 34 pet SiO,. In the silica-saturated melts the transport number of ferrous ions is near unity, indicating that

Jan 1, 1957

By W. A. Cole

The sulfur shortage that existed during the Korean conflict stimulated interest in coal measures as possible sources of sulfur. One of the areas brought to the attention of the Bureau of Mines was in Marion County, Iowa, where comparatively high-sulfur coals and other marcasite-bearing strata were known to occur. A Bureau of Mines engineer inspected the marcasite occurrence on December 4, 1954; this prompted further work on the Iowa coals and associated formations as a source of iron sulfides. An investigation of the Iowa high-sulfur coals was undertaken including core drilling, field reconnaissance, and compilation of data pertinent to consideration of the following: 1. Upgrading Iowa coal by mechanical cleaning and the feasibility of recovering sulfur from coal brasses. 2. Possibility of processing the high-sulfur coals by adaptation of methods employed in processing industrial gases to produce sulfur and sulfur products. 3. Possibility of finding concentrations of iron sulfides in associated rock formations in sufficient quantity for economical recovery.

Jan 1, 1957

By A. U. Seybolt, R. A. Oriani

The pressure and composition of the solid solution of nitrogen in chromium has been investigated as a function of temperature. The partial molal heat of solution, the activity of nitrogen in solid solution, and the partial molal free energy have been computed. The enthalpy of three reactions is summarized: N + 2Cr(3) = Cr2N(4), H° = —28,500 cal per mol 1/2N2(p) + 2Cr(8) = Cr2N(3)1 ?HO = —23,500 cal per mol 1/2N2(p) = N, ?H° = 5,000 cal per mol. WORKERS who have investigated the problem of the preparation of ductile chromium have been concerned with the effects of minor amounts of impurities upon this refractory metal. In particular, gaseous impurities such as oxygen and nitrogen have been suspected of causing trouble because of many known cases where brittleness in transition elements has been definitely traced to these elements. In order to evaluate the possible effects of the nitrogen impurity in chromium, it appeared desirable to learn something of the dependence of the nitrogen solubility upon temperature and pressure. Previous Work Maier3 in 1942 in his treatise on sponge chromium reviewed the thermodynamics of the chromium nitrides Cr2N and CrN, both of which are well-estab- lished compounds, but which apparently have not been studied in much detail. Maier presented some free energy-temperature expressions for the reactions 2 Cr,N = 4 Cr + N2 [1] and 4 CrN = 2Cr2N + N2 PI based mainly on the work of Satoh2 and Sano." Pearson and Ende3 in 1953 briefly reviewed the thermodynamics of Cr-N using the same data available to Maier, and also derived a free energy-temperature expression for reaction 1. Of the two nitrides mentioned previously, the present investigation was only concerned with Cr,N, since this nitride is in equilibrium with the metal phase, at least over most of the temperature range, Blix4 in 1929 established the structure of Cr2N (close-packed-hexagonal) by X-ray diffraction methods, and indicated that its homogeneity limits extend from 11.2 pet to 15.1 wt pet N. At a temperature of 1200°C, 38 mm Hg from the Maier expression and 43 mm Hg from the Pearson

Jan 1, 1957

By L. A. Bromley, A. W. Petersen

The van Arkel-deBoer method for producing ductile titanium by thermal decomposition of Til, vapor and deposition on an electrically heated filament is modified by film boiling Til liquid on a heated filament, resulting in similar titanium deposition on the filament and liberation of gaseous iodine. The deposition rate is higher and the energy requirement smaller than in the van Arkel process. Many problems must be solved before the process is commercially feasible. TITANIUM of 99.9 pct purity, called ductile titanium, has been produced by a modification of the van Arkel-deBoer&apos; method. In the van Arkel-deBoer method, an electrically heated wire is suspended from two electrodes, which are placed in a container holding TiI, vapor at a low&apos; vapor pressure (usually <5 mm Hg). The vapor diffuses to the hot wire, usually maintained at 1100" to 1600°C,&apos; and decomposes according to the reaction liberating gaseous atomic iodine and depositing solid crystalline titanium on the wire. Estimations based on the data of Runnalls and Pidgeon,&apos; indicate that the rate-control ling step is the diffusion of atomic iodine away from the wire. There appears to be nearly thermodynamic equilibrium at the wire with TiI, and iodine as the main gaseous species. TiI, is almost certainly an important gaseous species in the cooler regions.&apos; The liberated iodine diffuses to a heated source of crude titanium and reacts to form more TiI, vapor, which again diffuses to the hot wire and completes the cyclic process. The foregoing process may be modified by suspending the hot wire in liquid TiI,, instead of the vapor, and obtaining film boiling. This type of boiling is characterized by the formation of a continuous film of vapor over the wire surface. Since only vapor contacts the wire sul.face, the temperature of this surface may be raised as high as desirable, within the limit of mechanical strength requirements for the wire. By properly adjusting the input voltage. the temperature of the wire may be maintained above U0C"C; and by evacuating the vessel holding the liquid TiI, and maintaining a suitable condenser temperature, the vapor pressure of TiI, may be held low. Thus, the conditions of operation of the van Arkel-deBoer method may be approximated with film boiling; and hence, it is postulated that ductile titanium may be produced by this method. Preparation of Til, There are many methods available for the preparation of TiI,; that used in this research was prepared by the direct reaction of titanium sponge in controlled amounts with liquid iodine. Although no difficulty was encountered with this reaction, it has since been pointed out that this method is sometimes dangerous and should be used with caution. The resulting TiI, was purified by distillation. First Film Boiling Experiments Apparatus: The apparatus shown in Fig. 1 was used for film boiling TiI, on short wire filaments. The current to the filament was supplied through a bank of three 5 kva transformers connected in parallel. The current was controlled by adjusting the voltage over a 0 to 67.5 v range with a 7 kva variable transformer on the low voltage side of the bank of transformers. The current and voltage were measured by Weston meters. The sealed-in-glass tungsten electrodes were hard-soldered to the filament for the film boiling of TiI,. The bottom part of the reactor, containing TiI,, was wrapped with ni-chrome heating wires to maintain the TiI, in the liquid state. An ice or liquid nitrogen trap, for solidifying I, vapor and any TiI, not condensed, was attached to the low pressure side of the air-cooled condenser. A Megavac vacuum pump was used. Procedure: A 0.010 in. diam tungsten filament was hard-soldered to the tungsten electrodes. TiI, was melted (mp 156°C) and poured into the reactor chamber; the top of the reactor chamber, containing the electrodes, was replaced. Freezing of the TiI, was prevented by controlling the current to the ni-chrome wires wrapped around the reactor with a 1 kva variable transformer. The mechanical vacuum pump was started and the system evacuated to about 2 mm Hg TiI, vapor pressure. The current to the filament was turned on and the impressed voltage slowly increased with the variable transformer. A sudden drop in current at nearly constant im-

Jan 1, 1957

By J. Gordon Parr, D. H. Polonis

IN a previous study of hypereutectoid Ti-Ni alloys&apos; a substructure was observed in quenched powder specimens when the constitution was 100 pet retained ß body-centered-cubic phase. The alloy powders were quenched from 1000°C by a blast of helium gas and precautions already described were observed throughout the work, to minimize contamination. Ogden et al.2 have previously observed subboundaries in the ß phase of a Ti-Mn-N alloy; but this structure was attributed to nitrogen-rich a precipitation. The nitrogen content of the Ti-Ni alloys does not exceed 0.02 pet and the quenching rate was sufficiently rapid to suppress precipitation reactions. Since X-ray diffraction results have confirmed the absence of any second phase which might account for this phenomenon, it seems unlikely that this substructure is explicable in terms of nitrogen content. Fig. 1 shows the substructure in adjacent grains of 100 pet ß phase in a quenched 6 atomic pet Ni alloy. Fig. 2 shows adjacent ß grains in a similarly treated alloy; one grain contains marked intracrys-talline boundaries and the other is completely free from any substructure. The suberystals appear to have fairly regular shapes, suggesting a regular orientation relationship among them. Tempering the retained ß structure at temperatures below the eutectoid eliminates the substructure at an early stage of ß decomposition. At the present time it is possible only to guess at an explanation for this subboundary phenomenon, since very little work has been reported on substructures resulting from phase changes. It is believed that the present phenomenon is due to poly-gonization resulting from unrelieved stresses set up

Jan 1, 1957

By L. O. Bacon

IN the spring of 1952 Calumet and Hecla Inc. began a geophysical program near Shullsburg, Wis., in the Wisconsin-Illinois lead-zinc district, to assist the geological and drilling exploration programs. Sphalerite, the ore mineral in this area, occurs with a considerable amount of marcasite. In general the higher the percentage of sphalerite in the ore, the higher the percentage of marcasite; however, there may be mineralized zones high in marcasite but low in sphalerite. Orebodies in general are relatively narrow and elongated. Reconnaissance exploration of virgin areas consisted of drilling along lines at 500 to 1000-ft intervals. Whenever a mineralized zone was intersected additional drilling was done to determine whether or not the zone carried zinc percentages of ore grade and, if so, to delineate the body. Calumet and Hecla Inc. was interested particularly in a method that would show the direction and position in which to drill from the original discovery hole. This suggested a method of contacting the orebody, which occurs at depths ranging from 100 to 200 ft, with one electrode. After a number of procedures had been considered it was decided to use equipotential line methods. Instrumentation and Field Procedure: The power source used was a 400-cycle Signal Corps motor-generator having a rated output of 1200 w at 115 v. The detection unit consisted of test probes, a two-stage amplifier, and &apos;head phones for determining the equipotential line by audio null. Field procedure consisted of contacting the sulfide body in the hole by a specially built spring-loaded expanding electrode which would be lowered into the hole, in the closed. position, until it reached the mineralized zone. At that point the mechanism was released so that the arms would make contact with the walls of the hole in the same manner that a well-bore caliper does. This electrode was then connected to the generator, the other terminal of which was connected to the surface electrode. The surface electrode was either a point, a straight line, or a circular line electrode. The point surface electrode was placed at a considerable distance from the hole, that is, 2500 to 5000 ft, depending somewhat upon the depth to the sulfide zone and the distance from the hole containing the subsurface electrode to which exploration was considered. A higher voltage output from the power source would have been desirable, although no difficulty was encountered in determining null points to a distance of 500 ft. Straight line electrodes used were approximately 1000 ft in length at a distance of approximately 1000 ft from the hole containing the subsurface electrode. The circular line electrode used consisted of 4400 ft of bare No. 10 copper wire, which provided a circle of 700-ft radius. All line electrodes were fastened to the ground at 20-ft intervals with copper staples 4 in. long. Equipotential points were determined at 25 to 100-ft intervals. Location of the points was made by plane table and stadia. In open country with a three-man crew, the points were plotted as they were determined. With a two-man crew, pegs were placed at equal potential points and surveyed in after several equipotential lines were determined. Although interpretation of results given in this paper is qualitative, the paper as a whole would not be complete without a discussion of the theoretical distribution of potential due to a circular line electrode. The theoretical distribution would be required if a quantitative interpretation of the measured potential distribution were to be made. The theoretical potential distribution due to a circular line electrode can be obtained by means of Legendre polynomials. Using the method as developed by Weber,&apos; the potential for a circular line electrode in a semi-infinite, homogeneous, isotropic medium can be expressed, using the spherical coordinate system, as: V(r,n) = pi/2pR[S(r/R)nPn(cos?)Pn(cosa)]r<R [1] er V(r,a) =pI/2pr[S(r/R)Pn(cos?) Pn(cosa)]r>R [2] where: 0 is the angle at the origin, taken on the axis of the circular electrode between the axis and the line drawn to the circumference of the circular electrode. a is the angle between the axis and the radius, r.

Jan 1, 1957

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By L. R. Page, J. J. Norton

EFFECTIVE methods for determining grade and reserves of pegmatites in advance of mining have been developed in recent years. When intensive work began on the economic geology of pegmatites during the early years of World War 11, it was widely believed that grade and reserves could be estimated only in a most general way. The literature indicated that not all pegmatite deposits are unpredictable, but statements emphasizing unpredictability and irregularity seem to have been more widely accepted. Many standard references reflect the prevailing opinion that minerals: are unsystematic in their occurrence in pegmatites. Pegmatites have been described as "notorious for their irregular structure," and minerals within pegmatites as "irregularly distributed." "irregularly disseminated," of "erratic occurrence," "proverbially erratic in distribution," "characterized by extreme irregularity in ... size and distribution of the essential minerals, and variety and proportion of the accessory minerals," and "spotty.&apos;"" Over many years, however, geologic techniques have been applied with increasing success to economic analysis of pegmatites. Investigations, chiefly since 1939, have shown that mineral distribution and structure of pegmatites are largely systematic and that detailed geologic study can be used to predict the size and shape of mineral deposits in pegmatites. Because the writers are most familiar with the pegmatites of the Black Hills, S. D., examples cited are from that area." Pegmatites mined in other dis- * All examples are described more cornpletely elsewhere.: tricts are similar to those in the Black Hills," and the techniques described here have been applied by geologists and engineers working in other districts. In actual practice few pegmatite mine operators attempt to make accurate estimates of grade and reserves in advance of mining. Many deposits are too small for mining except on a very small scale; few pegmatite mines have more than ten employes. Hence there is little systematic preparation for mining, and the capital outlay may be so small that only a general knowledge of reserves is necessary. Technical personnel are rarely employed by pegmatite mine operators to make such estimates. In the future, however, as capital outlay becomes larger, estimates of grade and reserves will have to be more accurate. Geologic Aspects of Determining Grade and Reserves Estimating grade and reserves requires that the type of pegmatite, the size and shape, and the internal structure be determined by detailed geologic mapping and careful mineralogic study. The wide variations in the texture and distribution of minerals within many pegmatite deposits make a thorough geologic study of this kind necessary before it is possible to decide what sampling methods should be used to determine mineral content or grade. Types of Pegmatites: The first step in economic appraisal of a pegmatite is to determine the min-eralogical and structural type. In general, pegmatites may be classified into two groups: 1) those in which component minerals are more or less evenly distributed throughout the entire body and show relatively minor variations in texture, and 2) those in which component minerals have been segregated into units with recognizable differences in texture, mineralogy. or both. Johnston" has classified these types of pegmatites as homogeneous and heterogeneous, respectively. Cameron et al.10 have used the terms ~inzoned and zoned for similar types. The difference between the homogeneous and heterogeneous types is of great commercial importance. Homogeneous pegmatites can seldom be mined where the products are concentrated by the hand methods now commonly used, but they have been mined in a few places where a milling process has

Jan 1, 1957

By C. E. Birchenall, R. H. Condit

THREE surface activity procedures are in com--L mon use for the determination of diffusion coefficients in solids. In the oldest of these&apos; the activity observed at the original surface is compared before and after diffusion, where all the activity is in a thin, plated layer on the surface before diffusion. Partial absorption of the radiations from active atoms which have diffused below the surface reduces the effective activity after diffusion. The formula employed to calculate the diffusion coefficient is where F, is the ratio of final to initial activity at the surface, measured with identical counting geometry; Z=u3Dt, where D is the diffusion coefficient; t is the diffusion time; and u is the absorption coefficient for the radiation in the solid as defined by Lambert&apos;s law. This absorption law implies that all the rays are parallel to each other and normal to the specimen surface. This assumption of a collimated beam used by Steigman, Shockley, and Nix has been adopted by all other investigators and, although it gives results which are approximately correct under restricted physical conditions, it does not represent many actual circumstances. It is the purpose of this paper to show the importance of the divergent rays and to indicate a procedure for taking them into account. In the residual activity method the activity is determined on a series of surfaces ground on the specimen at progressively greater depths in the diffusion layer parallel to the initial surface. Gruzin2 has de- rived a formula for this procedure, which may be put in the form where I is the ratio of the activity measured at a newly ground surface at distance k below the initial surface to the activity at the initial surface measured after diffusion, and K= k/2p Dt. A third procedure involves the autoradio-graphic determination of activity on a plane ground at a small angle to the initial interface through the penetration zone. Aut oradiography can be particularly sensitive to the oblique rays. Unlike most counters which detect essentially all ß particles or X-rays which enter the active volume as a single event, the photographic emulsion may be thin enough so that oblique rays with longer path length in the emulsion produce more darkening than rays which move normal to the film plane. Consider a plane containing a source of radiation uniformly spread over a circle and a point counter located on the perpendicular through the center of the circle. As the counter moves along this line, the total angle 6, at the counter subtended by the specimen will vary. For a fixed counter distance, let 6 be angle between the counter axis and the line connecting the counter to a point P on the active plane. If an absorber of thickness X is interposed parallel to the source between counter and source, the ray from point P to the counter will pass through an absorber thickness X secant 6. Exponential absorption is assumed to hold for all rays. If r, is the ratio of intensity at the counter with absorber to the intensity without absorber and a = pX, 1 00 The behavior of this integral, evaluated numerically,

Jan 1, 1957

By Benny J. Nelson

To obtain information on the effect of gallium upon the corrosion of magnesium alloys, tests were made on the commercial alloy AM52S (Mg-3 pct Al-1 pct Zn-0.2 pct Mn) and experimental

Jan 1, 1957

By G. E. Veins

A three-phase, continuously-operated, 250 kv.a. electric smelting furnace has been installed at the Mines Branch, Department of Mines and Technical Surveys, Ottawa, for the experimental treatment of ores and by-products of interest to the Canadian mining, metallurgical, and chemical industries. In the operation of this furnace particular emphasis is placed on the accumulation of quantitative data which will be useful in determining the most suitable smelting technique and the nature of the products, and in arriving at preliminary conclusions regarding the cast of power and electrodes. The results obtained in the experimental smelting of iron, manganese-iron, titanium- iron, nickel, and chromiumiron ores, and of a number of industrial by-products, clearly show the value of such treatment for materials of this type.

Jan 1, 1957

[Allan, Andrew Thompson Creek Coal & Coal Corp., Glenwood Springs, Colo. Allen, Earl W Mine Safety Appliances, 257 Rio Grand St., Salt Lake City, Utah Allen, Louis B C. F. & I. Corp., P.O. Box 1738, Salt Lake City, Utah Allen, Thomas Chief, State Coal Mine Inspector, Colorado, Argonaut Hotel, Denver Ambler, J.B P.O. Box 591, Denver., Colo. Anderson, A. R Jeffrey Mfg. Co., Columbus, Ohio Anderson, Merlynn D U. S. Fuel Co., Hiawatha, Utah Anderson, Nephi W Books Cliffs Coal Co., Dragerton, Utah Arnston, E. K Standard Oil Co., 4601 West 26th Ave., Denver 12, Colo. Audin. Clement, Jr Paonia,Colo.]

Jan 1, 1957

By T. S. Hutchinson, C. E. Kemp

The bottom water drive analysis presented by Muskat has been extended to include fields with wider well spacings. Curves are presented from which volumetric sweepout, water-oil ratio, and rate relations may be calculated. The effects of non-unity ratios on sweepout eficiency and productivity decline have been studied by an approximate method. Also, the effect of gravity on volumetric sweepout has been approximated for a particurlar geometry. INTRODUCTION The purpose of this paper is to report work done in applying the analysis of bottom water drive reservoirs given by Muskat1 to a larger class of reservoirs, to extend this analysis to include the effects of gravity and non-unity mobility ratios in an approximate manner, and to investigate the rate of decline of productive capacity. The bottom water drive type reservoir is one where the oil is underlain by a water zone of sufficient thickness that water movement is essentially vertical. This system is defined in more detail in the appendix and a one well element is shown diagrammatically in Fig. 1. Muskat obtained solutions to the equations describing the volumetric displacement efficiency of idealized bottom water drive systems by assuming that gravity effects due to differences in density betwecn oil and water were negligible and that the mobilities of oil and water were the same. If either of these assumptions is not made, the complexity of the system makes an analytical solution well nigh impossible at the present stage of mathematical development. Coles and Stade&apos; developed an approximation to consider these factors. The authors have refined approximations, starting with the same basic assumption, which should give a somewhat quantitative picture of bottom water drive performance when mobilities are not equal and the effects of gravity are not negligible. The results of these approximate calculations can then be used to obtain the decline in well productivity as the field is depleted.

Jan 1, 1957

By S. J. Aresco

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove grindability index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions4/ issued by the Bureau of Mines, the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor and, if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous sampling of coal as delivered is a check on the practical results obtained in burning the coal.

Jan 1, 1957

By S. J. Pearce

The Bureau of Mines has prepared, as circumstances have dictated, a series of schedules setting forth the minimum requirements that various types of equipment should meet to be considered safe and satisfactory for use under certain hazardous or unhealthful conditions. These schedules cover a wide variety of devices ranging from explosives to electrically operated mine locomotives. This paper discusses the functions and operations of schedules under which respiratory protective devices are tested and approved. It emphasizes that the aim of the Bureau respirator-approval system is to make available to the public respirators that meet definite performance requirements. The responsibility of the respirator manufacturer in pre-testing the device and in maintaining its quality after it is approved are explained. Aid is provided for the user in selecting the proper device for specific application, and a plea is made for better education of all concerned in the proper use of the devices. DISCUSSION Provisions have been made for testing and approving the following types of respiratory protective devices: Self-contained breathing apparatus,2/ supplied-air respirators,3/ gas masks,4/ dispersoid respirators,5/ and chemical-cartridge respirators.6/ These devices are tested at the Central Experiment Station of the Bureau of Mines in Pittsburgh, Pa. Self-contained breathing apparatus is tested by personnel of Health and Safety District B; other types of respirators are tested by the Branch of Health Research.

Jan 1, 1957

By Joseph Berman

The wolframite mineral series was studied to determine the effect of the FeO - MnO ratio on unit cell symmetry and thermal stability. This work was undertaken to evaluate the analytical procedures now in use for wolframite in scheelite and to aid in the development of improved methods of analysis. Wolframite grains were hand-picked, crushed, and screened; impurities were removed by selective magnetic separations using a Frantz isodynamic separator. The samples were further checked by optical spectroscopic and microscopic examination.

Jan 1, 1957

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

By David B. Burrows, Francis R. Conley

INTRODUCTION A prerequisite to the evaluation and management of oil properties is accurate information derived from the analysis of core samples; but reliable data, such as porosity and permeability, can result only if all oil and water have been removed from the core samples analyzed. The most common method of core cleaning used to date has been Soxhlet extraction—a somewhat static technique, which depends upon the slow diffusion of hot solvent through the core sample. Soxhlet extraction performs satisfactorily only with highly permeable samples and at best requires long cleaning periods. The centrifuge method was developed in 1951 by Continental Oil Co. to overcome the inefficiencies inherent in the Soxhlet method. The new method is basically an operation in which hot solvents are caused to flow through the samples under the influence of centrifugal force. The centrifuge unit has proved so successful that samples which formerly required days for partial extraction can now be completely cleaned in approximately one hour. The original idea was conceived in 1950 by Elmer S. Messer, whose early experiments consisted of flowing solvent over sandstone samples suspended in a revolving basket and driven by a vertically mounted vacuum cleaner motor. Results were so outstanding that more permanent units were constructed. A modified model using this basic design was recently built by Core Laboratories, Inc., and is now used regularly in their operations. DESIGN Fig. 1 shows a photograph of the two extractors routinely used to clean small core plugs in the Production Research Div. of Continental Oil Co.&apos;s Ponca City laboratories. For illustrative purposes, the basket from one of the units has been removed, and because both extrac- tors are of identical design only one is described in the following discussion. Each extractor unit consists of a centrifuge and a solvent still. The core basket of the centrifuge is made of mild cold rolled steel 7 1/2 in. in diameter and 1 1/8 in. deep. The basket holds 18 1-in. samples (cubical or cylindrical) and is attached directly to a cone fitted to the shaft of the motor. Both the outer rim and the hollow hub of the basket contain perforations for the passage of solvent and extract. The solvent is delivered to the perforations by means of a copper tube inserted into the hollow hub. The motor is a vertical tool post grinder motor; (115 v, 5.6 amp, 0-60 cycles, AC-DC, rated at 1/3 hp). It has a rated speed of 10,000 rpm under full load and 15,000 rpm with no load. Variation of speed is obtained by the use of a variable transformer. The solvent still was constructed from one end of a stainless steel oxygen bottle by inserting a heating element, sight glass, and piping as shown on the schematic diagram, Fig. 2. The heater used was a three-position, 1,000 w, 115-v, immersion type. Intermittent flow of solvent to the centrifuge is obtained by means of a siphon bottle inserted between the condenser and the centrifuge.

Jan 1, 1957