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By W. M. Robertson

The formation of grain boundary grooves on surfaces of poly crystalline samples of cobalt and iron immersed in liquid lead has been studied. The grooves form by volume diffusion of the solutes cobalt and iron in the liquid. The diffusion coefficients of the solutes in liquid lead are derived from the measured rate of grooving. The diffusion coefficients are described by the relation D = Do exp (-Q/RT), with, for cobalt, Do = 4.6 x 10-4 sq cm per sec and Q = 5300 ± 800 cal per mole, and for iron, DO = 4.9 x 10-3 sq cm per sec and Q = 10,500 ± 1500 cal per mole. LIQUID metal-solid metal interactions occur at solid-liquid interfaces. Interfacial energy provides a driving force to change the morphology of the interface. Mullins1,2 has derived expressions for the kinetics of interface morphology changes driven by capillarity. These expressions can be applied to an isothermal system of a solid in equilibrium with a liquid saturated with the solid. Surface profile changes can occur by volume diffusion of the solute in the liquid, by volume self-diffusion in the solid, and by interfacial diffusion at the liquid-solid interface. A groove will form at the intersection of a grain boundary with a solid-liquid interface, reducing the total interfacial free energy of the system. The solid-liquid interfacial energy ? must be greater than half the grain boundary energy of the solid ?6 for Mullins' calculations to apply. If ? is less than ?b/2, then the liquid penetrates the boundaries, separating the grains rather than forming grooves. Boundary penetration did not occur in the work described here. where CO is the equilibrium volume concentration of the solid in the liquid, Dv the volume diffusion coefficient of the solid in the liquid, ? the interfacial free energy of the solid-liquid interface, O the atomic volume of the solid crystal, k Boltzmann's constant and T the absolute temperature. Eqs. [1] and [2 ] also apply to grooving by volume self-diffusion in the solid,1 with CoODv = D Self, where DSelf is the volume self-diffusion coefficient of the solid. For a grooving mechanism of interfacial diffusion at the solid-liquid interface, the groove width is given by2 where CS is the interfacial concentration of the diffusing species, and DS is the interfacial diffusion coefficient. Eqs. [1] and [3] can be used to determine the mechanism of groove growth. A t1/3 dependence of the growth indicates volume diffusion and t1/4 indicates interfacial diffusion. In some cases, volume diffusion and interfacial diffusion both can contribute substantially to the grooving process, causing the time dependence to be intermediate between t 1/3 and t1/4.3 For these cases, the relative contributions of the two processes can be separated.4 However, in many cases, one process will be dominant, and the data can be analyzed on the basis of Eq. [1] or Eq. [3] alone. The time dependences for volume diffusion in a liquid and volume self-diffusion in a solid are the same. However, the self-diffusion contribution of the solid is usually negligible compared to volume diffusion in the liquid. After the grooving mechanism has been determined, Eq. [1] or Eq. [3 ] yields the kinetic parameter A or B. The kinetic parameter can be used to calculate values for the unknown quantities in the product CD?. Usually C is known or can be estimated. If ? is known, then D can be calculated. In a measurement of grain boundary grooving of copper in liquid lead,' the time dependence indicated volume diffusion in the liquid. The quantities Co, Dv, and ? were obtained from the literature, giving excellent agreement between the observed values of A and the values calculated from Eq. [2 ].5 In a study of the grooving of several refractory metals in liquid tin and liquid silver, A1len6 educed that grooves formed by volume diffusion in the liquid. In a study of nickel in a nickel sulfide melt, Steidel, Li, and spencer7 found volume diffusion grooving kinetics. Both Dv and ? were unknown, so they could not obtain either one separately, though they did obtain a reasonable value for the temperature dependence of the product Dv ?. Several methods have been used to obtain surface profiles. It can be done by sectioning through the interface7 or by chemically removing the liquid from the solid surface after solidification of the liquid.6 However, if the liquid dewets the solid on removing the solid from the melt, then the interface can be observed directly. This method was used previously' and was utilized also in the present study. EXPERIMENTAL PROCEDURE Lead of 99.999 pct purity was obtained from American Smelting and Refining Co. Cobalt sheet was obtained from Sherritt-Gordon Mines, Ltd., with a nominal purity of 99.9 pct, the principal impurities being nickel, iron, copper, carbon, and sulfur. The sheet was

Jan 1, 1969

By C. C. Harris

An analytical solution of the integro-differential equation of batch grinding is proposed as a first appoximation to the xYt surface. The size distribution equation (xY plane) is a three parameter equation previously suggested. Possible refinements are outlined. Comminution kinetics research is presently following several related courses. Some are equivalent, in that they represent different ways of viewing the same facet of the problem, though the entire endeavor cannot be described as being completely integrated. The purpose of this note is to propose and discuss a framework into which the various approaches might be fitted. This must clearly be founded upon an analysis of the xYt surface.' (See also Fig. 1 of Reference 26.) The investigations referred to above comprise mainly researches into the following: (1) The kinetics of the creation of the finer sizes during relatively small grinding times. This is the Fahrenwald-Arbiter-Bhrany 2-3 approach which leads to equations equivalent to a special case of the charles4 relationship. It emerges that initial production of fines follow essentially zero order* kinetics. (2) Disappearance kinetics of the coarser fractions. This appears to be a first order relationship.5-6 (3) Prediction of the xYt surface via the selection and breakage functions utilizing computer-programmed or approximate solutions of the integro-differential equation of batch grinding.5,8-17 A recent discussion by Mika et al.5 references the relevant literature up to about 1966. In addition to these main-stream researches there is some work on the minor topic of extremely long grinding time considered as a limiting case.18-19 The field is supported by investigations into the size distribution of fragments produced by breakage processes, some of this work being most valuably statistical-mechanical in nature.20-25 Better fitting equations, however, are obtained by statistical and curve-fitting methods.26 This

Jan 1, 1969

By E. P. Abrahamson

The effect of transition element binary solid solution additions upon the recrystallization temperature of titanium has been investigated. All additions, except columbium and tungsten, raised the recrystallization temperature. A correlation is obtained between the logarithm of the absolute rate of change of recrystallization temperature with atomic percent solute and the number of uuter d shell electrons attributed to the free atom of the solute element in its ground state. The work of Abrahamson, et aL.1-6 on dilute binary solid solution alloys indicated a correlation between the free atom ground state electron configuration of the solute and both the brittle-ductile transition and recrystallization temperature. It is shown in these studies that the number of outer s and d electrons in the solute are of prime importance in determining the absolute rate of change of recrystallization or transition temperature with composition. Furthermore, the limit of initial linearity (in the curve of recrystallization temperature vs at. pct solute) has been shown to be a function of the number of d shell electrons in the solute for dilute iron- and vanadium-base alloys. To date no complete systematic recrystallization study of dilute binary titanium base alloys has been made. This study together with that of zirconium base alloys 6 will provide the data for the comparison of the effect of the same solutes upon two solvents with the same number of outer d shell electrons.

Jan 1, 1962

By Alfred H. Bell

IN 1945, Illinois produced 75,210,000 bid. of oil, or 4.4 percent of the total for the United States, and ranked sixth in the nation in oil production for the third consecutive year. Production decreased about 3 per cent from that of 1944, when the total Illinois production was 77,413,000 bbl. This is the smallest percentage of decrease in production in the state for any year since a peak was reached in 1940. Daily average production for 1945 was approximately 206,000 bbl. Daily averages by months were as follows:

Jan 1, 1946

By Rudolph Emmel

THE mines operated by the South American Development Co. are located in the Zaruma mining district of southwestern Ecuador. They are near the old mining town of Zaruma, which is the only important city in the canton of the same name. The district is situated in the upper end of a valley lying between two spurs of the Cordillera, one of which may be considered the Coast Range and the other an intermediate range. The mining camp proper, known as Portovelo, and the plant are 2.4 km. south of Zaruma, on the north bank of the Amarillo River, a tributary of the Tumbes River, which flows southwestward through Peru to the Pacific. Portovelo is difficult of access; it is reached from Guayaquil by means of river steamers and muleback. Embarking at Guayaquil, the route is down the Guayas River, across the Jambeli Canal, and up the Santa Rosa River to Santa Rosa, a distance of 177 km. From Santa Rosa, the road or trail follows the Santa Rosa River, then across the summit of the Coast Range into Portovelo, a distance of 74 km.-a two-day trip on muleback. The mining property of the South American Development Co. comprises 297 lode claims and 142 placer claims. The combined lode claims cover an area, roughly rectangular in shape, 9000 m. long from north to south by 4000 m. wide; the northern edge of the rectangle is about 3000 m. north of the central plaza of Zaruma. Mineral lands in Ecuador are held by virtue of an annual tax per claim paid to the central government, no surface rights being included.

Jan 1, 1925

By Charles H. Fulton

(Cleveland Meeting, October, 1912.) I. INTRODUCTION. THERE are comparatively few accurate data on the melting-or the freezing-point temperature of metallurgical slays, or on related physical phenomena, such as fluidity near the melting-point, specific heat, latent heat, etc. With the exception of the work of H. 0. Hoffman,1 and some older work by R. Akerman, P. Gredt, and H. M. Howe, no information is available that is of direct interest to the metallurgist. Hofman's valuable work is the only one that refers to slags produced in the metallurgy of copper and lead. The classic work of J. H. L. Vogt,2 who views slays from the standpoint of physical mixtures (solutions in which the entities are minerals), has opened up a. new field in the study of slags, and has placed the investigation of such properties as melting-temperatures, etc., on a rational basis. The recent work of A. L. Day, E. T. Allen, and W. P. White, of the Carnegie Institution, at Washington, and of European investigators 3 on certain systems of silicate minerals confirms the value of the investigation of silicate series from this standpoint, and it is my aim to apply this method to metallurgical slaws, in order to gain exact data of value in metallurgy. The work recorded in the present paper is the result of an investigation of reverberatory-furnace slags made for a Western smelting company to determine exactly the influence of change in composition, within comparatively narrow limits, on the melting-point. For a general discussion concerning the mineralogical character of slaws and the principles on which this investigation is based, reference should be made to other work,4 for the subject is too large to be stated in this paper, except very briefly in the following outline 1 Trans., xxix., 682 (1899). 2 Die Silikatschmelzlösungen; I. Ueber die Mineralbildung in Silikatschmelzlösungen; II Ueber die Schmelzpunkt-Erniedrigung der Silikatschmelzlösungen (Christiania, 1903-04). 3 Doelter, Handbuch der Mlineralehevu:e (1911) 4 C. H. Fulton, Principles (of Metallurgy. Chapter viii., on Slags, p. 24.5 (1910).

Dec 1, 1912

By R. B. Tippin, J. S. Browning

The feasibility of multistage heavy liquid cyclone beneficiation of spodumene was successfully demonstrated in this investigation. The indicated recovery for the multistage circuits was mathematically estimated as continuous test runs would be necessary to determine the true influence of a middlings recycle. In the three-stage circuit, both the concentrate analysis and spodumene recovery exceeded 90%. The two-stage circuits were unable to simultaneously yield an acceptable produce with a satisfactory recovery. With the Nation's growing industrial mineral requirements, the U.S. Bureau of Mines has undertaken the task of investigating new mineral dressing techniques and improving the existing concentrating methods of ore beneficiation. One such project is the gravity concentration of minerals using heavy liquid separation (HLS).1-3 Heavy liquid separation is based on the simple principle that a material, whose specific gravity is less than the density of a solution, will float on top of the liquid and a material with a greater specific gravity will sink. Heavy liquid separation techniques were developed in the laboratory over half a century ago but the process has yet to be commercially adopted. In the past, commercial operations have failed because of numerous problems.4 Industrial interest has recently been reactivated because of engineering advances. The number and quality of the heavy liquids suitable for mineral processing has increased while the cost has sharply dropped. New and improved liquid recovery systems5,6 are under consideration with present emphasis on 1) solvent extraction, 2) thermo-evaporation, and 3) water washing. The toxicity of the heavy liquids7 presents a problem, but throughout the chemical and mining industries, many similar hazardous materials are safely handled. A distinct advantage of using heavy liquids is its ability to provide a near perfect separation of fine-sized mineral particles even when the specific gravities are close. Effective separations have been made on minerals down to 200 mesh and with a density

Jan 1, 1968

By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith's data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy's obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:'l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

By C. H. Mathewson

MY treatment of the subject of "Metals of the Future" is imaginative rather than statistical or scientific, because reliable information concerning useful concentrations in the form of ore deposits of by far the majority of the elements does not exist and the chemical, physical, and mechanical properties of the unfamiliar metals are recorded only in fragmentary and uncertain form or not at all.

Jan 1, 1944

By Earl S. Bardwell

The determination of suitable and safe annealing temperatures is one of the most important problems arising in the operation of a copper rolling mill. Certain of the larger mills have worked this problem out for themselves and in these mills the operation has become more or less standardized. In some of the mills pyrometers are used to measure the temperature of the annealing furnaces and careful watch is kept to see that overheating does not take place. In a considerable number of the mills, however, dependence is placed entirely on the judgment of the operator. The almost total lack of literature bearing on this subject seems sufficient warrant for the publication of this paper. ' The discussion of this subject naturally divides itself into two parts: (1) The effect of annealing temperature on physical properties; and (2) changes in the microstructure of refined copper due to cold rolling and annealing. I. The Effect of Annealing Temperature on Physical Properties For the purpose of investigating this phase of the subject six test bars were selected, varying in oxygen content between the limits of 0.036 and 0.070 per cent. The chemical composition of each of these test bars was as follows: Bar Number 1 2 3 4 5 6 Copper + silver...... 99.95 99.92 99.945 99.94 99.95 99.93 Oxygen.............. 0.041 0.070 0.046 0.050 0.036 0.058 As + Sb............. 0.0038 0.0038 0.0038 0.0038 0.0031 0.0031 The bars were heated in an electric muffle to about 1,650" F. and rolled into rods. The rods were annealed, pickled, and drawn to No. 12 B. & S. gauge wire. The wire which was to be used for the annealing test was cut into 38-in. lengths and each length made into a coil 6 in. in diameter. The separate coils were marked so that they might readily be identified

Jan 1, 1915

By J. Ruben Velasco, Roland B. Mulchay

CANANEA has long been recognized as a remarkable field for geologic study. The copper deposits and rocks of the district have been described by many geologists and engineers, but only the most general correlations have been made between Cananea sedimentary rocks and other known sedimentary sections in the southwestern United States and northern Mexico. The present paper describes the Cananea sediments in greater detail than has been done before and attempts to fit the Cananea sedimentary section more closely into the geologic time table. The lack of well-preserved fossils has made it difficult to date the sediments accurately in geo- logic time, but it is possible to make tentative correlations between the Cananea sediments and the southeastern Arizona sections, based largely upon lithology and general position in the geologic column. It appears that sedimentation at Cananea and Bisbee may have been closely similar during Paleozoic time. Even such generalized correlations, however, may be subject to considerable modification in the future. The present study has led to the recognition of other problems of age and mineralization relationships in the Cananea district. Cananea is located in the north-central part of the state of Sonora, Mexico, at an elevation of 5270 ft. It is about 135 miles northeast of Hermosillo, the state capital, and 25 miles south of the international boundary. By road Cananea is 40 miles from the twin towns of Naco, Ariz., and Naco, Sonora, and about 50 miles from Bisbee, Ariz. It is served by the Nogales-Naco branch of the railroad, F.C. Pacifico, and is connected with Chihuahua and Mexico City by the Aeronaves airline.

Jan 6, 1954

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.

Jan 9, 1953

By George D. Graffin.

The first use of graphite is lost in the mists of time. It was used by primitive man to make drawings on the walls of caves and by the Egyptians to decorate pottery. As early as 1400 A.D. graphite crucibles were being made in the Haffnerzell district of Bavaria. Through the Middle Ages graphite was confused with other minerals, especially galena and molybdenite. Two common names that are still used for the mineral are "Plumbago," meaning leadlike, and "Black Lead." The latter name implied that graphite is either composed of lead or at least contains a large percentage of it. Gessner is credited with having recognized it as a separate mineral in 1565, but its composition was not determined until 1779, when Scheele demonstrated that graphite oxidized to carbon dioxide, thus proving its carbon constitution. In 1789, Werner named it "graphite" from the Greek word "graphein," meaning to write. The United States has long relied on foreign countries for its graphite supplies. This reliance has been due more to the lack of suitable domestic graphites than to any particular preference for buying minerals overseas. Ceylon (now Sri Lanka) graphites were imported as early as 1820, and Madagascar graphites have been imported since the properties on that island were opened up about a hundred years later. Mexico has long supplied the United States with most of its requirements for amorphous graphite. Physical Properties and Classification Graphite is found in laminated, flaky aggregates disseminated in schistose rocks. It also occurs in veins and exhibits a foliated or fibrous structure. Graphite is a black lustrous mineral that crystallizes in the hexagonal system, with rhombohedral symmetry. The crystals have tabular form and are six-sided; the faces are commonly striated. The flakes have perfect basal cleavage and are opaque. When well crystallized, the flakes have a black metallic luster while the amorphous material is black and earthy, with a microcrystalline compactness. The flakes feel greasy. Graphite is an excellent conductor of heat and electricity. It melts at approximately 3550°C at a triple point under 1250 psi. It sublimes between 3300-3500°C at 14.7 psi. At 3726°C a second triple point occurs at approximately 100,000 atmospheres. Thermal oxidation in the presence of oxygen begins at 300°C and the rate increases with temperature. The three forms of carbon (charcoal, graphite, and diamond) are distinguished by chemical and physical tests. The specific gravity of charcoal is 1.3 to 1.9, of graphite 2.266 g/ cm3 (crystal density), and of diamond 3.5. Graphite has a hardness of 1 to 2 (Mohs' scale). Natural graphite can be divided into three classes: disseminated flake, crystalline vein (fibrous or columnar), and amorphous. Flake graphite is a lamellar form found in metamorphic rocks, such as marble, gneiss, and schist. Each flake is separate, having crystallized as such in the rock. Crystalline vein graphite is found in the form of well defined veins or as pocket accumulations along the intrusive contacts of pegmatites with limestones. The graphite of such deposits is of two types, foliated and columnar. The important Sri Lanka (Ceylon) deposits are vein type. Amorphous graphite is commonly found as minute microcrystalline particles more or less uniformly distributed in feebly metamorphic rocks, such as slates and shales, or in beds consisting practically entirely of graphite. The latter usually are metamorphosed coal seams and carry as much as 80-85% graphitic carbon, while the former, being altered carbonaceous sediments, commonly range from 25 to 60%

Jan 1, 1983

By A. B. Parsons

AT the outset, the authors of this paper desire to file a disclaimer and an, explanation. They have no inside information from occult sources; neither of them feigns clairvoyant powers in the slightest degree. It is true that they have indicated on be graphs an approximate trend for the consumption of seven important mineral commodities up to the year 1954. At best this is a risky business; the figures do not pretend to be any- thing more than reasoned conjectures that are predicated on an attempt to evaluate some of the more obvious of the many factors that are likely to have a bearing on the future.

Jan 1, 1937

By R. B. Rosene, G. L. Foster, A. R. Hendrickson

he properties of some of the common fracturing oils, such as sand-falling rate, fluid loss and viscasity, are a function of the three major constituents of the oil. These are: asphaltic material, parafin waxes and a base oil. The base oil can be either high or low viscosity. Asphaltic material increases viscosity by thickening the oil, decreasing the rate of fall of sand through the oil. at temperatures up to 200" F. When large arnorrnts of parafin wax are present, much of the wax i.s not dissolved, but is present in the form of rnicroscopic crystals. 7'his, of course is limited to temperatures below the melting points of waxe.s. As a result, parafin waxes clo not function primarily as thickener.7, but rother as bullting materials. The functiori of wax, without asphaltic material, in a low viscosity base oil is uniquely unlike that of wax with asphalt coexistent in the oil. The resulting difierence in wax crystal size governs the sand-falling rate to a large extent. An ideal type of fracturing oil is one containing neither asphalt nor waxes. In such cases, the viscosity and resulting low sand-falling rate are apparently due to soluble resin- ous hydrocarbons, which are compatible with formation oils. INTRODUCTION Since the introduction of hydraulic fracturing as a method of stimulating production from oil and gas wells, a variety of fluids have been employed to open the fractures and carry the propping agent. Such fluids include gels, emulsions, and oils. In the latter category, the use of refined oils has increased tremendously, and it is probably safe to assume that such oils represent more than one-half of the total fluid used in fracturing. The general acceptance of refined oils for fracturing can be accounted for on the basis of their relatively low cost and general applicability. To minimize transportation costs, such refined oils are generally obtained within the local areas of operation. As a result there are several kinds of oil used in different areas, with a wide variation in the basic composition. These types may vary from a fair grade of lubricating stock to a highly viscous cut-back asphalt. or road oil. Originally, little attention was paid to the composition of the oils used for fracturing, and any oil which would carry sand was considered satisfactory. Recently, however, service companies and well operators have become more concerned with the type of oils used for fracturing. With this in mind, the present work was undertaken to evaluate and compare many widely used fracturing oils to determine which constituents were most desirable for fracturing purposes. Some of the important properties of fracturing fluids are sand-falling rate, viscosity, and fluid loss. Other properties, that are actually of no less importance, include flash point, pour point, emulsifying tendencies with formation brines, and compatability with the formation oils. This discussion has been limited, however, to the first mentioned properties in order to give some idea of the general composition of the refined oils, how they function, and why. PROPERTIES OF FRACTURING OILS The properties of fracturing oils are a function of the three major constituents of the oil. These may be designated as: (1) asphaltic material, (2) paraffin waxes and (3) a base oil, which may be of either high or low viscosity. The asphaltic material clas-

Jan 1, 1956

By W. N. Poundstone, G. R. Spindler

A comprehensive report on extensive experimentation in degasification of the Pittsburgh Coal seam is presented. Detailed accounts of the procedures and results are given for permeability tests, vertical bore hole tests, measurement of gas flow from sealed drainage areas, horizontal rib hole tests, and water infusion tests. The removal of methane gas from coal seams in advance of mining is not a new idea with mining men—much attention has been given to the possibility for many years. In other parts of the world, a principal concern has been in the recovery and utilization of the gas and a number of successful projects have been developed in Europe and elsewhere. In this country, the principal motivation has been related to the safety aspect with some possible side benefits concerning costs and efficiency in mining as secondary objectives. To date, experimental work in this country has been largely or entirely exploratory to determine bed characteristics with respect to the liberation of combustible gases to investigate or establish the possibility of degasification in advance of mining and as an aid in projecting mine ventilation systems to provide for safe, effective and economical handling of combustible gases liberated during mining. With these objectives in mind, the School of Mines and Engineering Experiment Station at West Virginia University, in cooperation with the Christopher Coal Co. of Osage, W. Va., initiated some experimental work in May 1952 and the project has been more or less continuous since that time. The work has been centered entirely in mines of the cooperating company in Monongalia County, W. Va., and Greene County, Pa. LOCATION AND GENERAL CONDITIONS OF THE AREA The principal mining in the area involved is in the Pittsburgh coal seam which lies at the bottom of the Monongahela series of the Pennsylvanian. The Pittsburgh coal in the area is generally uniform in its structure and physical characteristics. The bed thickness averages about 7 to 8 ft and the coal has a characteristic blocky structure as the result of pronounced face cleats and definite, but somewhat less pronounced, butt cleavage. It is a medium volatile coal, averaging about 37 pct, and is marketed principally as a steam fuel and for metallurgical purposes. The Pittsburgh coal outcrops along the Monongahela River and dips gradually, but not uniformly, slightly north of west (about N75°W). The westward extensions of the bed, from the areas contiguous to the Monongahela River which have been heavily mined, constitute the principal reserves and are all well below drainage with the depth of cover increasing with the distance from the river. In general, with deeper cover, it may be expected that methane liberation will be more of a problem in future mining as compared to areas mined previously; therein lies the interest in possible de-gasification in advance of mining. Fig. 1 shows the Pittsburgh coal area in the vicinity of Morgantown in Monongalia County, W. Va., and Greene County, Pa., in which the experimental work discussed is located. Fig. 2 shows the contours on the Pittsburgh coal in the test area. It will be noted that the first two bore holes for the experiments were at the edge of a bench or terrace with considerable change in the gradient in the immediate vicinity of the test holes and that the same general condition applies to later test areas. Mining is intensively mechanized in the area and in the mines involved in the experimental work with corresponding rapid advance of working faces a typical characteristic. In the areas now mined the total methane liberation ranges from moderate to relatively heavy, but the actual face liberation is extremely variable and may range from practically

Jan 1, 1961

By G. S. Brooks

WITH the gradual depletion of the natural-gas pools of the Kansas district, together with the uncertainty of further cheap fuel developments, some. of the western zinc companies turned to the coal fields, attracted by their permanency and the 'success of the Matthiessen & Hegeler Co. and the Illinois Zinc Co. Being then confronted with the problem of using a relatively high-priced fuel, although the ultimate' supply was very great, the fuel economies of the kilns and furnaces became of far more importance, and the more modern equipments, as a result, embodied distinct gads in this phase of the business. In addition, there have been some pronounced advances in the actual making of gas from these coals. Increased efficiency in gas making has contributed its share to lowering costs and those plants located in the higher priced fuel districts have probably been obliged to study these economies somewhat more closely. Naturally, many beneficial changes have resulted in both practice and apparatus in these sections. On, certain western coals, for instance, the actual saving in fuel consumption has been 50 per cent. By this is meant that, where about 1.75 tons were burned to smelt 1 ton of oxidized ore, 0.7 to 0.9 ton is now required. While comparisons by W. R. Ingalls1 of fuel economies in smelting in this country and Germany before the war may, in general, be correct, they do not appear to-do justice to the more progressive. American practice. It is doubtful whether German plants were substantially bettering these fuel ratios. Data furnished by Bender and Frams do not afford records averaging less than 0.9 ton coal per ton ore on materials from 40 per cent. to 50 per cent. zinc.

Jan 9, 1919

Edward Keller, Baltimore, Md. (communicatioin to the Secretary*):—It is pleasing to note the increasing amount of work on metallurgical problems that is being carried on by exact scientific methods, and the results of such labor issued by the laboratories of our universities. Without doubt, Mr. Bolles's paper will be welcomed by all progressive practitioners. Many of the results which Mr. Bolles presents to as are new; and I take exceptioil to a few minor points only. The first of his concluding remarks is as follows: "Mattes are not homogeneous, but are composed of distinct mineral entitier, and may be likened to igneous rocks, in which the mineral constituents fall out upon the lowering of the temperature and ensuing solidification." He quotes an introductory remark to a paper1 of mine, as follows: "The true chemical character of copper-mattes does not yet seem to have been definitely determined, i.e, it is still more or less of an open question whether they are true chemical compounds, or mixtures, such as igneous rocks." This quotation, taken alone, would convey the impression that Mr. Bolles's conclusion is entirely new. Had he quoted also another paragraph from my paper in question, it would be clear that he was, to a certain extent at least, anticipated. I take the liberty, therefore, to state the substance of my own work. In the paper referred to, I showed the existence of the phenomenon of liquation in mattes, and, continuing, said: " A more direct method to test whether a matte is a compound sulphide or a mixture of individual sulphides was attempted by applying hydraulic separation. A clean piece of matte was selected containing practically no magnetic oxide and of the following composition: Cu, 37.96; S, 24.45; Fe, 33.63; Zn, 1.25; Pb, 1.02 ; Sb, 0.26 ; As, 0.065 ; insoluble, 1.15 per cent. ; Ag, 26.7 ; Au, 0.04 oz. per ton. For such a test it is essential to select a chemically uniform piece, other-

Jan 1, 1905

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6'K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.' have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-' Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen's method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.' EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By G.A. Moore, C. E. Sims

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949