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By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher' estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,' however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,' in his test of Cottrell's theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell's theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley's assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12'13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a', an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

By G. M. Schwartz, D. M. Davidson

THE Duluth gabbro outcrops containing sulphides of copper, nickel, and iron are located on both sides of State Highway No. 1 an airline distance of 8.5 miles southeast of Ely in northeastern Minnesota. The region of known sulphide occurrences includes parts of sections 5, T. 61 N., R. 11 W., and parts of sections 25, 26, 32, 33, and 34, T. 62 N., R. 11 W. These sections, given in Fig. 1, are all in Lake County, Minnesota. Part of the area, which lies entirely within the Superior National Forest, is shown on the topographic map of the Ely quadrangle. The original discovery was made in 1948 when a small pit was opened in weathered gabbro rubble for use on a forest access road. A shear zone had caused unusual decomposition in this glaciated area, and the resulting copper stain was noted by Fred S. Childers, Sr., an Ely prospector, who began searching the outcrops along the base of the intrusive. He was joined in further exploration by Roger V. Whiteside of Duluth. In the summer of 1951 a small diamond drill was moved into the area and a hole 188 ft deep was drilled, passing through 11 ft of glacial drift into sulphide-bearing gabbro. This paper is a preliminary report on the geology of the newly discovered ore. The Duluth gabbro is one of the largest known basic intrusives and may be defined as a lopolith.1 It extends northeastward from the city of Duluth as a great crescent-shaped mass that intersects the shore of Lake Superior again near Hovland, 130 miles to the northeast, see Fig. 2. The distance around the outside of the crescent is nearly 170 miles. The form of the intrusive is simple at Duluth where it ends abruptly north of the St. Louis River; at the east end, however, the gabbro splits into two elongated, sill-like masses separated mainly by lava flows and characterized by minor irregularities. The outcrop reaches a maximum width in the central part where it is about 30 miles across, and a maximum thickness of about 50,000 ft. It may be significant that the sulphides occur at the base of the thickest part. The lopolith has segregated into rock types ranging from peridotite to granite. The most abundant types are olivine gabbro, gabbro, troctolite, anorthosite, and granite. Of lesser importance quantitatively are peridotite, norite, pyroxenite, magnetite gabbro, and titaniferous magnetite. Grout estimates that two-thirds of the gabbro at Duluth is olivine gabbro. Variations in the percentages of plagioclase, augite, olivine, and magnetite-ilmenite constitute the only essential differences found among the basic rock types. The predominant mineral is plagioclase, mainly labradorite. Plagioclase and olivine seem to have crystallized early, and the olivine rich rocks, usually troctolite, are found in the lower part. Segregations of titaniferous magnetite are abundant near the base of the gabbro along the eastern part and also occur far above the base. These have recently been described in detail by Grout' Near the top, segregation has produced a gradation to granite, or "red rock," as it is known locally. This consists of quartz, red feldspar, and hornblende. The red rock forms a. zone with a maximum width of nearly 5 miles but is quantitatively unimportant from Duluth northward for 35 miles. In Cook county, where the gabbro splits, each of the two sill-like masses has a red rock top somewhat thicker in proportion to the gabbro below than in the main central mass. The intrusive ranges from coarse to medium in grain size and from granitoid to diabasic in texture. Throughout much of the Duluth gabbro in Minnesota banding and foliation are well developed, as Grout has emphasized! The bands are mainly a result of variation in the percentage of minerals, as in troctolite with alternating bands high in olivine and in plagioclase. A few bands may consist largely of one mineral, as is true of some segregations of magnetite. Many of the banded rocks show a clearly developed parallelism of platy plagioclase crystals, and both banding and foliation are believed to conform to the floor of the lopolith. Throughout its extent in Minnesota the Duluth gabbro dips east and south toward Lake Superior. It is generally believed to extend beneath Lake Superior and is found as a smaller mass exposed along the north side of the Gogebic district in Wisconsin and Michigan. The dip at and near the base ranges along most of its length from 20 to 40°, but at places the internal banding dips even more steeply. The dip of the upper part is much less, and if it is assumed that the flows along the north shore of Lake Superior are a dependable indication, it does not exceed 15º. The formations shown in Table I which are intruded by the gabbro range from Keewatin to Middle Keweenawan in age. They present a significant picture. At the top, the gabbro and its accompanying

Jan 1, 1952

By G. M. Schwartz, D. M. Davidson

THE Duluth gabbro outcrops containing sulphides of copper, nickel, and iron are located on both sides of State Highway No. 1 an airline distance of 8.5 miles southeast of Ely in northeastern Minnesota. The region of known sulphide occurrences includes parts of sections 5, T. 61 N., R. 11 W., and parts of sections 25, 26, 32, 33, and 34, T. 62 N., R. 11 W. These sections, given in Fig. 1, are all in Lake County, Minnesota. Part of the area, which lies entirely within the Superior National Forest, is shown on the topographic map of the Ely quadrangle. The original discovery was made in 1948 when a small pit was opened in weathered gabbro rubble for use on a forest access road. A shear zone had caused unusual decomposition in this glaciated area, and the resulting copper stain was noted by Fred S. Childers, Sr., an Ely prospector, who began searching the outcrops along the base of the intrusive. He was joined in further exploration by Roger V. Whiteside of Duluth. In the summer of 1951 a small diamond drill was moved into the area and a hole 188 ft deep was drilled, passing through 11 ft of glacial drift into sulphide-bearing gabbro. This paper is a preliminary report on the geology of the newly discovered ore. The Duluth gabbro is one of the largest known basic intrusives and may be defined as a lopolith.' It extends northeastward from the city of Duluth as a great crescent-shaped mass that intersects the shore of Lake Superior again near Hovland, 130 miles to the northeast, see Fig. 2. The distance around the outside of the crescent is nearly 170 miles. The form of the intrusive is simple at Duluth where it ends abruptly north of the St. Louis River; at the east end, however, the gabbro splits into two elongated, sill-like masses separated mainly by lava flows and characterized by minor irregularities. The outcrop reaches a maximum width in the central part where it is about 30 miles across, and a maximum thickness of about 50,000 ft. It may be significant that the sulphides occur at the base of the thickest part. The lopolith has segregated into rock types ranging from peridotite to granite. The most abundant types are olivine gabbro, gabbro, troctolite, anortho-site, and granite. Of lesser importance quantitatively are peridotite, norite, pyroxenite, magnetite gabbro, and titaniferous magnetite. Grout estimates that two-thirds of the gabbro at Duluth is olivine gabbro. Variations in the percentages of plagio-clase, augite, olivine, and magnetite-ilmenite constitute the only essential differences found among the basic rock types. The predominant mineral is plagioclase, mainly labradorite. Plagioclase and olivine seem to have crystallized early, and the olivine rich rocks, usually troctolite, are found in the lower part. Segregations of titaniferous magnetite are abundant near the base of the gabbro along the eastern part and also occur far above the base. These have recently been described in detail by Grout.' Near the top, segregation has produced a gradation to granite, or "red rock," as it is known locally. This consists of quartz, red feldspar, and hornblende. The red rock forms a zone with a maximum width of nearly 5 miles but is quantitatively unimportant from Duluth northward for 35 miles. In Cook county, where the gabbro splits, each of the two sill-like masses has a red rock top somewhat thicker in proportion to the gabbro below than in the main central mass. The intrusive ranges from coarse to medium in grain size and from granitoid to diabasic in texture. Throughout much of the Duluth gabbro in Minnesota banding and foliation are well developed, as Grout has emphasized.V he bands are mainly a result of variation in the percentage of minerals, as in troctolite with alternating bands high in olivine and in plagioclase. A few bands may consist largely of one mineral, as is true of some segregations of magnetite. Many of the banded rocks show a clearly developed parallelism of platy plagioclase crystals, and both banding and foliation are believed to conform to the floor of the lopolith. Throughout its extent in Minnesota the Duluth gabbro dips east and south toward Lake Superior. It is generally believed to extend beneath Lake Superior and is found as a smaller mass exposed along the north side of the Gogebic district in Wisconsin and Michigan. The dip at and near the base ranges along most of its length from 20 to 40°, but at places the internal banding dips even more steeply. The dip of the upper part is much less, and if it is assumed that the flows along the north shore of Lake Superior are a dependable indication, it does not exceed 15". The formations shown in Table I which are intruded by the gabbro range from Keewatin to Middle Keweenawan in age. They present a significant picture. At the top, the gabbro and its accompanying

Jan 1, 1953

By Thomas P. Forbath

THE sudden realization that known sulphur reserves amenable to mining by the Frasch hot water process are nearing exhaustion focused attention on widely scattered surface deposits throughout the world. These deposits are not necessarily of lower sulphur content than ores located underneath Louisiana or Texas salt domes which usually average about 30 pct sulphur disseminated in limestone matrix. Their near surface occurrence, however, renders exploitation by the Frasch process impossible. As is well known, the Frasch process depends on the presence of 500 to 1000 ft of overburden and cap rock above the sulphur deposits to permit melting underground sulphur in place by diffusing hot water under pressures of 200 to 600 psig in the formation and raising the molten sulphur to surface by air lift. This process renders possible the production of pure sulphur which is 99.5 pct pure without any subsequent treatment. Surface deposits contain sulphur in the same range of concentrations as the salt dome deposits, i.e., from 10 to 50 pct sulphur, associated with various gangue materials such as silica, limestone, and gypsum. The pirincipal distinction, then, does not lie in the percentage of sulphur contained in the ore, but in the geological nature of the deposit. A recent study' of the world sulphur supply situation estimated 1950 sulphur production in the free world countries at 5.6 million long tons, of which the United States produced 5.2 million tons, or 93 pct of the total. While America's domestic needs alone would have been covered by national production, about 1.4 million tons were exported during the same year. Despite all the steps which are being taken to restrict use of elemental sulphur and to force the fullest possible development of alternate sulphur sources here and abroad, the deficit in elemental sulphur production will probably increase with time. As a result of intensive prospecting for oil throughout the Gulf Coast area discovery of significant new salt domes is held unlikely. With the growing scarcity of sulphur and what appears to be an inevitable rise in price, recovery from deposits not amenable to Frasch-process mining assumes greater economic importance. Untapped Reserves The most important deposits in this category are located in Sicily, where elemental sulphur occurs in Miocene limestone and gypsum formation. Sulphur content of these ores ranges from 12 to 50 pct with an estimated average of 26 pct. Although quantitative estimate of these reserves is not available it is held that they exceed 50 million tons of sulphur. Similar deposits occur also on the mainland which contribute about one-third of Italy's total current annual production of 230,000 tons, but these are known to be nearing exhaustion. Significant surface deposits of volcanic origin are located in South America, Japan and western United States, silica being characteristic gangue con-stituent. The largest of these deposits are in South America. More than 100 extend over a zone 3000 miles long, paralleling the west coast of South America. 'Total sulphur content of these deposits has been estimated to be as high as 100 million tons. The main islands of Japan also possess at least 40 known volcanic sulphur deposits with probable reserves of 25 to 50 million tons.' Prospected reserves in western United States might amount to 2 million long tons, principal deposits being located in the northwestern part of Wyoming, southern Utah, and eastern California. Volcanic deposits of lesser importance are found around the Mediterranean, in Turkey and Greece, and in Africa, Egypt, Abyssinia, and Somaliland. Beneficiation Methods Different methods of beneficiation have been used in these various locations. In Italy the Calcarone kiln and Gill regenerative furnaces are used exclusively. Both utilize heat liberated by burning part of the sulphur in the ore to liquify or vaporize the remaining sulphur, which is recovered by solidification or condensation. The Calcarone kiln is of conical shape, generally 35 ft in diam at base and 18 ft high. A kiln of 25,000 cu ft capacity burns for about two months and yields about 200 tons of sulphur. The Gill furnace consists of a series of chambers with domed roofs. Sulphur is burned and melted in one chamber at a time and the hot combustion gases are used to preheat the ore charge in the subsequent cell. These furnaces operate on a cycle of 4 to 8 days. The recovery yield of both systems is about 65 pct. Sulphur losses amount to 25 pct through the combustion to sulphur dioxide; about 10 pct is retained in discarded calcines. Ores containing less than 20 pct are not considered suitable as furnace feed. These methods are not only wasteful because of the low recovery obtained, but represent a serious atmospheric pollution problem. Sulphur produced ranges from 96 to 99 pct purity and thus does not match Texas or Louisiana sulphur. Owing to the present shortage, sulphur in the Middle East sells

Jan 1, 1954

By S. E. Szasz, E. J. Moore, B. F. Whitney

An accurate value of formation water resistivity R, is essential in calculating formation porosity and fluid saturation from electrical well logs. In the cases where R, has not been measured directly, it must be obtained from other data, e.g., the SP curve. This paper deals with another approach: how to calculate R, from the chemical analysis of the formation water. INTRODUCTION It is known that the resistivity of aqueous solutions of pure salts depends on their concentration and on the temperature; the concentrations are given in MPL (mg of solute per liter of solution), or sometimes in ppm (mg of solute per kg of solution): MPL = ppm X specific gravity. Values for different pure salts are available in the literature, but not for solutions of mixtures which are of practical interest. The major component of the dissolved material in almost all formation waters being sodium chloride, it is customary to express the resistivity of formation waters in terms of equivalent sodium chloride concentration, i.e., the concentration of a solution of pure NaCl which has the same resistivity at a given temperature as that of the formation water under consideration. Thus, the problem of calculating R, from the chemical anaylsis can also be stated as how to convert the other constituents of the solute into equivalent NaCl concentration. Salts dissolved in water are at least partly dissociated into ions, and do not conserve their identity. If known amounts of several salts are dissolved in water, the solution does not necessarily contain the same salts in the original proportion, but perhaps some other combination of the ions, along with free ions in solution. This is why the chemical analysis of formation waters is often given in terms of ions, as if all dissolved salts were completely dissociated. Our problem then boils down to how to convert the concentrations of the various ions to equivalent concentrations of Na' and C1-. Dunlap and Hawthorne' have proposed to convert the concentration of all other ions to equivalent Na' and C1-concentrations by means of constant multipliers; e.g., 0.95 for Ca"; 2.0 for Mg"; 0.27 for HCO 3-; 0.5 for SO, -, etc. Their factors were based on measurements made at 68F on 26 formation water samples from the Texas Gulf Coast, ranging in concentration from 1,500 to 75,000 ppm. The Dunlap method is widely used in electric log interpretation, and is often extrapolated beyond its original concentration range. A comparison of R, values calculated by this method and values actually measured on formation water samples has shown large discrepancies, especially at higher concentrations. Therefore, two new methods were developed at Sinclair Oil Corp.'s Tulsa Research Center to calculate equivalent sodium chloride concentration from the chemical analysis of formation water samples. FUNDAMENTAL CONSIDERATIONS The resistivity of a solution, or its reciprocal the conductivity, at a given temperature is determined by the charge, concentration and mobility of the ions actually present. Monovalent ions such as Na' or C1- always carry the same charge. Compounds of polyvalent ions, however. may show incomplete dissociation, e.g., NaSO; + Na' instead of SO,-- + 2Na'. This happens especially in more concentrated solutions. Only very dilute solutions are completely dissociated, as assumed in the chemical analysis report. At higher concentration, the degree of dissociation depends not only on the nature and concentration of the particular salt under consideration but also on the nature and concentrations of the other solutes. Mobility of the ions depends on the viscosity of the solution. It also depends on the degree of hydration of the ions, which in turn is a function of the nature and the charge of the ions and also of the amount of free water available per ion, i.e., the total ionic concentration. The net effect is that the conductivity increases slower than proportional to the concentration, even if a solution contains only one salt such as NaC1, and is different for different salts (Fig. 1). Conductivity can even decline with a further increase in concentration, e.g., if additional salt is little dissociated but ties up some of the free water and/or causes an increase in viscosity. In solutions containing more than one salt, the contribution of one salt to the total conductivity depends not only on the fractional concentration of this same salt, but also on the concentration of all other solutes. A perfect method would give the conductivity or resistivity of a solution as a function of the concentrations of all solutes present. This is so complicated as to be impractical, and a simpler method must be found which is of acceptable accuracy. The Dunlap method, on the other hand. is too simple because it askmes that at any concentration the contrih-

Jan 1, 1967

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By R. H. Frazier, J. M. Hodge, F. W. Boulger

This paper reports the results of studies of the impact properties of quenched and tempered alloy-steel plates as a function of sulfur content. It was found that the impact energy levels decreased continuously as the sulfur content increased and that there was a straight-line relationship between impact energy and sulfur content when plotted on logarithmic coordinates. Cross rolling raised the level of these Lines for transverse tests and lowered the level for logitudinal tests proportionately to the amount of cross rolling. ALTHOUGH it has been generally recognized that, for applications in which notch toughness is critical, the sulfur content of the steels used should be held to a low value, quantitative information on the effect of sulfur on notch toughness has not been available. For such applications, it is a common practice to specify minimum impact values, and in order that these may be met consistently it is important that the steel producer know quantitatively the effect of sulfur on notch toughness so that realistic sulfur content limits can be applied to the steels they produce. In many instances, particularly in flat-rolled products, impact properties are specified in the direction transverse to the principal rolling direction, so that the factors affecting the anisotropy or directionality of impact properties are also of concern to the steel producer. For some applications, furthermore, it is a common practice to increase the sulfur content of steels in order to improve their machinability, and, in such instances, the effect of this practice on notch toughness may often be of concern. This paper reports on an investigation, carried out at Battelle Memorial Institute, designed to furnish this quantitative information on the effect of sulfur on notch toughness and also to furnish further information on the factors affecting the anisotropy of impact properties in wrought heat-treated alloy steels. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental steels were of intended base analysis: 0.30 pct C, 0.80 pct Mn, 0.25 pct Si, 2.5 pct Ni, 0.80 pct Cr, and 0.45 pct Mo. Steels were made with sulfur contents varying from 0.005 to 0.179 pct. The steels were prepared from 600-lb induction-furnace melts. Steels containing 0.020 pct or more sulfur (at meltdown) were melted from a charge of ingot iron (except for one heat): lower-sulfur steels were made from electrolytic iron. The charge consisted of ingot or electrolytic iron, ferrosilicon to give 0.10 pct Si, and ferromanganese to give 0.05 pct Mn. At meltdown, electrolytic nickel, ferromolybdenum, iron phosphide, and pyrite were added followed in sequence by ferrochromium, sili-comanganese, ferrosilicon, and ferromanganese. The slag was then removed and graphite added to give the desired carbon content. Bath temperature was adjusted to 2850°F and, when no other additions were to follow, 2 lb per ton of aluminum was added, immediately before tapping. Compositions of the experimental steels appear in Table I. Analyses are from single determinations, except sulfur which was analyzed in duplicate. A test sample (3 in. in diam by 6 in. long) and a 575-1b ingot were poured from each heat. The test sample was poured in a sand mold; the cooling rates of the test sample and the large ingot were approximately the same. Chemical analysis chips and metal lographic specimens were taken from the test samples. The ingot was 8 in. sq at the base and 9 in. sq at the top. A 5 X 5 X 6-in. sand mold hot top was completely filled in teeming the ingot. After solidification, the mold was stripped from the ingot which cooled to room temperature. Ingots were reheated to 2250"F and rolled to 1.9-in. slabs on a commercial mill. The slabs were box-cooled to room temperature. Sections of the 1.9-in. slabs were heated to 2250°F and rolled on a Battelle laboratory mill according to one of three schedules: 1) rolled straightaway to 0.5-in. plate; 2) rolled straightaway to 1.3-in. thickness, then cross rolled to 0.5-in. plate (29 pct cross rolling); or 3) cross rolled from 1.9-in. to 0.5-in.-thick plate (46 pct cross rolling). The 0.5-in.-straight- or cross-rolled plates were normalized at 1700°F for 1 hr and then water quenched from 1600°F. Plates were then tempered 2 hr at 1240°, 1170°, 1080°, or 860°F to obtain Rockwell C hardness of 25, 30, 35, and 40, respectively. Tempering was followed by quenching to room temperature to avoid temper embrittlement. Slack-quenched plates were isothermally transformed for 26 min at 800°F, quenched, and tempered 2 hr at 1170°F. Pearlitic microstructures were obtained by holding 168 hr at 1200° F, followed by quenching. Charpy V-notch specimens were taken both transverse and longitudinal to the main rolling direction, notched perpendicular to the plate surface, and tested. Slabs and plates which were to be homogenized

Jan 1, 1960

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By W. A. Thomas

Steam is, and doubtless always will be, the basic power in the anthracite industry, either directly applied through engines and pumps or electrically. The rapidity with which electric power is being applied to the mining and preparation of anthracite leaves little doubt as to its utility and economy. There is practically no operation, except possibly the drilling of hard rock, that has not been successfully electrified and the matter of drilling is handled economically with electrically driven compressors and the standard compressed-air drills. Conservation and the seemingly ever-increasing cost of production, justify careful consideration of the possible results of the more extensive use of electric power in the industry. It is not planned to discuss, herein, the relative economies of individual applications but to consider the relative economy and flexibility of steam and electric power. The reports available for the year 1920 indicate a production of slightly over 80,000,000 tons of anthracite, of which 8,843,500 tons were used for power and heating purposes; in other words, over 11 per cent. of the production was used at the mines. Some of this was used to generate electric power at the mines, about 160,000,000 kw-hr., while 150,000,000 kw.-hr. was purchased from the public utility companies. One large producer, who is buying some electric power and generating some, used over 13 per cent. of the production for power and heating at the mines. Another producer, where considerable electric power is generated on the properties, is using less than 9 per cent. of the output for power and heating. One of the largest producers has a fuel consumption of over 15 per cent. of the output, besides which considerable power is purchased. A careful study of the field indicates that steam-operated plants use upwards of 13 per cent. of the production for power and heating, while electrically operated plants use about 1 per cent. for heating; so that, for steam-power purposes at least 12 per cent., or 268.8 Ib., are used for power out of each ton produced. In the complete electrification of anthracite mining operations, no set rule can be given for the power requirement, in kilowatt-hours per ton, as conditions vary widely in the matter of pumping, ventilation, and transportation, but the following cases are given as a basis of determining a range and a possible average power requirements:

Jan 1, 1922

By Sidney Swensrud

ABOUT a year ago, I attempted in a general way to trace the origin and development of some of the marketing problems of the petroleum industry, and to describe certain trends which it then seemed possible to foresee. To summarize briefly, it was pointed out that the consumption of gasoline, after increasing for more than a decade at an almost unbelievable rate, was slowing down, but that the two factors which determined the supply of gasoline-namely, the production of crude oil and the percentage of gasoline derived therefrom-were tending steadily to mount. It was suggested that, while the increase in gasoline outlets began with and probably was justified at the start by the rapidly increasing demand, long after all reasonable requirements as to number of outlets had been met the number continued to increase-if anything, at a still more rapid rate-because by that time the overproduction of crude had begun to exert an impelling urge upon the owners of that crude to seek assured outlets for it in the form of gasoline. As more and more companies became integrated all the way from crude oil to marketing, there took place an ever-increasing competition among them, not only for the existing outlets but for new ones. The wide margin between wholesale cost and retail price, which is characteristic of the early stages of most new industries, persisted in the oil industry longer. than in most industries, for various reasons. The existence of that wide margin provided in large measure the means of attracting new outlets, for as the gallonage per outlet declined with the increasing number of outlets, competing companies simply offered the dealers a larger part of the total margin. The very nature of competition suggests that such a process would continue until practically all of the available margin was thus given away, and such was clearly the, tendency. It was a system that in turn produced increasing marketing expense per gallon on account of the -diluted gallonage per outlet; this increased expense might seem to have provided a justification for continuing wide margins. Economics, like its parent, nature, however, progresses by mutations and so began to throw out new types of marketers, in the form cf tank-car service stations, cut-price jobbers, and the like-heretics or

Jan 1, 1932

By William Metcalf

It is the object of this paper to oppose unnecessary changes, and the introduction of new and confusing terms. From the earliest times of which we have ally record on the subject, iron has been divided into general classes. Whether iron was first known in the form of wrought iron or of steel, is a matter of no importance; but at the time when cast iron first became a prominent article of commerce, wrought iron and steel were old products— steel, at that time, being generally made from wrought iron by the process of cementation. As steel was then properly defined as iron containing more carbon than wrought iron, so cast iron was appropriately defined as iron containing more carbon than steel. Until the year 1776, when Huntsman first began the manufacture of a new kind of iron by melting wrought iron and steel in crucibles, the above definitions were all that could be desired. At first, probably, owing to imperfect appliances, only a highly carburized iron was melted in crucibles, and this led to its being called cast steel. If our ancestors had found a name for this material not involving the use of the word steel, we would have been saved the trouble of the present discussion. As the arts developed, new uses were found for steel, and the products of the crucible were varied, until at the present day it is quite common to find steel containing no more carbon than average wrought iron, and other steel containing nearly or quite as much carbon as some cast iron. All of these various products of the crucible have retained, or received, the name cast steel, usually abbreviated to the simple word steel, without caus-ing any confusion among producers or consumers in regard to terms or their meaning. In 1865, twenty-one years ago, the Bessemer process was introduced ; this was followed in a few years by the Siemens-Martin process, and the products of both were at once, and have ever since been, called steel, from the fact that they were identical in chemical and physical properties with crucible cast steel. At the present time, then, we have three subdivisions of cast steel, viz.: Crucible cast steel, Bessemer cast steel, and Siemens-Martin,

By B. H. Lehnhard, C. J. Cecil

The paper describes the use of the Electric Pilot in the Permian Basin for making permeability surveys of wells and for the selective acidization of wells. A general summary of the information obtained from the many permeability surveys run in this area is given, and the possible application of this information to reservoir control problems is discussed. The application of the Electric Pilot on specific wells, involving well completion, acidizing and workover operations is also included. Introduction The Electric pilot is a comparatively new tool in oil-producing areas. From the beginning, the possibilities of this new service caught the imagination of many of the oil operators and acidizing engineers. Through the continued and ever increasing use of the pilot during the past year, and the close cooperation of the oil operators who have used this service, the efficiency and utility of the Electric Pilot service has been increased to a point where it is now a well established and recognized service. There are two major uses for the Electric Pilot: (I) permeability survey; (2) selective acid treatments. Permeability surveys are made to determine the thickness of the various permeable sections at the borehole, the vertical position of these zones at the bore hole, and the relative capacities of the various zones. Nomenclature Data obtained from the permeability survey are used to calculate three different indexes that pertain to the volume of fluid injected into the various permeable zones. A nomenclature for these various indexes has been set up, which correspond with the various productivity indexes, except that they are a measure of injected fluid rather than produced fluid. The nomenclature and definition of the indexes used in connection with a permeability survey by the Electric Pilot are as follows: 1. Capacity.—The volume of water injected into an individual permeable zone, in gallons Per minute. 2. Capacity Index.—The volume of water injected into an individual permeable Zone, in gallons Per minute Per pound Per Square inch differential Pressure. 3. Specific Capacity Index.—The volume of water injected into an individual permable zone in gallons Per minute Per pound per square inch differential per foot of thickness of the zone at the borehole. Capacity is the most generally used index, and for planning initial acidizing procedures and most workover jobs it is sufficient. For comparing permeability surveys on the same well before and after

Jan 1, 1945

By F. V. Lenel, M. V. Rose, A. B. Backensto

WHEN aluminum-flake powders are compacted and hot pressed and the resulting compacts are extruded or hot forged, a group of materials with unique properties is obtained. Not only do they exhibit high room-temperature strength of the order of some of the aluminum alloys, but they maintain this strength even after prolonged heat treatment at temperatures up to 900°F. Moreover, their strength decreases much less with increasing temperature than that of aluminum alloys of comparable room-temperature properties. Irmann,'" who discovered and first described this group of materials, which was called SAP, showed that the room-temperature mechanical properties of the extrusions are a function of the oxide content of the powders and therefore the oxide content of the extrusions. The higher the oxide content, the higher are their tensile strength, yield strength, and hardness, and the lower their ductility. Lyle" investigated the relationship between mechanical properties at elevated temperature and oxide content in the course of the development work of the Aluminum Co. of America on materials, called APMP, similar to those developed in Switzerland. He found that at 600 °F, just as at room temperatures, tensile strength and yield strength increase and elongation decreases with oxide content. A careful study of his data (Fig. 3, loc. cit.) shows, however, that the scatter is more pronounced than at room temperature. Gregory and Grant's data on the creep5 and stress-ruptureb roperties of the one commercial grade of the Swiss SAP and the various grades of APMP indicate that creep strength and stress to rupture also generally increase with increasing oxide .content. Ever since this new group of materials was discovered, attempts have been made to explain the mechanism by which they obtain their high room-temperature and particularly their elevated-temperature strength. In most of the attempts the new material was considered as a dispersion of aluminum oxide particles in a matrix of aluminum. Ir-mann, Von Zeerleder, and Rohner' applied a theory on dispersion strengthening developed by Rohners to the flake-powder extrusions. According to this theory the elastic limit S, of a dispersion would depend upon the average distance between the dispersed particles L according to the equation: 2 E ¦ a where E is the modulus of elasticity and a the distance between nearest neighbors in the lattice of the matrix material. Irmann and co-workers assumed

Jan 1, 1958

By G. C. Stone

The method of making oxide of zinc direct from the ore was invented and developed at the works of The New Jersey Zinc Co. at Newark in the middle of the last century. The process was invented by Burrows, who had not the ability, financial or technical, to work out the details necessary to make it of commercial value. This was done by Col. Wetherill, whose name is commonly attached to this process. The grate bars used are also frequently called Wetherill grates, which is a misnomer because they were in common use for boiler firing at the time, and he never claimed their invention. The invention of the process was due to the efforts of The New Jersey Zinc Co. to find a profitable means of working the ores from Franklin and Sterling Hill, N. J. These are a mixture of franklinite, willemite, and zincite, containing about 20 per cent. of zinc. The first attempts were to make spelter, which were not successful, owing to the low grade of the ore and the fusibility of the residue. Failing in this, the next attempt was to make oxide in large muffles and reverberatory furnaces. This succeeded, although the cost of operation was high, the recovery low, and the quality of the product uncertain. In 1855, the new process was patented and has been in successful operation ever since. Essentially, the process is to spread a mixture of coal and ore on a body of burning coal on a perforated grate, and blow an excess of air through the grate. The zinc is reduced in contact with the coal, volatilized and burned by the excess of air in the upper part of the furnace and in the flues. It is then carried to the bag rooms by the excess air and products of combustion which are foreed through the flues by fans. In its main features, the process is the same today as at the time of its invention, but the details have been so modified that it would hardly be recognized by its originators. OrEs The process is applicable to all the oxidized ores of zinc and to roasted sulphides, provided the gangue is not so fusible as to leave a residue that is impervious to the blast. In many cases the ores contain impurities that make it impossible to produce an oxide of a good enough color to be

Jan 1, 1918

By John Blandy

EVERY new mining district has had its own peculiar experiences in inventing and experimenting upon new methods for the various operations of mining, and more particularly in the processes of crushing and dressing ores. As a matter of course, during this period many old things have been reinvented, patented, and cast aside, there to remain until at a future day other geniuses shall bring them forth again as new. In this respect the Copper Region of Michigan has not been behind other mining centres, and probably in no other part of the country has more money been expended in devising new machines and improvements upon old ones for the crushing of the rock. The appliances for washing the sand have not been so varied, simply for the reason that, having but one mineral, or rather metal, of high specific gravity to separate from rock material which varies but little in its character in any one mine, it requires much less care than is necessary in most mining centres of the world. At the beginning of operations in that district most of the work was in the control of Cornish miners, who introduced the simplest of Cornish mills, namely, wooden stem pestles, with wooden shafts and cams. These were well suited to the small mines, and particularly to the limited means of transporting more expensive machinery. As these facilities improved, they were enabled to change to iron, and to vary their patterns of rods, shafts, cams, and mortars. The most approved pattern, finally obtained, is the square or round stem, with collar adjustable by means of keys. In its present form it is a bar of cold rolled shafting, an eye in the top, an adjustable collar with key-plate and keys, the head and a shoe of chilled iron. The stem is fitted into the head by a slight taper. The battery has heretofore been of wood, lined with chilled cast plates, and bed-plate of the same, but within the past year the California pattern has been introduced. The screens are of sheet-steel, drilled with 16 holes to the inch. During this period of trial and gradual improvement in the pestle stamps, in the years 1855-6, the Ball steam-stamps were intro¬duced, and after years of labor and expense, have been made the most efficient and powerful machines ever yet used for the purpose. It is ostensibly the Nasmyth steam-hammer, and yet the

Jan 1, 1874

By Gilbert H. Cady

Extensive sampling of coal in Illinois during the past 10 or 12 yegrs by the State Geological Survey, in cooperation with various organizations, such as the U. S. Bureau of Mines, the University of Illinois, and the Illinois Cooperative Mining Investigations, has made possible the delineation of two areas of low-sulfur coal in the southern part of Illinois. The $fur content is less than 1.25 per cent., so that, if otherwise suitable, these coals can be employed for metallurgical uses and for the manufacture of water-gas and retort gas. One of these areas is small and lies in Jackson County, near Murphysboro, the other is much larger and includes a large part of the famous Franklin County field. A small area of No. 2, or Murphysboro, coal has been worked for many years near the town of Murphysboro, Jackson County, Ill. In two mines, at least, the coal has a sulfur content of less than 1.25 per cent. It is doubtful, however, whether this field will ever be a source of large tonnage as the total area underlain by low-sulfur coal in workable thickness is probably less than 15 sq. mi. (24.14 sq. km.), and a large part of it has already been worked out.. The location of the area of low-sulfur coal in the Franklin County field is shown in the accompanying map. The small area underlain by the Murphysboro low-sulfur coal is shown near the town of that name in the central part of Jackson County. The larger area lies in the west side of Franklin County, extending also about 6 mi. (9.65 km.) south into Williamson County, about 4 mi. (6.43 km.) west into northern Jackson and western Perry County, and northward an undetermined distance into Jefferson County. All but the northern limit of the area is fairly well defined by sampling in numerous mines. The inner cross-lined area is underlain by coal having less than 1 per cent. sulfur, the outer boundary surrounding the area underlain by coal having less than 1.25 per cent. sulfur. The coal mined in the district is No. 6 or Herrin coal, commonly known as the Carterville or Franklin County coal. The bed has a thickness varying from about 8 ft. (2.4 m.) on the border of the low-sulfur area up to more than 10 ft. (3 m.) in the central portion, locally having a thick-

Jan 1, 1920

By Edward S. Cook

For several years past, dating particularly from the days of serious "ore-dirt" complications at the Warwick furnace, I have been desirous of providing some safe, quick and easy method of relieving the tuyeres of slag, when the cinder- and iron-notches are chilled through loss of heat in the clucible or when, from dropping or jumping of stock, the molten slag is forcibly driven into the bellyand leg-pipes. Various methods were proposed, but objections of one kind or another always presented themselves, and the subject was postponed to a more convenient season. In the summer of 1887, while running on anthracite alone, 1 found the various expedients in use to be so utterly valueless, that the importance of a practicable tuyere slagging-valve impressed me more forcibly than ever. The holes left in the cast-iron jacket at one side of the bottom of the water-blocks were found to be of no value whatever. The swinging or hinged cap on the elbow of the belly-pipe, while convenient to permit the removal of lag after the belly-pipe was partially or wholly filled, could not be adapted to discharge the slag before solidifying, except at great risk to the men and loss of time just when the constant running of the engine and the keeping of blast on the furnace was of the utmost importance. By removing keys from the caps and holding them in place with props, the slag could be discharged through the tuyeres and belly-pipes, with the engine running, by knocking the props away at a given signal. This method is extremely hazardous to life and limb, and I have always hesitated to make use of it. When the furnace is in such condition as to require the adoption of some method of the kind, the stoppage of the engine, cooling the blast and the contents of the crucible, always aggravates the trouble. When the caps are blown open and the slag is discharged by removal of the props, it is necessary to stop the engine to replace them. An hour or more will elapse before this can be done, as the slag must be partly removed before the tuyeres can be approached by ordinary mortals, and the caps handled and fastened in place again. Any movement of the stock is liable to burn the workman, as he stands, securing the cap in front or at one side of the open belly-pipe.

Jan 1, 1889

By Fred C. Bond

THE process of comminution by grinding is properly classified as an art, rather than as a science. Like most other operations concerned in ore dressing, or in the treatment of nonmetallic minerals, the mathematical relationships of rock breaking are still obscure, and much disputed. If some basic formula exists, comparable for instance to E = RI in electricity, it has not yet been placed in, common use. The absence of such a comprehensive mathematical background undoubtedly is the cause of many inefficient designs and installations, as well as of much poorly oriented experimental work. On the other hand, the mathematical immaturity of the process constitutes an opportunity for a real contribution on the part of those who enjoy mental pioneering. Some of the statements made in any such exploratory work may be little more than opinions, and it is to be expected that some will later be proved untrue; but such an evolutionary development is necessary if we are ever to arrive at the fundamental laws, the discovery of which can change the empirical art into a mathematically exact science. The most significant principle of comminution that we possess is probably Rittinger's law, which states that the work done in crushing or grinding is proportional to the area of the new surface produced. There is an alternative theory, known as Kick's law, which formerly was preferred to Rittinger's but which now is rather discredited. According to Kick, the work done in comminution is proportional to the volume, or weight, of the pieces broken, or to the cube of their diameters, while according to Rittinger it is proportional to the square of the diameters. Careful determinations of size distribution below the limit of sieve sizes1 indicate strongly that under ordinary grinding conditions the amount of new surface area produced is directly proportional to the net power input. Changes in the size ratio between the balls and the particles cause important differences in the proportion of the product that passes a given mesh size, but do not affect the total amount of new surface area; they merely change the distribution of the surface among mesh sizes. The principle of constant surface area is the logical result of Rittinger's law, and it may well have an important bearing on the comminution theories of the future. FORMULA FOR BALL WEAR Grinding tests have been made in the Allis-Chalmers laboratory for more than 9 years, using a standard charge of mixed balls of different sizes; and a continuous record has been kept of the rates of wear of each size. These results have been combined and plotted in various ways in order to discover the relationship that exists

Jan 1, 1940

By C. Fairhurst, A. M. Starfield

As a practicing mining engineer, I face many rock mechanics' problems daily and would like to mention one or two examples to illustrate the current gap between laboratory investigations and actual field problems. I would like to endorse Dr. Obert's suggestion that more field measurements and observations should be undertaken. There is an ever-increasing body of data beginning with Hast's results in Sweden,l then measurements at Elliot Lake, Canada, and so on, including our own measurements at White Pine, which clearly indicate that the horizontal stresses underground are often at least as large as the vertical stresses. Visual obsenation of the deformation of roof and pillars (including failure due to horizontal compression) also demonstrates that the horizontal stresses are often most important. Yet almost every laboratory investigation begins with the assumption that the only stresses acting are vertical. Roof spans in layered formations. for example, are calculated on the assumption that the rock behaves as a gravity loaded beam. This is all too often unrealistic. Roof bolts are also often considered to be simply means of suspending the gravity loaded beams. As Dr. Reed has mentioned they are probably, in fact, acting to restrain a beam which is attempting to buckle due to lateral pressure. The fact that moisture can reduce the strengths of some rocks as much as 50 percent has been known for many years. In the mine me are almost always faced with wet rock, yet no one has investigated ways in which this wakening effect can be overcome. as, for example, by waterproofing the rock. C. Fairhurst, University of Minnesota I would like to mention that we have found,2 from stress-relief determinations, that appreciable (over 1000 lb per sq in.) horizontal pressures occur also at the surface in granites quarried in central Minnesota. Whilst I agree that more field measurements are desirable, it is important to point out that most university research is undertaken by graduate students who must attend classes daily. Their research is therefore restricted to the laboratory. A.M. Starfield, University of Minnesota No one denies the importance of obtaining: data from field measurements. It is equally important, however, that field measurements be guided by theory. Much time and money can be wasted by indiscriminate measurement. An example of the value of theory in interpreting measurements is given in Dr. Obert's comments on the time dependent strain observed in a salt mine. He anticipated that the stress at the wall of the opening would change with time because salt is viscoelastic rather than elastic. It can be shown from theory that if an excavation in a viscoelastic medium is unsupported, then the stress at the wall does

Jan 1, 1967