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By O. D. Sherby, J. E. Dorn

SEVERAL years ago Zener and Hollomon1 suggested that the flow stress of metals might be related to the temperature and strain rate in accord with the functional equation: s=s(eeh/rt) [1] at the same state. The Zener-Hollomon relation also contains the significant tacit implication that the energy for activation, AH, is substantially independent of the state of the material. The utility of this method for correlating creep data with tensile data was illustrated in a preliminary reportL on the effect of alloying additions on the secondary creep rates of binary a solid solutions in aluminum as shown for Al-Mg alloys in Fig. 1. Not only do the secondary creep and ultimate tensile properties for each alloy correlate well on this plot but in addition the activation energy, AH = 17,900 R cal per mol. is identical for the various compositions. Similar types of curves correlating the secondary creep rates at 422°K (300°F) with ultimate tensile data were also obtained for a series of dilute a solid solutions of copper, germanium, zinc, and silver in aluminum. In all cases the activation energy for creep, AH, was found to be equal to about 17,900 R cal per mol independent of the type of alloying element or its concentration. The coincidence of the activation energies for these alloys is probably due to the fact that the activation energies for creep are rather insensitive to small composition changes. Alloying additions, as shown in Fig. 1, however, increased the stress necessary to obtain equivalent values of ee?H/RT. Thus the stress level in curves of the type represented by Fig. 1 gives the relative creep strengths of the various alloys. Inasmuch as these correlations between creep and tensile data were obtained for creep tests at 422°K, it appeared advisable to ascertain the range of secondary creep rates and temperatures over which correlations between creep and tensile data could be made on the basis of the Zener-Hollomon relationship. If, for example, the activation energy changes with different ranges of creep temperatures, the utility of the proposed analysis would be severely weakened. But if AH is constant not only for all dilute alloys, but also over wide ranges of temperature and secondary creep rates, confidence will be developed not only in the broad utility of the Zener- Table I. Chemical Analysis':' and Grain Size of Alloys Mean Grain Residual Impurities. Wt Pct Diam- Alloying Atomic-eter, Element Pct Si Fe Cu Mg Mn mm Aluminum 99.987 0.003 0.003 0.006 0.001 0.25 Magnesium 1.617 0.003 0.004 0.006 0.26 Copper 0.101 0.003 0.003 0.0006 0.001 0.29 Zinc 1.616 0.003 0.005 0.007 0.001 '0.26 * The authors express their appreciation to the Aluminum Company of America for the preparation and chemical analyses of these alloys. Hollomon relationship, but also in its theoretical justification. The following investigation was instituted in order to ascertain the range of validity of the Zener-Hollomon relationship when it is applied to creep and tension data. Materials, Equipment, Technique In view of rather extensive correlatable data now available on the plastic properties of a series of binary a solid solutions of magnesium, copper, germanium, zinc, and silver in aluminum, these alloys were again selected for the present investigation. Previous reports have already covered the tensile properties of these alloys at subatmospheric temperatures," and at elevated temperature," as well as their fatigue properties at atmospheric temperatures, nd their creep properties at 422°K.' Resistivity measurementsa as well as precision lattice constant determinations? evealed that these alloys are a solid solutions. After homogenization. 0.100 in. thick sheets were rolled to 0.070 in. in thickness and recrystallized to about the same grain size. Since the details of these treatments were reported previously," they will not be repeated here. In order to appropriately reduce the scope of creep tests in this investigation only the typical alloys shown in Table I were investigated. All creep specimens were machined such that their tensile axes were in the rolling direction of the 0.070 in. sheet stock. The gage section was 2 in. long and 0.500 in. wide with a reduced section of 3.50 in. Creep strains were measured by means of rack and pinion type extensometers with a sensitivity of 0.005 in. per division. Readings were estimated to 1/10 of

Jan 1, 1953

By W. H. Bassett, C. H. Davis

ALTHOUGH brasses and bronzes have been made for ages, a systematic study of their physical properties has been carried out only during the years of the present century. Among these properties may be included those which are to be detected by means of microscopic examination; in other. words by the science of metallography. The earlier workers in this field, both in this country and abroad, gave their attention to steel. When the senior author explored the situation in 1902, there was little encouragement to be found in undertaking the study of the non-ferrous alloys. A start was made, and the metallography of the brasses and bronzes, as well as of the copper-nickel-zinc alloys developed materially under his direction. Annealing experiments were begun in 1902, and in the succeeding years the effect of temperature, and the influence of previous working, on the grain size of brass were studied. The conclusions so well known and widely published today were largely reached during those earlier years. . In 1905 the first complete annealing series were made. By this it is meant that brass and copper sheet, 5 B & S Nos. hard, was machined into tensile test specimens, then annealed under accurate control for 30 min. at temperatures up to the melting point of the material. Various determinations were made, including tensile strength and elongation in 2 in. There rapidly followed similar series on all of the copper-zinc alloys from 100 to 60 per cent. copper, on the bronzes, cupronickels, and on copper-zinc-nickel alloys. At this point there was published by Grard, in October, 1909,1 the very comprehensive and complete work on the tensile properties of cartridge brass, 90-10 copper-zinc, and electrolytic copper. The excellent photomicrographs in that paper illustrated the changes in structure produced by cold rolling as well as by annealing at different temperatures, but where Grard's work was confined to copper and to two alloys, the investigations in this laboratory have been over the entire fields of the commercial copper-zinc alloys, copper-tin alloys, representative copper-nickel and copper-nickel-zinc alloys as well as aluminum bronzes and others of a more special nature.

Jan 1, 1928

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß') does not change significantly between 322o and 8000 K, confirming that the ß' alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp's law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß') has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß') were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

By Robert Bosworth

THE liability for damages to the surface caused by subsidence is an ever present threat in all underground mining. In ordinary lode mining, this threat rarely materializes into an action, due to the method of mining metalliferous ores, the dip of the veins, and the nature of the ground itself. In the mining of coal, however, this threat is very real. The coal frequently lies close to the surface, in beds underlying large areas of land of which the surface is suitable for agricultural or urban development. Furthermore, the coal is generally mined by the "room and pillar " method and when the pillars of coal are removed, the subjacent support is destroyed. This question of the duty of surface support has now become a very live one in Colorado. What was waste prairie land a few years ago has become valuable agricultural land dotted here and there with growing towns. Frequent references will be made here to Colorado conditions and adjudicated cases, but those conditions and cases and the conclusions to be drawn therefrom are applicable to all coal-mining states. Briefly stated, the question is "Does the owner of the substrata or underlying mineral owe any duty of surface support to the owner of the superjacent strata or surface?" There is no absolute duty of support owed by the mineral owner and this assertion is made with full knowledge of numerous expressions to the contrary by courts of Pennsylvania, Illinois, Colorado and other coal-mining states. Whether or not any duty exists depends upon the circumstances surrounding each case, and since in the nature of things those circumstances are rarely identical, there can be no absolute rule.

Jan 1, 1928

By John M. Cigan

Samples of copper-lead concentrates from the mine of Cia Minerals Santander, Inc., a Peruvian subsidiary of the St. Joseph Lead Co. were recently subjected to special analysis. This concentrate was known to contain bismuth which, under some circumstances, might have incurred a smelter penalty. In this case, customers for the concentrate accepted it and requested a higher concentration of bismuth. Although chemical analysis would disclose the presence of the metal, it was not possible with equipment available at the mill in Peru to determine the mode of occurrence in the fine grained ores.

Jan 11, 1964

By John M. Kelly

New Mexico produced 39,751,868 bbl. of oil in 1941 and ranked seventh among the oil-producing states. Its 1941 production established an annual record, exceeding the 1940 record year by 854,498 bbl. The average daily production for the year was 108,909 bbl. The average daily non-marginal well allowable for New Mexico on Jan. I, 1941, was 36 bbl.; at the close of the year it was 43 bbl. The average daily pipe-linc runs were approximately 3 per cent less than the allocations of the New Mexico Oil Conservation Commission, which followed closely the recommendation of the United States Bureau of Mines in setting the daily outlet demand. The production in Lea County was 34,333,448 bbl.; Eddy County, 5,009,354 bbl.; and northwestern New Mexico (San Juan and McKinley Counties), 406,306 barrels. The total number of completions in the state was 402, of which 301 were oil wells, 19 gas wells, and 82 dry holes. Drilling during 1941 was 68 per cent of 1940, and the ratio of dry holes to producers, I to 4, was the greatest since 1935. Of these dry holes 43 were drilled in proven fields and 39 were wildcats. One new oil field and one new gas field were discovered as a result of the 1941 wildcatting program. However, numerous extensions were made to the existing fields, which, although they were called extensions to proration areas, were in reality field discoveries, being on separate geologic structures. Southeastern New Mexico Lea County The Monument field was the largest producing field in Lea County, with 6,973,808 bbl. It was closely followed by the Eunice field, with 6,644,181 bbl.; Vacuum field, with 4,800,608 bbl. and Hobbs, with 3,624,159 bbl. Hobbs field, however, still has the largest total recovery, this being 97,407,929 bbl. at the end of 1941. The new oil-field discovery in Lea County during 1941 was the Salt Lake field, T. 20 S., R. 33 E. The discovery well was Leonard-Welch State No. I, NW. NW. of sec. 18, T. 20 S., R. 33 E. This well was drilled to a total depth of 3103 ft. and was completed for an initial production of 250 bbl. per day pumping. The oil is 26" gravity and the producing horizon is in the San Andres limestone of Permian age. The discovery well was completed on June 22, 1941, and since that date four more producers have been completed, with no failures. The area is about 10 miles north-west of the Lynch pool, to which the oil from this field is being trucked because there is no pipe-line connection. The greatest drilling activity during 1947 was in the Maljamar field of western Lea County, with 62 completions, 59 being oil wells and 3 dry holes. The limits of this pool are now being defined on the north and south but to date have not been defined either to the east or west. The total number of 40-acre oil-producing units in the field at the close of the year was 158. On April I, 1941, a pressure-maintenance project was installed at the southern end

Jan 1, 1942

By John M. Kelly

New Mexico produced 39,751,868 bbl. of oil in 1941 and ranked seventh among the oil-producing states. Its 1941 production established an annual record, exceeding the 1940 record year by 854,498 bbl. The average daily production for the year was 108,909 bbl. The average daily non-marginal well allowable for New Mexico on Jan. I, 1941, was 36 bbl.; at the close of the year it was 43 bbl. The average daily pipe-linc runs were approximately 3 per cent less than the allocations of the New Mexico Oil Conservation Commission, which followed closely the recommendation of the United States Bureau of Mines in setting the daily outlet demand. The production in Lea County was 34,333,448 bbl.; Eddy County, 5,009,354 bbl.; and northwestern New Mexico (San Juan and McKinley Counties), 406,306 barrels. The total number of completions in the state was 402, of which 301 were oil wells, 19 gas wells, and 82 dry holes. Drilling during 1941 was 68 per cent of 1940, and the ratio of dry holes to producers, I to 4, was the greatest since 1935. Of these dry holes 43 were drilled in proven fields and 39 were wildcats. One new oil field and one new gas field were discovered as a result of the 1941 wildcatting program. However, numerous extensions were made to the existing fields, which, although they were called extensions to proration areas, were in reality field discoveries, being on separate geologic structures. Southeastern New Mexico Lea County The Monument field was the largest producing field in Lea County, with 6,973,808 bbl. It was closely followed by the Eunice field, with 6,644,181 bbl.; Vacuum field, with 4,800,608 bbl. and Hobbs, with 3,624,159 bbl. Hobbs field, however, still has the largest total recovery, this being 97,407,929 bbl. at the end of 1941. The new oil-field discovery in Lea County during 1941 was the Salt Lake field, T. 20 S., R. 33 E. The discovery well was Leonard-Welch State No. I, NW. NW. of sec. 18, T. 20 S., R. 33 E. This well was drilled to a total depth of 3103 ft. and was completed for an initial production of 250 bbl. per day pumping. The oil is 26" gravity and the producing horizon is in the San Andres limestone of Permian age. The discovery well was completed on June 22, 1941, and since that date four more producers have been completed, with no failures. The area is about 10 miles north-west of the Lynch pool, to which the oil from this field is being trucked because there is no pipe-line connection. The greatest drilling activity during 1947 was in the Maljamar field of western Lea County, with 62 completions, 59 being oil wells and 3 dry holes. The limits of this pool are now being defined on the north and south but to date have not been defined either to the east or west. The total number of 40-acre oil-producing units in the field at the close of the year was 158. On April I, 1941, a pressure-maintenance project was installed at the southern end

Jan 1, 1942

By C. A. Hartnagel

The production of petroleum in New York state in 1942 amounted to 5,410,000 bbl. This represents an increase over each of the four preceding years, and, with the exception of 1937, is the largest production since the peak of over six million barrels in 1882, shortly after the discovery of oil in Allegany County. The oil industry in New York is virtually stabilized and there has been little or no exploration for new sources of supply in recent years. The boundaries of the present fields were established more than 30 years ago and since then no additional reserves have been found. Deep drilling for natural gas during the past 10 years both within and without the oil fields has failed to find oil in quantity below the present producing sands of Devonian age. Oil Since 1882, the New York fields have produced approximately 140 million barrels of oil. Of this amount, 65 million was produced up to the year 1919 by ordinary pumping methods; that is, without flooding by water or the use of other secondary-recovery methods. In the year 1919, when a law was passed making the use of water-flooding methods legal, the oil production, of the state amounted to only 851,000 bbl. In the 23 years since 1919, there have been produced in the state 75 million barrels, or 10 million more than in the previous 37 years, which included the period of flush production. Price.—On March 26, the price of crude oil was raised from $2.75 to $3.00 per barrel, hut this increase had little or no effect on the number of wells drilled. In the Allegany field, which accounts for three fourths of the state's oil production, 1259 wells were completed in 1942, 7 less than in 1941. The smaller number of wells drilled was not only due to the shortage of labor but also was caused by the fact that in water-flooding territory a definite program for drilling wells is followed, and the flush period of an oil well is not usually reached in time to profit by any given price increase. Daily Production.—All of the oil wells in New York state, some 21,000 in number, are small producers. The average daily oil production is 7/10 bbl. per well. Under good flooding conditions, a maximum production of 5 to 8 bbl, a day is reached about one year after the flood begins to act on the well. In 5 years the daily production usually is less than one barrel. Although most of the oil in New York is produced by flooding, an estimated 2500 old wells produce without flooding. Some of these produce as little as 1/20 bbl. a day and are pumped only at intervals. The small producing Wells are mostly on lands leased to the larger oil companies and later will be included in a flooding program. At present, they are pumped only because the owners of the land insist on the royalty. Government Aid Needed.—Because of its good lubricating qualities, New York oil is one of those for which there is an insistent and growing demand, but even at its present price of $3.00 per barrel, many of the operators are producing at a loss.

Jan 1, 1943

By C. A. Hartnagel

The production of petroleum in New York state in 1942 amounted to 5,410,000 bbl. This represents an increase over each of the four preceding years, and, with the exception of 1937, is the largest production since the peak of over six million barrels in 1882, shortly after the discovery of oil in Allegany County. The oil industry in New York is virtually stabilized and there has been little or no exploration for new sources of supply in recent years. The boundaries of the present fields were established more than 30 years ago and since then no additional reserves have been found. Deep drilling for natural gas during the past 10 years both within and without the oil fields has failed to find oil in quantity below the present producing sands of Devonian age. Oil Since 1882, the New York fields have produced approximately 140 million barrels of oil. Of this amount, 65 million was produced up to the year 1919 by ordinary pumping methods; that is, without flooding by water or the use of other secondary-recovery methods. In the year 1919, when a law was passed making the use of water-flooding methods legal, the oil production, of the state amounted to only 851,000 bbl. In the 23 years since 1919, there have been produced in the state 75 million barrels, or 10 million more than in the previous 37 years, which included the period of flush production. Price.—On March 26, the price of crude oil was raised from $2.75 to $3.00 per barrel, hut this increase had little or no effect on the number of wells drilled. In the Allegany field, which accounts for three fourths of the state's oil production, 1259 wells were completed in 1942, 7 less than in 1941. The smaller number of wells drilled was not only due to the shortage of labor but also was caused by the fact that in water-flooding territory a definite program for drilling wells is followed, and the flush period of an oil well is not usually reached in time to profit by any given price increase. Daily Production.—All of the oil wells in New York state, some 21,000 in number, are small producers. The average daily oil production is 7/10 bbl. per well. Under good flooding conditions, a maximum production of 5 to 8 bbl, a day is reached about one year after the flood begins to act on the well. In 5 years the daily production usually is less than one barrel. Although most of the oil in New York is produced by flooding, an estimated 2500 old wells produce without flooding. Some of these produce as little as 1/20 bbl. a day and are pumped only at intervals. The small producing Wells are mostly on lands leased to the larger oil companies and later will be included in a flooding program. At present, they are pumped only because the owners of the land insist on the royalty. Government Aid Needed.—Because of its good lubricating qualities, New York oil is one of those for which there is an insistent and growing demand, but even at its present price of $3.00 per barrel, many of the operators are producing at a loss.

Jan 1, 1943

By D. I. Bardos, A. M. Bardos, Paul A. Beck

The approximate effective silicon radii in ternary Laves phase alloys with transition elements and silicon were found to range between 1.16 and 1.21A, i.e., considerably smaller than the atomic radius calculated for elemental silicon. The atomic radii were found to increase with the size of the transition element atoms in the structure. It has been noted by Aronsson1 that silicon in solid solution in iron, cobalt, and nickel has an effective CN 12 atomic radius of approximately 1.20Å, a value very much smaller than the CN 12 radius of 1.34Å derived from the interatomic distances in elemental silicon.7 The unusually short metal-silicon interatomic distances in transition element monosilicides and disilicides have been also pointed out by various investigators.1 A similar tendency was observed by Nevitt in Cr3O type silicides.2 Recent work on Laves phases in ternary systems of silicon with transition elements4"8 suggested that extensive Laves phase fields may occur in such systems.8 It has been pointed out by Laves7 that the MgCu2 and MgZn2 type structures lend themselves particularly well for the determination of the effective radii of the component atoms. In these AB2 phases the B atoms are arranged in close packed straight lines, and their distances are related in a simple manner to the lattice parameters.8 The present work was undertaken in order to find out whether or not the B transition element in such AB2 Laves phases can be replaced to an appreciable extent by silicon. In cases where extensive substitution proves to be possible, the "average atomic radius for the B site" at various silicon contents was to be determined, and the effective atomic radius of silicon calculated by extrapolation to complete replacement of the B component by silicon. The following ternary systems were studied: Ti-Mn-Si, Ti-Fe-Si, V-Co-Si, V-Ni-Si, Nb-Fe-Si, Nb-Co-Si, Ta-Fe-Si, Ta-Co-Si, and Mo-Fe-Si. In all of these alloy systems, the Laves phase solid solutions were found to extend over a considerable range of silicon content. As previously reported,4"8 in the V-Co-Si, V-Ni-Si, and Mo-Fe-Si ternary systems Laves phases do occur, even though there are no corresponding binary Laves phases. In stabilizing the Laves phase, silicon acts as if it were decreasing the effective electron concentration of the alloy.8 A more detailed study of the boundaries of the Laves phases in the V-Co-Si and V-Ni-Si systems has been made and will be published elsewhere. In both cases, the elongated Laves phase fields extend parallel to the B-Si side of the composition triangle, clearly showing that silicon is substituting for cobalt, respectively, nickel over a wide range of compositions. The binary Laves phases NbCo2 and TaCo2 have the cubic MgCu2-type structure. It was found that, in both ternary systems with silicon, again the MgZn2-type hexagonal Laves phase is stabilized and that this phase extends to high-silicon contents. In each ternary system at least three Laves phase alloys of the composition A(B1_xSix)2 were used, x here denoting the fractional substitution of the B-transition element atoms by silicon. The alloys, listed in Table I, were prepared by arc melting in argon. Each specimen was water quenched after a homogenizing anneal of 3 days at 110(FC, except for the Mo-Fe-Si alloys, which were annealed at 1200°C. Metallographic examination showed that most of the homogenized alloys consisted of a single phase, although some had minor amounts of a second phase, as shown in Table I. X-ray diffraction patterns were prepared using an asymmetrical focusing camera of large resolution and Fe Ka radiation. The patterns were indexed, and the lattice parameters of the hexagonal Laves phases were determined from the available diffraction lines of highest indices: (213), (205), and (313). The lat-

Jan 1, 1963

By H. H. Kellogg, T. R. Ingraham

Three anhydrous zinc sulfates have been identified. They are: ZnSO,(a), stable below 1007°K; ZnS04(/3), stable above 1007OK; and ZnO.ZZnSO,. The decomposition pressure of each sulfate has been measured and the following relations calculated from the results: The measured data have been combined with the known themzodynamic properties of ZnS, ZnO, Zn, SO,, and SO, to yield univariant and bivariant phase diagrams for the system Zn-S-0. The application of these diagrams to problems of roasting zinc concentrates is discussed. PRESENT knowledge of the equilibrium chemistry of the system Zn-S:O, so essential to scientific control of zinc-blende roasting, is deficient in several respects. A basic sulfate of zinc has been reported by many investigators, but its composition is in doubt and its thermodynamic properties have not been measured. Our scanty knowledge of the properties of the normal sulfate at roasting temperatures is based on old and inexact studies. A crystal transformation in the normal sulfate, involving a sizable heat effect, has been noted by several investigators but has never been quantified. The studies reported herein were designed to fill these gaps in knowledge and to make possible a reasonably complete thermodynamic description of the system Zn-S-0 at roasting temperatures. The results make possible a far more exact understanding of zinc roasting chemistry than was hitherto possible. EXPERIMENTAL The principal experimental technique employed was the measurement of the total gas pressure developed from decomposition of either ZnSO, or ZnO2ZnS0, in a closed system. The apparatus employed was essentially the same as that described by Warner and lngrahaml and Flengas and tngraham.' The unusual feature is a flexible Pyrex bellows used to separate the reaction gas mixture (S03, SOz, and 02) from the mercury in the manometer and thus prevent corrosion of the mercury by SO3. The bellows operates without evidence of hysteresis and, barring accidents, may be used for several months. The response of the bellows varies from manometer to manometer, but is generally of the order of 0.6-cm displacement for a l-cm change in pressure. The response for all manometers has been linear over the range 0 to 1 atm. To prevent condensation and polymerization of sulfur trioxide, the bellows-manometer was maintained at 100.0" * 0.5" by a circulating bath of silicone oil. The connecting tubing between the manometer and the furnace was maintained at 100.0" * 0.2"* also, with a stirred air bath. The open end of the manometer was connected with a chamber which was maintained at a known pressure. The pressure could be varied so that readings of the height of the mercury column, measured with a cathetometer, could be made with both rising and falling mercury column. By using the average of the readings, any error due to sticking of the mercury column was minimized. The sample was placed in a 2-in.-long platinum boat formed into the shape of a half-cylinder. The sample was prepared as a fine powder and pressed against the inner wall of the platinum boat. A silica thermocouple well, covered with a platinum sleeve, was placed lengthwise along the center of the boat. The temperature of the sample was read on a calibrated Pt-10 pct Rh theirnocouple. The temperature profile of the furnace was constant within ± 0.2 C over the length of furnace occupied by the sample. The horizontal furnace used to contain the sample and the quartz reaction tube was electrically heated, with the control thermocouple placed 1/4 in. from the windings. A Brown Pyro-O-Vane temperature controller with a 3-sec response time was used to maintain the furnace temperature. Before beginning a run, the apparatus, including the bellows manometer, was thoroughly washed in sib with acid and distilled water to remove any

Jan 1, 1963

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920's, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930's, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940's were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960

The Library of the above-named Societies is open from 9 A.M. to 10 P.M., except on holidays. It contains about 70,000 volumes and 90,000 pamphlets, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend a portion of their time in localities isolated from sources of information. To these the Library, through its Library Service Bureau, can render valuable service through correspondence; letters requesting information will receive especial attention. The Library is prepared to furnish references and photographic copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information on the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape.

Jan 7, 1917

By Walter E. Hopper

The Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five railroad-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. During the winter of 1908-09 I spent 'four months in the Caddo field, under the direction of the Louisiana Geological Survey and the U. S. Geological Survey. II. History and Development. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser" Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905,

Jan 1, 1912

By L. B. Herring, Harold Decker

The area under discussion includes districts 2 and 4, so designated by the Texas Railroad Commission,‡ and comprises the following 26 counties: Bee, Brooks, Calhoun, Cameron, De Witt, Duval, Goliad, Gonzales, Hidalgo, Jackson, Jim Hogg, Jim Wells, Karnes, Kenedy, Kleburg, Lavaca, Live Oak, Nueces, Refu-gio, San Patricia, Starr, Victoria, Webb, Willacy, Wilson and Zapata. Drilling and Production The total number of wells drilled in this district during 1944 is shown in Table 5. This indicates a 41 per cent increase in all drilling over 1943. In spite of every handicap created by the war, the oil industry more than met the crisis in its drilling program in this district. Last year we thought it would be impossible to add to the total number of wells drilled in the previous yea;, but in spite of the lack of manpower and materials this large increase was shown. During 1944 this district produced 124,201,978 bbl. of oil from 11,607 producing wells, whereas in 1943 it produced 88,421,693 bbl. from 11,211 producing wells. This is an increase of 35,780,285 bbl. of oil. Some decline has been shown in the older fields arid undoubtedly the majority of wells in the district are producing at too high a rate. However, this district has been able to meet any demands made on it by the Petroleum Administration for War for increased production. Discoveries and Extensions There was a slight decline over the preceding year in the number of wildcats drilled, but the number of discoveries increased. In most instances subsequent development has not been sufficient to arrive at preliminary valuations but it appears that the over-all oil discoveries were below normal and that the gas discovcrics were relatively more important. The Canolis and Tijerina pools, Jim Wells County, and the Dan Sullivan pool, Brooks County, appear to be the outstanding oil discoveries of the year. No important oil reserve was discovered or developed in the Wilcox horizons, although considerable wildcatting was done. Important extensions were made at Agua Dulce and Stratton in Nueces and Teleberg Counties. Production was increased appreciably at Willimar, Willacy County, and Seeligson, Jim Wells County, in sands and areas which were apparently productive at the beginning of the year. Refining Most of the major work in the changing and completing of refineries was finished this past year. Some of the most modern refineries in the industry are now located in the Corpus Christi area. Gas and Condensate No new recycling projects were commenced during the year, nor were there any important additions to the old operations. No major gas reserve was developed, although several new discoveries suggest potentid possibilities.

Jan 1, 1945

By S. Weinig, J. Winter

The grain boundary adsorption of solutes as a function of bulk concentration and solution temperature was studied using internal-frictimz techniques. From the variation of the cor-responding energy of activation for the Phenomenon, the inter-actior2 energy between a solute atom and a high-angle boundary was calculated. Interaction energies in the range of 0.3 ev were obtained, and were used to obtain the actual concentration of solute at the grain boundary. In corroboralory creel, studies the direct grain boundary contribution to the total creep strain was measured. It was found that the interface creep varied with the type and magnitude of the solute adsorbed. Subscribing to the theory of their being energetically favorable sites at the grain boundary for solutes of both Positive and negative size deviations, ternaries were investigated in Which solutes of both types were present. A marked increase in the resistance to grain boundary creep was manifested. THE major difficulty which has been encountered in investigations of the grain boundary segregation of solutes has been the lack of a sufficiently sensitive method of measuring the amount of adsorbed solute at the boundary. For the general case of a high-angle boundary, no direct method of measuring the adsorption at the boundary has been found to date. Internal friction has been used in several studies of grain boundary adsorption1-3 and although it is somewhat indirect, it was demonstrated to have the necessary sensitivity. In this investigation the authors have used internal-friction techniques in conjunction with a study of the grain boundary contribution to the total creep strain. As both parts of the investigation were performed on the same specimens it was possible to combine a highly sensitive technique with a somewhat more direct method in order to obtain information about the adsorption phenomenon. From internal-friction studies the rate of increase of the activation energy was observed to be a function of the difference in size between the solute and solvent atoms. It was proposed that if Gibbs' adsorption isotherm is considered, i.e., where r is the excess solute at the boundary, c is the bulk concentration, and ay/ac is the change in grain boundary energy with bulk concentration, then AH b/ac must vary in the same way as ay/ac and therefore In this way a relative measure of the grain boundary adsorption of solutes is directly obtainable from in-ternal-friction studies. If the previous work in the field of grain boundary adsorption of solutes is examined, certain apparent information is desirable if the phenomenon is to be understood. The most important questions that must be asked are as follows: 1) Is the adsorption of solutes at the grain boundary an equilibrium process? 2) Can the Mott model of the grain boundary be used as a basis of setting up an elastic interaction between the grain boundary and solute atoms? 3) Is it possible to obtain an exact measure of the excess solute at the grain boundary as a function of temperature and bulk concentration rather than merely a relative measure of the adsorption 4) Are the conclusions obtained from an indirect method such as internal-friction studies meaningful in considering gross grain boundary effects such as creep? EXPERIMENTAL PROCEDURE The material used in this investigation was Bureau of Mines "superpurity" titanium (79 Bhn—1500 kg

Jan 1, 1960

By M. H. Forester, John D. Cooner

ANTHRACITE ALTHOUGH the unmined anthracite will last for approximately 150 years, most of the thicker and cleaner coal beds have been almost entirely first-mined and pretty well robbed, leaving much of the present and future production to come from thin and dirtier beds. Herewith is a section of one of the dirty beds being mined in the Wyoming region [ ] This section shows that 45.8 per cent of the bed is made up of impurities and that the 45 in. of coal in the bed is in five benches, the thickest of which is 19 inches. In some localities of the anthracite region there are 14 beds of minable coal. Orderly and proper mining of the coal makes it necessary to rob or second-mine-almost all beds have already been first-mined-in sequence from the top downward. Therefore the robbing of the few remaining portions of the thicker and cleaner beds is in many instances being held up by the mining of the overlying thin and dirtier coal beds. Impurities Impurities consist of fire clay, slate, rock, and bone. The latter, which is black, contains 40 to 60 per cent carbon and often resembles good coal. In some beds there are also bands of "blue" coal, which, as the name implies, is of a bluish slaty color. Although much of this "blue" coal has a carbon content almost as high as the good anthracite, it is not

Jan 1, 1943

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By C. R. Hayward

CARLE R. HAYWARD.-I do not want it understood that I think that the conclusion that the time of tempering temperature is immaterial has been definitely proven, but since these are the first definite figures put out, I thought before continuing on more work ourselves, it would be well to present them as progress and for information. J. A. MATHEWS, Syracuse, N. Y.-I think that if Prof. Hayward would consult the paper of Profs. Barus and Strouhal,1 1885, he would find about 250 pages, mostly figures, on this subject, in which they investigated the tempering effect by electrical and magnetic methods. There are so many figures in the paper that it is very difficult reading. One point particularly brought out was that even at a low temperature, such as the boiling point of alcohol, about 60° C., there is a tempering effect, increasing up to 4 hr. One reason they obtained those results, with which the present authors are at variance, was that they started with a high-carbon steel which hardens thoroughly, whereas the steel Prof. Hayward and his collaborator used was a comparatively mild steel which does not take a great deal of hardening. About 3 years ago Mr. Stagg and I published 2 a few figures bearing on the same subject, but we used .a low-carbon alloy steel of high tempering qualities and found a great deal of improvement, particularly in ductility, by continuing the drawing up to 4 hr. We used a chrome-vanadium steel showing after heat treatment 250,000 tensile strength. On short drawing, we got almost no ductility, but by continuing to 4 hr., we raised it to 12 per cent. I believe Prof. Hayward's results are due to using comparatively mild steel, whereas Prof. Barus used drill rod and carried out a, wonderfully exhaustive

Jan 4, 1917

By C. W. Allen, L. C. Moore

The Mather mine, of the Negaunee Mine Co., is within the limits of the City of Ishpeming. on the Marquette iron range in Michigan's Upper Peninsula. It is named for William G. Mather, who has served as President, and Chairman of the Board, of The Cleveland-Cliffs Iron Co. for well over 50 years. The property comprises nearly the square mile of section 2, T.47 N. R.27 W., which, except for 20 acres in the northeast corner, was leased by The Cleve-land-cliffs Iron Co. to the Negaunee company. The latter is a partnership of Cleveland-Cliffs and the Bethlehem Steel Co., organized to equip the property, retaining Cliffs in charge as operator. Shipments of ore from this area are mainly through Marquette, which is 16 miles to the northeast on Lake Superior, or through Escanaba, a Lake Michigan port, 65 miles to the south. Cleveland-Cliffs, in 1943, operated 12 mines in the Lake Superior district, with shipments of 6,635,576 tons for the year. Geology The north footwall of the Marquette Range synclinorium outcrops near the north line of set. 2, the iron formation dipping to the south at an angle of about 40. The south side of the trough reappears at a distance of 4J5 miles on sec. 26 and the surface geology between shows iron forma- tion or intrusive diorites. The latter are harder than most phases of the iron formation and, as a result of glacial action, appear as buttes or low-lying hills. The general elevation of sec. 2 is about 1450 ft. above sea level, or 850 ft. above Lake Superior, and the higher diorite outcroppings about 1600 ft. above sea level. The geological structure has been complicated by a series of major and minor faults, one of which may be illustrated by the diorite sheet, which tilts south with the iron formation in the north half of the section and then reappears near the center to repeat this sequence. Sectionally the geological series includes a nearly eroded capping of Goodrich quartzite followed by the considerable thickness of Negaunee iron formation, which is cut by intrusive dikes or diorite sheets, and underlain by the Siamo slates grading into quartzites. The ore deposits occur mainly in troughs formed by the intersection of impervious dikes and the footwall slate, but include locally enriched lenses or bands in the iron formation and also interbedded with the Siamo slate. The ore is a soft red hematite with an indicated dried analysis from the surface drilling to date of 61.50 per cent Fe, 0.134 Per cent P, 5.40 per cent Si, 2-87 Per cent A1 and 0.015 per cent S. Exploration A diamond-drilling campaign started in 1937 actually had its inception in 1917, when a number of shallow test holes were put down for the purpose of locating ore that might be quickly developed and mined

Jan 1, 1946