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By R. D. Mollison, C. F. Fogarty

Sulfur is widely distributed in nature. It is present in the earth's crust, the ocean, the meteorites that come to us from cosmic space and in practically all animal and plant life. According to Clarke,9 the earth's crust contains 0.06 pct sulfur. Large quantities of free or combined sulfur are found in coal, natural gas and petroleum. Mineral waters contain sulfates and hydrogen sulfide. Sulfur is rather plentiful in the crust of the earth; however, only under special circumstances can it be produced profitably. Sulfur is one of the cheapest raw materials used by industry; and, therefore, the economic feasibility of a given deposit is strongly dictated by the law of supply and demand on local as well as world-wide levels. The forms which are commercially important are elemental sulfur or brimstone, and the sulfides such as pyrite (FeS2), pyrrhotite (FenSn+1), chalcocite (Cu2S), sphalerite (ZnS), and galena (PbS); the sulfates such as gypsum (CaSO4,2H2O), anhydrite (CaSO4), and kieserite (MgSO4,H2O). Elemental Sulfur Elemental sulfur is found in many localities, generally in solfataras and gypsum type deposits. The solfatara deposits are found commonly in the neighborhood of active or extinct volcanoes as in Italy, Japan and Chile, or fumaroles associated with mineral springs such as the Mammoth Hot Springs in Yellowstone Park. Here the sulfur is deposited in tufas or other porous host rocks. This type of sulfur deposit probably results from the oxidation of hydrogen sulfide or the reaction of hydrogen sulfide with sulfur dioxide. Most of the world's supply of elemental sulfur comes from the gypsum-type deposits. Here the mineral occurs as either crystalline or amorphous sulfur in sedimentary rocks in close association with gypsum and limestone. This association is characteristic and occurs in almost all the great gypsum beds of the world, although sulfur is not always present in quantities of economic importance. Various theories have been advanced to account for this association. Bischof5 suggested that the sulfur came from hydrogen sulfide which resulted from the reduction of calcium sulfate by carbon or methane in accordance with the following reactions: CaSO4 + 2C= CaS + 2CO2 CaS + C02+ H2O = CaCO3 + H2S CaSO4 + CH4= CaS + C02+ 2H20 2H2S + 02= 2H20 + 2S All of the sulfur-bearing domes on the Gulf Coast have calcium sulfate in great quantity in the cap. They all show the presence of hydrocarbons. The oxygen for the final reaction could have been supplied by circulating ground waters. The principal objection to this theory is that temperatures of 700° to 1000°C are needed to reduce the sulfate to sulfide with carbon compounds. The geologic evidence is that the temperature of the sulfur-bearing domes of Texas did not exceed 100°C. Proponents of the theory say that geologic time or a catalyst replaced temperature. According to another theory the sulfur in the salt domes is the result of bacterial action. Sulfate reducing bacteria have been detected in sulfur cores and in the formation water issuing from salt domes. It has, therefore, been suggested that these bacteria converted the sulfate to sulfide which subsequently was converted to elemental sulfur.

Jan 1, 1960

By A. E. Wells, H. O. Hofman, R. P. Reynolds

A Discussion of the Paper of H. O. Hofman, R. P. Reynolds and A. E. Wells, read by title at the London Meeting, July, 1906 ; presented at the New York Meeting, April, 1907, and printed in Bi-Monthly Bulletin, No. 13, January, 1907, pp. 37 to 52. GEORGE A. PACKARD, Boston, Mass. (communication to the Secretary*) :-The very interesting results obtained by Prof. Hofman and his assistants came to my attention when I had temporarily assumed charge of the metallurgical department of the Missouri School of Mines, and had found it, pending the completion of a new building, lacking a furnace in which to roast ore preparatory to the customary lead blast-furnace run. An attempt at lime-roasting had been already determined upon, but the use of a charge which would make a slag of definite composition was a new idea. The results following were obtained by Messrs. Aubrey Fellows, J. C. Long, E. R. Wash, and Dr. T. C. Tseung, under my supervision. It is regretted that the data are not more complete; but the work was done simply incidentally to securing the desired ore for the blast-furnace, with no idea of obtaining any results of especial interest. It is submitted because of the metallic lead obtained, no notice of which has been seen elsewhere. The ore was an aggregate of several lots of concentrates, apparently from Missouri ores. The analysis follows, with that of the limestone and sandstone used, as far as made:. Ore, SiO2, 3.04; Fe, 0.77; CaO, 2.53; Pb, 68.74; Zn, 5.77; S, 13.9 per cent.; limestone, SiO2, 1.0 ; CaO, 54.35 per cent.; sandstone, SiO2, 99.8 per cent. The converter was made in the shops from a sheet of No. 14 iron riveted in the shape of a truncated cone, 20 in. in diameter at the top, 15 in. at the bottom and 22 in. high. A grate of No. 8 iron, 17 in. in diameter, with 130 s-in. holes placed at about 1.25-in. centers, was held in place by the shape of the

Jul 1, 1907

By H. H. Wade, N. F. Schulz

The large quantities of iron-bearing materials, including taconite, semi-taconite,* and other low-grade ferruginous materials occurring in Minnesota and elsewhere, constitute an important potential source of iron. Satisfactory grade and recovery of iron ore concentrate cannot ordinarily be obtained from these ferruginous materials by simple methods of beneficiation. Iron is distinctive in that the free metal and two of its oxides [magnetite (Fe2O3) and maghemite (gamma-Fe2O3) ] are strongly ferromagnetic. The successful magnetic separation of natural magnetite from taconite has already been established on a commercial scale. The iron in semi-taconite, however, occurs largely as goethite (Fe2O3-H4O) and hematite (Fe2O3) which do not respond to ordinary magnetic separation methods. Magnetic roasting converts these iron oxides to magnetite, which can, after liberation, be magnetically concentrated. MAGNETIC ROASTING Hematite undergoes a stepwise reduction when exposed at moderately elevated temperatures to a reducing atmosphere containing hydrogen or carbon monoxide: Fe2O3? Fe3O4 ? FeO ? Fe Since the desirable product in magnetic roasting is Fe3O4, the conversion is halted after the first stage by controlling the reduction potential of the gas mixture with water vapor or carbon dioxide. The reducing gas mixture must be such that the oxygen partial pressure at the solid-gas reaction interface will be maintained intermediately between the oxygen partial pressures in equilibrium with Fe2O3 and Fe3O4 at the prevailing temperature. Because of the rapid increase in decomposition pressure of Fe3O4 with increase in temperature, the practical upper limit of useful reaction temperature is about 1400°F, above which over-reduction usually occurs in atmospheres containing hydrogen or carbon monoxide. On the other hand, useful reaction rates usually occur only above 800°F. Goethite reacts similarly except that the combined water probably has to be driven off thermally before the reduction to magnetite occurs. Iron carbonate must also be decomposed thermally to an oxide before conversion to magnetite. Iron silicates are apparently not amenable to magnetic roasting. The rate of penetration of the reaction toward the interior of a given ore fragment is dependent on the chemical composition and physical structure of the solid. Most ore fragments tested here reduced satisfactorily to 1/4-in. depth in less than 14 min at 1200°F. Some very dense fragments, however, were reduced to less than 1/32-in. depth under the same conditions. Determination of the optimum temperature, gas composition, ore fragment size, or time of exposure

Jan 1, 1961

By Everett Carpenter

THE average daily production of crude oil-in Kansas a1 the beginning of the year was about 71,000 1 bbl. and, at its close, 82,000 bbl.-an increase of 11,000 bbl. per day. The total production for the state during the year was about 28,250,000 bbl., or an average of practically 77,500 bbl. per day for the year. This increase in the production was the result of the discovery of several new pools of high-grade oil. COWLEY AND SUMNER COUNTIES One of the principal factors in bringing the production of the. state back to its former level was the newly discovered pools in western Cowley County. During December, 1923, the Waite Phillips Co. completed its Johnson No. 1 in Sec. 20, T. 33 S., R. 3 E., which opened up the Rainbow pool about 12 miles southwest of Winfield. In this pool, the production comes from the Burbank sand, locally called the "Rainbow," found at a depth of 3200 ft. The sand varies in thickness from 25 to 40 ft. in the seventeen wells completed during the year, and the initial productions ranged from 300 to 3000 bbl. per day of 40° Be. oil. The Rainbow pool is purely a wildcat discovery, for no. rocks suitable for the use of the geologist are present. To determine the geologic conditions, the larger companies core-drilled the Rainbow area immediately after the discovery. The Marland Refining, Co., drilling on the Graham farm in Sec. 9, T. 33, R. 3, failed to find the Burbank sand and continued to the Siliceous lime, often erroneously called the Wilcox, at 3505 ft., where a well with an initial production of 900 bbl. of 40 Be. oil was obtained. In the development following this discovery, 4 additional wells were completed, 3 of which encountered pay sand at 2500 ft., the initial productions each being about 200 barrels. Judging by the sands already proved and the area indicated as probably oil bearing by the development to date, these pools have a very promising outlook for the future. It is not unlikely that a field second only to El Dorado may have been opened.

Jan 3, 1925

By H. F. Seifert

THE classification and preparation of non-ferrous scrap metals is a subject of interest to every individual and corporation that employs in its processes of manufacture non-ferrous metals and alloys and accumulates in such manufacture scrap from these materials for disposition in the form .of turnings, borings, short ends, punchings, clippings, grindings, washings, etc. All too frequently the disposition-of such scrap is left to individuals who have no knowledge of the subject either from a metallurgical or a commercial standpoint, or both. Much money is thus lost which with a little more intelligent effort might be saved, and in this day of fierce competition and small profits such an opportunity cannot be ignored. The Mineral Resources of the United States for the year 1925, the latest issue available (Part 1, page 221), gives the secondary non-ferrous TABLE 1.-Some. Secondary Non-ferrous Metals Recovered in the United States for the -Year 1924-25 Material Short Tons Value Copper, including that in alloys other than brass.... 250,600 8 71,170,400 Brass, scrap remelted : 242,300 56,270,800 Lead as metal : 112,420 39,477,100 Lead as alloys 112,460 Zinc as metal 61,430 11,359,000 Zinc in alloys other than brass 13,300 Tin as metal 7,950 Tin in alloys 23,000, 35,165,400 Antimony as metal 1 3,794,000 Antimony in alloys : 10,839 Aluminum as metal 17,700 24,816,000 Aluminum in alloys 26,300 Nickel as metal 191 1,518,000 Nickel in non-ferrous alloys 2,109 Total l 882,600 $243,570,700

Jan 1, 1928

By Herbert Everest

THE idea of economical production is usually associated with large operations, tonnages, and mines, with even larger capital behind them. Nevertheless many small mines operate in the shadow of large competitors and make a good showing on the capital invested despite larger overhead expenses. For the purpose of this discussion I will divide the cost of production into classes, and specify opposite each the approximate percentage expended thereon: 1. Labor, including miners and company men; 60 to 75 per cent. 2: Development, including all necessary yardage, room turning, crosscuts, etc.; 7 to 12 per cent. 3. Deadwork, covering payment to miners for handling falls, drawslate, or faults, rock work, water, and in general, all nonproductive labor; 3 to 7 per cent. 4. Supplies: mine timbers, oil, brattice material, lumber, cement, and repairs to equipment; 2 to 6 per cent. 5. Expense: management, selling, office, taxes, etc.; 1 to 5 per cent. 6. Depreciation of coal reserves and royalties; 6 to 10 per cent. 7. Depreciation of equipment and interest on capital invested; 1 to 3 per cent. 8. Fuel; ½ to 1 ½ per cent. The labor cost for a small mine is relatively much lower than for a large mine, particularly the sum paid to company men. Idle-pay expense is cut to a minimum; the labor item being larger than all the others together, a saving in labor makes a decided showing on the total cost. The development charges in small and large mines are about the same. There should be a small showing on the Beadwork item in favor of the small mine. The unit cost for supplies is usually small in the small mine. The operator of the small mine finds, owing to a limited tonnage, that the expenses of management, selling, etc., are abnormally high.

Jan 1, 1916

By E. Maxwell, C. J. Bechtoldt, H. C. Vacher

IN the course of an investigation of the properties of metals at low temperature there was occasion to determine the constitution of four iridium-osmium alloys. There is very little information in the literature1 on the constitution of synthetic Ir-0s alloys. Zvyagintzev' s has made a comprehensive study of different natural Ir-0s alloys and concludes that alloys containing more than 32 pct 0s have the close-packed hexagonal structure of osmium, whereas those containing less than 32 pct 0s have the face-centered cubic structure of iridium. The alloys studied in this work were prepared by the American Platinum Works, Newark, N. J., and were received in the form of fragments approximately 1.5 mm average diameter. The fragments had been obtained by crushing ingots made by fusing charges of iridium and osmium under an arc and air cooling. The ingots were not given a homogenizing heat treatment. Sample fragments Table I. Results of X-Roy Diffraction and Microscopic Examinations Phases Present as Determined by X-ray Diffraction Osmium Alloy Close- Iridium Face- Packed Centered Osmium, Iridium, Hexagonal Cubic Mlcro- WtPot Wt Pct Structure Structure scope 0 99.9 None Present 1 23.6 76.4 None Present 1 38.7 61.3 Present Present 2 59.4 40.6 Present Present 2 79.0 21.0 Present Not detected 2 99.9 0 Present None 1 Note: Chemical analyses of the iridium, osmium, and alloys were furnished by the American Platinum Works. of the iridium and osmium used in making the alloys also were included. Several fragments of each metal and alloy were examined microscopically and by X-ray diffraction. For the X-ray method the fragments were crushed further to pass a 270-mesh screen, then sealed in evacuated fused-silica tubes, heated to 1100°C for 18 hr, and allowed to cool in the furnace. Powder X-ray diffraction patterns were obtained from the annealed fragments by means of a Norelco camera having a diameter of 114 mm, and unfiltered cobaIt radiation. For the microscopic examination several fragments in the as-received condition were mounted in Melmac, (American Cyanamid Co.) and ground using the conventional series of abrasive papers. The polishing was done with 0-2 diamond abrasive on a Microcloth (Buehler Ltd.) lap, wet with xylene. After polishing, the surface was etched electrolytically in a 10 pct solution of chromic acid or in a 10 pct solution of potassium cyanide. Both reagents attacked the osmium-rich constituent, whereas the iridium constituent was attacked slightly by the chromic acid reagent and not noticeably by the potassium cyanide reagent. The results of the X-ray diffraction and microscopic examinations are summarized in Table I. Fig. 1 shows the microstructure of a 21 pct Ir-79 pct 0s alloy. The results indicate an appreciable solid-solu-bility range of osmium in iridium as was reported by Zvyagintzev.' The solid-solubility range of iridium in osmium is more restricted, apparently less than 21 pct Ir. This implies a large range of composition in which two phases can coexist that was not reported by Zvyagintzev.

Jan 1, 1955

By R. J. Teitel

The Pb-U system has been investigated by X-ray, thermal, and microscopic analyses. Two pyrophoric intermetallic compounds were found; UPb3 and UPb. The crystallographic structure of UPb3 is reported. A phase diagram was drawn for the system showing three eutectic and one syntectic reaction. AS a result of the interest in uranium metallurgy, the Pb-U system has been investigated. Practically no quantitative data appears in the literature concerning this system. Chips were machined from bars of high-purity uranium obtained from Ames Laboratory and the lead was 99.9 pct high-purity grade from Bel-mont Smelting & Refining Co. The chips were pickled in a dilute solution of nitric acid, washed in water and then alcohol, and dried prior to use for alloy preparation. The lead was simply sheared from the pig with no chemical treatment. Lead and uranium were placed in graphite crucibles and loaded into an induction furnace. In order to insure good alloy formation, the lead was loaded above the uranium to wash the uranium chips into the melt. After the charge was held at the desired preparation temperature for 15 to 30 min, it was allowed to cool in the crucible. The entire melting operation was accomplished in an atmosphere of helium (double charcoal refined grade with no further treatment). The procedure was to outgas the furnace by first evacuating it to 10-% m Hg, admitting helium to 8 psi gage and sealing the furnace off. An optical pyrometer focused on the charge through a hole in the crucible cover was employed for thermal measurements. Usually a 50° to 70°C correction had to be added to the instrument value. The most suitable alloy preparation temperature range was found between 1220° and 1280°C. The reason for this is explained by the phase diagram, Fig. 7. Above this temperature range two liquids separate preventing alloy formation upon cooling at a reasonable rate. On the other hand, below this range the uranium was coated with a layer of both compounds and the rate of reaction was diminished by diffusion processes. The fastest reaction rate occurred in this narrow range of temperature because only UPb coats the uranium and it evidently does not protect the uranium as well as UPb,. Apparatus and Procedures The development of apparatus and techniques was determined by the peculiar properties of the alloys. All the alloys were pyrophoric, and, consequently, the alloys had to be protected from oxidation by handling them in a dry box or inert atmosphere furnaces. Other operations performed outside of this equipment had to be done as quickly as possible. Thermal analyses were conducted in a furnace and arrangement similar to that described by the author.' Graphite crucibles having a thermocouple well in the bottom were used to contain the prepared alloy, while a helium atmosphere protected the melt from oxidation. The furnace was outgassed by pumping a 10-3 mm Hg vacuum until the furnace had been heated to 400°C. Then helium was admitted and the furnace sealed under 8 psi gage pressure. Chromel-alumel thermocouples were used for thermal analysis and the accuracy of thermal measurements was judged to be k 5°C. At first, an attempt was made to use platinum-platinum-rhodium thermocouples, but evidently lead vapors attack it at high temperatures forming low melting alloys. These lead vapors had direct access to the thermocouple because the graphite crucible was porous. A differential temperature control was used to regulate thermal analyses. The thermal gradient across an alundum tube placed between the windings and the crucible was maintained constant by a controller.

Jan 1, 1953

By C. E. Arnold

A BRIEF description of this installation was included in a recent paper by H. Kenyon Burch.1 The purpose of the present paper is to amplify Mr. Burch's description, as it is felt by the writer that the subject merits more than passing attention. In making a comparison between the common method of hoisting men in mine shafts, and elevator practice in high buildings, the former shows to great disadvantage both as regards safety measures and smoothness of operation. It is surprising that in view of the inducements offered, the step of applying the building equipment direct to the mine shaft has not been taken before, as in many respects the conditions of service are similar, and the objects to be attained are identical. Even without doing this, it is certain that safety to life and limb in the usual method of hoisting men underground can be greatly enhanced by the application to the mine hoist, of some of the features of the building elevator. In the case under consideration, the elevator cage runs in a vertical, concrete-lined shaft compartment 5 ft. 11 in. by 5 ft. 6 in. (1.8 by 1.68:m.) in section and 585 ft. (178 m.) deep, while the counterweight runs in the pipe and ladder compartment of a twin shaft 102 ft. (31 m.) distant. The section of the division of this compartment occupied by the counterweight measures 2 ft. 4 ¼ , in. by 3 ft. 10 ½ in. (0.72 by 1.18 m.), and the counterweight is made in the form of a small cage which. suffices to carry two men for the purpose of making inspections or repairs in the pipe and ladder way.

Jan 12, 1917

By Lewis M. Haupt

Discussion of the paper of Mr. Granger, presented at the New Haven meeting, February, 1909, and published in Bulletin No. 25, January, 1909, pp. 1 to 37. LEWIS M. HAUPT, Philadelphia, Pa. (communication to the 'Secretary*) :-This subject is of great interest to me, and I am noting progress and conditions as a test of my own judgment in advocating what I believed to be the nearer, cheaper and better route at Nicaraugua. I have as yet learned nothing to change my views, or modify the convictions which led me to retire from the Commission; but that is not the issue to-day. Our government is committed to the Panama route, and is bound to " make good." There are many points presented by Mr. Granger which seem to me worthy of very serious consideration. But when all is said there remains the risk of seismic convulsions, to which either form of canal is subject; and I fail to see that the risk would be reduced by making the cut deeper, with greater surcharge of lateral pressure upon the side walls. A severe earthquake in the rainy season would doubtless close either type of canal. One of the arguments in favor of the Panama route most insisted on, was that Nature had provided good natural harbors at its termini. Recalling this, it has interested me to note that the cost of creating the necessary harbors is estimated at $27,000,000. Mr. Granger refers to this, and quotes the Board's report to the effect that, on the Atlantic side, it will require 5 miles of jetties to " make an excellent harbor out of a wretched one." The vulnerable part of Mr. Granger's paper seems to me to lie in the admission that the plant required is still in the embryonic stage, and that at least one machine should be built and tested " to demonstrate that the theoretical strains and forces work out in practice exactly as expected." This, how-

Jul 1, 1909

By R. C. Troxell, S. C. Sun

EFFORTS to obtain definite quantitative data when employing the currently used bubble pick-up method1,2 as a pre-flotation investigation tool led to the adoption of the magnifying mirror method and the microscopic method modifications. Quantitative data obtained by these two methods were converted into bubble pick-up indices and bubble pick-up coefficients. Rough correlations were established between the calculated indices and the results of contact angle testing as well as actual flotation under the same conditions. The basic steps of the magnifying mirror method are as follows: 1—mixing 200 ml distilled water, sized and cleaned mineral particles of approximately 0.5 g, pH regulator, and flotation reagents in a glass beaker; 2—swirling the mineral particles to the center of the beaker to leave a clear circumference; 3—pressing an air bubble against the mineral particles for about 1 sec, and then moving the mineralized air bubble to the clear part of the beaker; and 4—dropping all the attached mineral particles of the air bubble by tapping the bubble holder, and counting the number of the dropped particles by looking at the magnified image in the mirror positioned beneath the beaker. This method is impractical for mineral particles which are transparent in water or finer than 200 mesh. The microscopic method is essentially similar to the above described magnifying mirror method, with the exception that the mineralized air bubble was drawn up into the bubble holder and subsequently discharged onto an externally placed watch glass, where the number of pick-up particles was counted with the aid of a microscope or hand lens. Drying was necessary when the discharged liquid interfered with the counting. The results of the bubble pick-up tests can be simply expressed in the form of the actual count. However, this can be misleading because the number of pick-up particles varies not only with the size of bubble but also with the size of particles. This short-coming is largely remedied by the use of the bubble pick-up index. as calculated from the following equation: PI = (pn/p) 100 [1] in which PI and pn are respectively the pick-up index and the number of pick-up particles under any test conditions, and p is the maximum number of pick-up particles of the same mineral under optimum flotation conditions, with the same size holder and particle. The bubble pick-up coefficient is a term coined to denote the difference between the bubble pick-up index of mineral particles in a liquid and that of the same mineral-liquid mixture plus a chemical reagent at the same pH value. For example, the difference between the pick-up index of a naturally floatable bituminous coal in a solution of water and kerosene and that of the same coal in water alone is a bubble pick-up coefficient. Compared with the contact angle method, the quantitative bubble pick-up method is inferior in accuracy but superior in sensitivity. Other advantages of the bubble pick-up method are that the apparatus can be easily assembled, the mineral sample is conventionally prepared, and the test procedure is relatively simple. References S. R. B. Cooke: The Flotation of Quartz Using Calcium Ion As Activator, Trans. AIME (1949) 184, p. 306. 'G. A. Last and M. A. Cook: Theory of Collector-Depressant Equilibrium at Mineral Surfaces. Paper presented at St. Louis Meeting, AIME (February, 1951).

Jan 1, 1954

By Herbert A. Everest

The idea of economical production is usually associated with large operations, tonnages, and mines, with even larger capital behind them. , Nevertheless many small mines operate in the shadow of large competitors and make a good showing on the capital invested despite larger overhead expenses. For the purpose of this discussion I will divide the cost of production into classes, and specify opposite each the approximate percentagc expended thereon: 1. Labor, including miners and company men; 60 to 75 per cent. 2. Development, including all necessary .yardage, room turning, crosscuts, etc.; 7 to 12 per cent. 3. Deadwork, covering payment to miners for handling falls, draw-slate, or faults, rock work, water, and in general, all nonproductive labor; 3 to 7 per cent. 4. Supplies: mine timbers, oil, brattice material, lumber, cement, and repairs to equipment; 2 to 6 per cent. 5. Expense: management, selling, office, taxes, etc.; 1 to 5 per cent. 6. Depreciation of coal reserves and royalties; 6 to 10 per cent. 7. Depreciation of equipment and interest on capital invested; 1 to 3 per cent. 8. Fuel; ½ to 1½ per cent. The labor cost for a small mine is relatively much lower than for a large mine, particularly the sum paid to company men. Idle-pay expense is cut to a minimum; the labor item being larger than all the others together, a saving in labor makes a decided showing on the total cost. The development charges in small and large mines are about the same. There should be a small showing on the deadwork item in favor of the small mine. The unit cost for supplies is usually small in the small mine. The operator of the small mine finds, owing to a limited tonnage, that the expenses of management, selling, etc., are abnormally high. The item, depreciation of coal reserves and royalties, is usually about

Jan 1, 1916

By B. F. Decker, D. Harker

The recrystallization reaction in OFHC and spectroscopically pure copper has been followed by X ray diffraction determinations of the amount of material with the cold-worked and recrystallized textures in specimens which had been given various heat treatments. The heats of activation for recrystallization are found to be: 29.9 kcal per rnol for OFHC copper and 22.4 kcal per rnol for spectroscopic copper. A reliable and speedy method for measuring the amount of recrystallized material in a piece of rolled metal, together with a new scheme for low temperature heat treatment, have made possible a determination of the activation energy for recrystallization in rolled copper. This method for studying recrystallization rates is different from others reported in the literature.' Oxygen free, high conductivity copper—OFHC copper—of purity 99.98 pct gave an activation energy for recrystallization of 29.9 kcal per mol with recrystallization data taken in the temperature range 208-245°C. Copper of purity 99.999 pct from the American Smelting & Refining Co. gave an activation energy for recrystallization of 22.4 kcal per mol with recrystallization data taken in the temperature range 43-135°C. The great change in activation energy for recrystallization as the small amount of impurity in the metal is decreased suggests that the motion of grain boundaries is conditioned by the impurities which must be concentrated in them. Thus the OFHC copper recrystallizes with an activation energy of the order of magnitude to be expected for the diffusion of the kind of impurities likely to be present. The high purity copper, on the other hand, recrystallizes with a much lower activation energy, in accord with the notion that the grain boundaries need not wait for the impurities to diffuse with them. Copper when strongly cold-rolled has a well-defined crystallite texture which can be described by saying that the [111] direction of the face- centered cubic crystals is aligned approximately in the cross-rolling direction and that faces of the form {110} lie approximately in the rolling plane. When such rolled copper is completely annealed the crystallite texture is quite different: the [loo] direction is in the cross-rolling direction and faces of the form (100) are in the rolling plane. At intermediate stages of annealing, the copper contains both textures. If a Geiger counter X ray diffraction spectrometer is set up so as to measure the intensity of the (200) Bragg reflection from the rolled surface of a piece of copper strip, this intensity increases from a very small value in the cold-worked state to a maximum as the specimen is annealed. The same would be true for (200) reflections from planes normal to the rolling or cross-rolling directions. In view of this fact, the amount of material in the copper which has recrystallized can be measured by comparing the intensities of one of these reflections just mentioned with the intensity from a similar specimen after complete annealing. In much the same way the intensity of (111) reflections from planes normal to the cross-rolling direction could be used to measure the amount of unrecrystallized material in the specimen. In the work to be described here the amounts of recrystallized and unrecrystallized material in partly annealed rolled copper specimens were determined in this way. Experimental Procedure Samples of oxygen free high conductivity (OFHC) copper, cold-rolled 99.7 pct to 0.002 in. thickness, were subjected to heat treatments for various chosen times at four different temperatures, and high purity copper samples, cold-rolled 98.0 pct to 0.0015 in. thickness, at six different temperatures. Each sample, after treatment, was placed in an orientation sample holder for use with a Geiger counter X ray spectrometer and a reading was taken of the intensity of the (200) reflection from planes perpendicular to

Jan 1, 1951

By J. E. Hilliard

AS is well-known, the length per unit volume, Lv, of any lineal feature (such as grain edges in a polycrys-talline specimen) can be estimated from a count of the number of point intersections with a random plane of polish. Specifically:' Lv = 2NA in which NA is the expected number of intersections per unit area of the plane. As with all other measurements in quantitative metallography, the estimation of Lv is subject to a sampling error, the magnitude of which will depend on the number of observations. The analysis is usually performed by counting the number of intersections falling within a closed test figure of known area applied to a succession of different areas on the plane of polish. The test figure can be drawn directly on the screen of a projection microscope or else superimposed on the image of the structure by means of a reticule in a focusing eyepiece of an ordinary microscope. The use of micrographs is very inefficient unless, as in the present study, these are also needed for some other purpose. Consider an analysis in which n applications are made of a test figure within which the expected number of intersections is N. The expected total number of intersections counted is then given by NT = nN If (N) is the standard deviation in N for one application of the figure and if the latter is applied to non-overlapping regions so that the N's are independent in the statistical sense, then the standard deviation in Nt is given by: a(NT) = a(N)vn Eliminating n from Eqs. [2] and [3] we obtain: Thus, k will be a constant for a given specimen and test figure. From Eqs. [ I] and [4] we find As is to be expected, therefore, the fractional error in the estimation of Lv is inversely proportional to the square root of the total number of intersections counted. It is very desirable to have at least a rough estimate of k before starting an analysis, since it will then be possible to decide in advance by use of Eq. [5J how many counts should be made in order to achieve the desired accuracy in Lv. Without such information the investigator, unless lucky, will either do needless (and tedious) work or else obtain a result with too large an error. It is very easy to calculate k for the limiting case of N — 0, i.e., when the test figure is vanishingly small. In this case there is a negligible probability of two or more intersections falling within the figure. There are therefore only two possible outcomes: a count of one with a probability of, say, p and a zero count with a probability of (I-p). Thus and Therefore: We might expect k to depend on N and therefore on the size of the test figure. Such a dependence was observed2 in the analogous case involving the estimation of grain-boundary area per unit volume by a count of the number of intersections of a test circle with traces of the boundaries on the plane of polish. In this case the theoretical value of k at the limit N — 0 was 1.41. It was also predicted that k would display an initial sharp decrease with increasing N. Experimentally, k was observed to decrease to a value of 0.62 at N - 6 and thereafter remain approximately constant. Furthermore, the value of k for N > 6 was found to be insensitive to the form of the structure provided no pronounced anisotropy or grain-size variation was present. In order to determinewhether k would exhibit a similar dependence on N in the estimation of grain-

Jan 1, 1967

By N. M. Langdon

Spokane Meeting, September, 1909.) THE following corrections to the paper of Mr. Langdon (Bulletin No. 34, October, 1909, pp. 919 to 940), received after the publication of the paper in the Bulletin, will be incorporated in the paper as finally published in the forthcoming Vol. XL. of the Transactions, but are here presented for the information of members:' Page. 921. Table I., furnace M2, item 11. For " 8801 " read "0.8801." 922. Table II., furnace C, item 2, under gas. For " 0.011 C " read " 0.011 0." Furnace G, item 13, under gas. For " 5.074 air " read " 3.074 air." Item 15, 114.269 " should be " 4.289." Furnace H, item 2, under iron. For " 0.04 " read ".0.01." 923. Table II., furnace J, item 1, under iron. For " 0.95 " read " 0.93." Furnace N2, item 6, under gas. For " 0.66 CO," read 0.066 C02." 924. Table III., furnace C, item 17. For " 379 " read " 397." 927. Table IV., furnace C, item 4. For " 0.0124 " read 0.0424." Furnace G, item 15.. For " 4,060 " read " 4,066." 928. Line 2. Items 19 and 20 of heat-supply, should be items 20 and 21. 930. Line 3. Expunge remainder of paragraph after the word " supplied," and substitute the following : "As compared with the fusion-zone, the loss by radiation n C was 25.5 per cent. of the total (2,278 units) supplied to that zone, while in D it was 22.5 per cent. of the total heat (1,824 units) supplied to that zone. Finally, as compared with the reduction-zone, C lost by radiation 36.8. per cent. of the 1,580 units supplied to that zone,

May 1, 1910

By B. Chalmers, Stefan Wojciechowski

Rotary oscillation of the mold has been used to produce mechanical stirring of the melt during unidirectional solidification. Al-Cu alloys (1 to 4 wt pct Cu) were solidified to study the influence of alloy composition, temperature at which intensive cooling was initiated, and intensity of stirring on the temperature distribution in the sample, the resulting structure, and the copper microsegregation at the columnar to equiaxed transition. The Proposed explanation for the equiaxed solidification in stirred castings consists of the melting off of dendrite fragments, their partial remelting in hotter liquid, and the subsequent growth of the surviving part when the temperature of the melt is lowered. This may result in the formation of a crystal network, which can stop the growth of the columnar crystals and produce the equiaxed zone. It has long been known and many times affirmed that ultrasonic vibrations or relative motion of liquid and solid can significantly reduce the length of the columnar zone and refine the grains in the equiaxed zone in ingots and castings. Because of the technological importance of these phenomena many investigations have been conducted in which ultrasonic energy or mechanical vibration,1-6 electromagnetic stirring,7"10'17 magnetic stirring,"'12 or mechanical stirring13'14 were used to produce the relative liquid-solid motion. More recently, the question of the importance of natural (or thermal) convection has been raised.15-l7 Several possible mechanisms have been suggested.l,8,18-20 They can be divided into two main groups. The first group includes such nucleation hypotheses as nucleation frequency enhancement due to cavitation at the mold wall or other surfaces; cavita-tion in the body of the liquid resulting from the pressure wave, or an agglomeration mechanism, which involves the formation of nuclei by the accretion of subcritical nuclei. The second group considers the grain-refining action to be due to crystal multiplication phenomena such as the removal of the dendrite fragments by viscous forces or by a high-pressure cycle following cavitation or by a melting-off process. Sbme recent investigations give good experimental support to the melting-off proposa1.21-23 The purpose of the present study was to examine the effect of mechanical stirring during the unidirectional solidification on the structure of alloy samples and on the solidification variables. The motion of the liquid was produced by rotary oscillation of the mold around its vertical axis.

Jan 1, 1969

By William E. Ford, Edward Salisbury Dana

The important BARITE GROUP is the only one among the anhydrous sulphates and chromates. Mascagnite. Ammonium sulphate, (NH4)2S0,. Orthorhomhic. Usrially in crusts and stalactitic forms. p = 1.523. Occurs about volcanoes, as at Etna, Vesuvlus, etc. Taylorite. 5K2SOa.(N&)ySOd. 111 small compact lumps or concretions. From the guano of the Chincha Islands. Thenardite. Anhydrous sodium sulphate, Na2S04. In orthorhombic crystals, pyrarnidal, short prismatic or tabnhr; also as twins (Fig. 384, p. 160). White, to brpwnish. 0 tically +. p = 1.477. Soluble in water. Often observed in connection with salt lates, as on the shores of Lake Balkhash, Central Asia; similarly elsewhere; also in South America in Tarapaca, Chilc. In the United States, forms extensive deposits on the Rio Verde, Aria. In Cal., at Borax Lake, San Bernardino Co. Aphthitaiite. Arranite. Glmerite. (Ii,Na)&O1. Rhombohedral; also massive, in crusts. Color white. From Vesuvius, upon lava; at DouglashaU near Weateregeln, Ger- many, in hloditc; Stassfurt, Germany; Rocalmuto, Sicily.

Jan 1, 1922

William Kent, New York, N. Y.:—The Institute may congratulate itself on the opportunity of reading the splendid address of President Brunton. It is an admirable summary of the progress that has been made in the mining and metallurgical arts in recent years. The paper rightly gives the chief credit for this progress to the aid which has been rendered to these arts by the advances in mechanics, chemistry, and electricity. It is notable that most of the headings in Mr. Brunton's address refer to the work of the mechanical engineer, the electrical engineer, and the chemist, rather than to that of the specialist in mining-operations. It seems that the most successful mining engineer of the present day is the one who makes the most intelligent application of the inventions and designs of engineers and others who are not directly engaged in mining. A tabulation of the headings of the address, grouped as below, shows this most clearly. Work of the Mechanical Engineer—Rock-drills, hoisting-machinery, tramming, pumping, ventilation, dredging, Sampling, concentration, briquetting, fume-recovery. Work of the Electrical Engineer—Electric machinery for hoisting, pumping, tramming, lighting and signaling, electric transmission, electric smelting. Work of the Chemist and Metallurgist—Explosives, chlorina-tion, cyanidation, roasting, lead-smelting, and copper-smelting. Work of the Geologist—Economic geology. Work of the Mining Engineer—Mine-mapping, surface-mining, timbering, tunneling; and planning and supervision of the work in general. The mining engineer of the present day, who is in responsible charge of a large plant, finds his chief work not in doing those things he was trained to do as a specialist, but in making use of the knowledge of geologists, chemists, and electrical and

Jan 1, 1910

By P. M. Budge, William L. Fink, Kent R. Van Horn

The investigation of the phase relations of high-purity aluminum-base alloys is a part of the fundamental research program of the laboratories of the Aluminum Company of America. The results of a number of binary and ternary systems have previously been published in the Transactions of this society. The aluminum end of the binary aluminum-titanium system has been studied. This system has received relatively little attention. To the authors' knowledge, there are two previous papers on this subject. E. van Erckelensl determined the constitutional diagram reproduced in Fig. 1. According to this diagram, the liquidus represents the separation of TiA14, (Ti = 30.7 per cent.). He concluded that this is the composition of the compound, because in his work the eutectic horizontal terminated at 30.7 per cent. titanium and the metallographic examinalion of a sample of this composition revealed only one phase. According to the constitutional diagram developed by W. Manchot and A. Leber,² reproduced in Fig. 2 from data given in their article, the liquidus represents the separation of the compound TiA13 (Ti = 37.2 per cent. ). The composition of the compound was derived in a manner similar to that utilized by van Erckelens. Moreover, Manchot and Leber confirmed the composition of the compound by analysis of the constituent left as a residue after dissolving the alloys in weak sodium hydroxide solution. Although these are the only publications describing the constitution of the system, other investigators have studied the composition of the titanium compound. L. WÖhler3 says that there is a compound TiA13 which was later confirmed by W. Manchot and P. Richter4 and by

Jan 1, 1931

By Harvey T. Kennedy, Charles R. Olson

In many investigations of the performance of petroleum reservoirs the assumption is made that the liquid, if below its bubble-point pressure, is at all times in equilibrium with gas. On the other hand, observations by numerous investigators have indicated that gas-liquid systems including hydrocarbon systems, may exhibit supersaturation to the extent of many hundred psi in the laboratory. Up to the present, there has been no reliable data on which ti judge the actual extent of supersaturation under conditions approaching those existing in petroleum reservoirs. The work reported here deals with observations and measurements on mixtures of methane and kerosene in the presence of silica and calcite crystals. Bubbles were observed to form on crystal-hydrocarbon surfaces in preference to the glass-hydrocarbon interface or to the body of the liquid. Statistically, it was found that the number of bubbles formed per second per square centimeter of crystal surface was a function of the supersaturation only. and the function was evaluated graphically. Supersaturations were observed up to 770 psi, under which condition bubbles formed quickly and with considerable violence. With decreasing degrees of supersaturation, the frequency of bubble formation became less, until at 30 psi supersaturation and lower, no bubbles were observed to form, even though the observation at 30 psi was continued for 138 hours. It was found that silica and calcite crystals had identical effects, within experimental error, in accelerating the formation of bubbles, and that small amounts of water and crude oil had no effect on the results. It is shown that the maximum supersaturation that can exist in a reservoir may be calculated from the data presented and from the area of the rock surface. It is also shown that the number of bubbles formed in the reservoir, in order of magni- tude, may be calculated for any rate of pressure decline imposed on the reservoir by production. The bearing of the number and distribution of bubbles on reservoir performance is discussed. INTRODUCTION A liquid system is supersaturated with gas when the amount of gas dissolved exceeds that corresponding to equilibrium at the existing pressure and temperature. The degree of super-saturation may be conveniently expressed as the difference between the bubble-point of the mixture and the prevailing pressure. Thus, if a mixture having a bubble-point of 1,000 psi at a given temperature exists in single liquid phase at 700 psi at the same temperature. it is supersaturated to the extent of 300 psi. There are many examples of high supersaturations, mostly in aqueous solutions, reported in the literature. Thus, Kenrick, Wismer and Wyatt1 showed that water may be saturated with oxygen, nitrogen or carbon dioxide at 100 atmospheres, and the pressure reduced to one atmosphere without producing bubbles immediately. When liquids are in a state of tension, they may be considered as supersaturated at least to the extent of the tension. The tensile strength of water has been reported as 30 atmospheres by Meyer,1 60 atmospheres bv Budgett. 30 to 50 atmospheres by Temperley and Chambers,4,5 200 atmospheres by Dixon6. and 223 atmospheres by Briggs.7 Vincent8,9 determined the tensile strength of a mineral oil as 45 psi. Gardescu1 maintained pressures for short times in a model reservoir at 115 psi below the bubble-point. It should be noted that the high supersaturations observed were obtained on systems carefully purified to remove particles or surfaces which might promote the formation of bubble; These "nuclei" were considered as contaminants which interfered with the determination of a property of the liquid. In

Jan 1, 1952