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By C. R. Keyes

Discussion of the paper of C. R. Keyes, presented at the Chattanooga meeting, October, 190S, Bulletin No. 26, February, 1909, pp. 119 to 166. E. R. BUCKLEY, Flat River, Mo. (communication to the Secretary*) :-Some statements in the paper of Mr. Keyes relative to the nature and formation of the Ozark lead- and zinc-deposits seem to me erroneous and misleading, and I respectfully present the following criticisms, placing Mr. Keyes's original statements in quotations. Referring to the Ozark dome: (P. 127.) "It is a region that has been repeatedly upraised and planed off, until in the middle portion the oldest known' rocks only are exposed." Does he mean that the St. Francois mountains, which have always been considered as lying on the eastern flank of the Ozark dome, are the middle of the dome? Or does he mean that the Cambrian rocks of the generally-accepted middle are the oldest known rocks ? Certainly not the latter, and if the former, his idea of the middle of the dome is not in accord with that of others who are familiar with the region. (P. 138.) " . . . the ore-deposits are definitely associated with, or localized by, geologic structures of some kind that .produce in effect basins in which' the underground waters are impounded, or their flow retarded." This statement does not appear to be altogether consistent with the facts, since the ore- bodies of the Joplin district, as the rule, occur in those parts of the Mississippian formation which have a tendency to accel¬erate the flow of ground-water rather than retard it. I might name the open, breeciated ground near Joplin, Webb City, and Oronogo as especially noteworthy illustrations. The ore-bodies, everywhere, occur in positions where there must have been a free and copious circulation of dilute lead- and zinc-solutions in the presence of reducing constituents. The inequalities in the distribution of the ore-deposits are

Oct 1, 1909

By A. Faber du Faur

At the request of some of the members to whom I have shown a collection of specimens of sulphur from southern Utah, I herewith present some notes relating to the mines and the method of extracting the sulphur from the ore. In preparing these notes I have borrowed from a paper by Prof. G. vom Rath, published in the Neue Jahrbuch fur Mineralogie, vol. i., 1884, dated Salt Lake City, December, 1883. The Cove Creek sulphur-bed, now worked by the Dickert & Myers Sulphur Co., is in Beaver county, near the line of Millard county. It was first discovered by Mr. Ferdinand Dickert in 1869 ; other beds in the same neighborhood mere found by him from 1872 to 1875, making altogether 22 mining claims. The want of railroad communication prevented the early development of these claims; but in 1883 Mr. F. Dickert put up a plant for extracting sulphur from the ore, which proved a perfect success; and in 1885 the property was transferred to a stock company organized under the laws of Utah. The railroad station nearest to the Cove Creek mines is Black Rock, on the Utah Central Railroad, 204 miles south from Salt Lake City, and about 26 miles west of the mines. The road from Black Rock to the mines passes through desert and lava-bed, to the road leading from Kanosh to Beaver, which latter road it joins near Cove Creek fort, a square stone enclosure, erected by the Mormons for protection against the Indians. Cove Creek fort is situated near the eastern limit of a plain bounded on the west at a distance of about 12 miles by the Mineral range, and on the east by the Sulphur mountains, forming part of the Tushar mountains. To the northwest the plain runs into the Sandy desert. About 3 miles from the fort rises a solitary hill about 1000 feet above the

Jan 1, 1888

By Truman Aldrich

THE Clinton group of the Silurian holds the red or fossiliferous ore; its outcrops have been mapped by the State or U. S. Geological Survey. This group is from 100 to 500 ft. thick in Alabama. There are places where it is entirely missing (doubtless islands in the Silurian Sea). In Etowah County, in part of Greasy Cove and vicinity, the upper seam is a coral reef impregnated with the red ore; in this same county, step, faults bring up the ore in three or four separate ridges practically parallel. In Blount County and on Raccoon Mountain, the ore runs under the carboniferous rocks and outcrops in the valleys. In examining some bore holes made in drilling for oil, the writer found the Clinton group continuing under the Warrior coal field wherever the drill has gone deep enough. It demonstrates the possibility of a source for red ore not seriously thought of until lately. The following bore holes made principally for oil, given in Bulletin No. 22, Geological Survey of Alabama, show the presence of either ore or red rock, and suggest vast resources yet to be outlined and developed for ore in the future. The locations are given by number on the map. Hole No. 1 was drilled 6 miles southeast of Russellville, Franklin County, by the Woodward Oil & Gas Co. It passed through 160 ft. of Clinton, but only a small show of red ore was found at 1280-1400 feet. A test well, No. 2, drilled near Atwood, Franklin County, in section 26, township 8, range 14, penetrated the Clinton at 1608 ft. and found 38 ft. of limy red rock, also 8 ft. of some blood red ending at 1820 ft., making 46 ft. of red rock in all. It is reported that some good ore was cut through but this work was done by a churn drill. The hole was continued by diamond drill from here. At least 400 ft. of the formation was classified as Clinton.

Jan 10, 1924

By F. F. Hintze

Petroleum production in the Rocky Mountain district during 1929 registered a small decline from that of the previous year, conforming with a gradual decrease in the amount of oil produced during the last few years. A number of causes may be mentioned to account for this result, chiefly overproduction in other regions and the apparent desire of operators in this territory to conform to the policy of proration and retrenchment adopted by special agreement among operators in many of the fields. Unit operation has been adopted to control oil production from the Sundance sands in the Salt Creek field, Wyoming, in line with the general effort to stabilize this phase of the industry and prevent excessive drilling of new wells. Another factor which greatly retarded development in the Rocky Mountain region was the executive order of President Hoover issued in March refusing the award of new prospecting permits to future applicants and threatening cancellation of all existing permits upon which actual drilling had not been done as specified by law. Only four states in the Rocky Mountain region are important oil producers. In 1929 Wyoming led with an average daily output of 52,600 bbl., followed by Montana, with 10,730 bbl.; Colorado, with 6500 bbl., and New Mexico with 2700 bbl. daily average. These states bear the following percentage relation to total production in the Rocky Mountain district: Wyoming, 72; Montana, 15; Colorado, 9; New Mexico, 4., (Table 1.) The total average daily production was approximately 73,000 bbl. and the total production of all four states during the year was 26,534,606 bbl. This is 2.7 per cent. of the total oil production of the United States during this period. Colorado Although Colorado is not a large producer of oil and natural gas, its oil operations are widely distributed over the state. The Florence field is one of the oldest oil fields in the country, and there are good reasons for believing that the state will retain its place for many years to

Jan 1, 1930

By R. V. Whetsel, Valentin R. Garfias

Mexican petroleum production for 1928 was approximately 50,000,-000 bbl., the lowest in 12 years, showing a decrease from 1927 of over 14,000,000 bbl. The steady downward trend for the past 7 years has allowed Russia to outrank Mexico by a wide margin for third position and if the expected decline continues during 1929 it should place Persia ahead of Mexico as fourth in rank. The year 1928 was characterized by a continuation of the reentrench-ment previously begun by the oil industry in Mexico in an attempt to adjust itself to the adverse conditions caused by the steady depletion of the fields, the rapidly increasing competition from Venezuela and the United States and the as yet unsettled petroleum legislation and taxation situation. With the exception of the Isthmus of Tehuantepee, drilling in proved fields was considerably curtailed and although the number of wildcats completed exceeded those of the previous year, no extensive drilling programs were undertaken. Practically without exception, the major companies reduced personnel and operations to a point where they could meet existing conditions and mark time while awaiting a more stable basis for the future testing of unexploited regions. Many terminal and transportation facilities were abandoned during the year. Development Only 371 wells were completed during 1928, as against 583 in the previous year and 808 during 1926, and although the percentage of producers in 1928 was 34 per cent., compared to 26 per cent. in 1927, the initial production of -wells was considerably lower than during the previous year, a great number of the wells showing salt water and becoming "strippers" from the time they started to flow. Development is summarized in Table 1. Drilling in the Northern fields did not prove any new pools of importance, the most successful wells being located in the old producing areas of Cacalilao, Panuco and Topila. (Fig. 1 Very few of the producers made more than 1000 bbl. daily, and a great many less than 300 bbl. a day.

Jan 1, 1929

By Ellsworth Daggett

The ore smelted in the Winnamuck furnace during the year 1872 consisted, for the most part, of oxidized ores from the Winnamuck mine, only sixty tons of outside ore (from the Spanish mine) having been smelted. The latter, like the principal Winnamuck ore, was oxidized or so-called carbonate ore. There was mixed with these oxidized ores three hundred to four hundred tons, or 7 to 10 per cent. of galena, some of which was mined with the oxidized ore, while a part was mined separately from the lower portion of the mine, and afterwards mixed with the ore, with a view of preventing the formation of deposits of metallic iron in the furnaces. The average assay in silver of all the ore handled was 51.46 oz. per ton, most of it existing as chloride of silver. The lead contents were 34.98 per cent,, all, or nearly all, in the form of carbonate of lead. The relative amount of silver is not at all constant, the best silver ore often being poorest in lead. The predominant gangue was silica, several determinations of which have been made on representative samples, yielding in three such samples 26, 38, and 58 per cent. silica, the latter test being ore containing but little lead. The average contents in silica are about 35 per cent., with 6 to 7 per cent. sesquioxide of iron, and small quantities of alumina and lime. Mechanically, the ore was very fine, and so thoroughly disintegrated that it presented few distinguishing characteristics, rendering sorting or separating of ore from waste difficult, and often impracticable. Experiments on a small scale have been tried, with a view to separate the silica by washing; but these were unsuccessful, as the finest slime, requiring a long time to settle in still water, contained a large amount of silver; and on a careful sizing and washing of the sands and coarser parts, the silver contents were found to be less dependent upon specific gravity

By Chung Yu Wang

During the time I was in charge of this mine, from 1914 to 1915, I had occasion to read the interesting papers by T. T. Read and C. M. Weld about these deposits, to find how far their observations corroborated mine. To quote from the paper on "The Mineral Production and Resources of China" by T. T. Read:' "The iron ores at Tayeh * * * * lie along the contact between a marble and an intrusive body of a dark gray syenitic rock. * * * * At one place it is slightly magnetic, apparently having been partly reduced to the magnetic oxide by the action of reducing solutions, which have deposited small amounts of copper and iron sulphides along the foot wall." To quote from the paper on "The Tayeh Iron Ore Deposits"2 by C. M. Weld: "I find the orebodies described as occurring along an approximately E-W contact between hornblende-granite and limestone. * * * * The granite is a granitoid rock consisting essentially of quartz, potash-feldspar and hornblende."' These quotations show the differences of opinion entertained by two observers. My own study of these interesting deposits has been intermittent amid the manifold duties devolving upon a superintendent. General DescriptLon of the Deposits The deposits are situated to the west of the Yangtse River, being connected with the river by a standard-gage railroad of 66 li (18.16 miles, 26 km.) in length, as shown in Fig. 1. The general topography of the region is of mature age, showing broad valleys with sluggishly meandering streams. These deposits are worked as two mines, named the Tieh Shan Mining Department and the Teh Tao Wan Mining Department; the former consisting of three orebodies more or less connected, named Tieh Man Kan, Sha Mau Tze and Lung Tung, and the latter consisting of Chang Pei Shan, Sze Tze Shan, Ta Shih Men, Yeh Chih Ping and Tsin Shan, also more or less connected, as shown in Fig. 2.

Jan 1, 1918

By Arthur Wade

During the year 1938, there was some drilling in Queensland, New South Wales and Victoria, as follows: Queens1and.—At Hutton Creek, lat. (approx.) 25° 45' S.; long (approx.) 149°, drilling was done by Drillers limited (subsidiary Oil Search) to a depth of 4688 ft., to the Lower Permian(?). There were small gas showings. The hole mas abandoned. At Mt. Bassett, lat (approx.) 26" 20' S.; long. (approx.) 149", Roma Blocks Oil Co. No Liability drilled to a depth of 4033 ft. The hole bottomed in granite. There were small showings of' oil and gas above bedrock in what may be Permian but is not yet determined. The company intends to run a formation tester. New South Wales.—At Kulnura, lat. (approx.) 33" S., long (approx.) 151°, the Kamilaroi Oil Company Ltd. (subsidiary of Oil Search Ltd.) drilled to a depth of 6293 ft. The Permian, probably Upper Marine Series, was reached. Drilling is to continue. Victoria.—At Romawi, lat. (approx) 37" 50' S., long. (approx.) 147" 45', a dry hole 3246 ft. deep bottomed in the Jurassic and was abandoned. It was drilled by the Governments of the Commonwealth and the State of Victoria. At Lakes Entrance, 1st. (approx.) 37" 50' S.; long. (approx) 748", a small showing of' oil (a few pints a day) was obtained from a well drilled 1275 It., to the Upper Oligocene-Glaucnnitc series, by the Austral Oil Drilling Syndicate, No Liability. Future Drilling Preparations is are being made by companies fur further test drilling in 1939, and the Governments of the Common wealth and the State of Victoria are continuing test holes for information only in the Gippsland district of Victoria. In Papua and New Guinea, no test drilling was done in 1938, but several companies are carrying on geological investigation and it is expected that, some test holes will be drilled during 1939.

Jan 1, 1939

By Arthur Wade

During the year 1938, there was some drilling in Queensland, New South Wales and Victoria, as follows: Queens1and.—At Hutton Creek, lat. (approx.) 25° 45' S.; long (approx.) 149°, drilling was done by Drillers limited (subsidiary Oil Search) to a depth of 4688 ft., to the Lower Permian(?). There were small gas showings. The hole mas abandoned. At Mt. Bassett, lat (approx.) 26" 20' S.; long. (approx.) 149", Roma Blocks Oil Co. No Liability drilled to a depth of 4033 ft. The hole bottomed in granite. There were small showings of' oil and gas above bedrock in what may be Permian but is not yet determined. The company intends to run a formation tester. New South Wales.—At Kulnura, lat. (approx.) 33" S., long (approx.) 151°, the Kamilaroi Oil Company Ltd. (subsidiary of Oil Search Ltd.) drilled to a depth of 6293 ft. The Permian, probably Upper Marine Series, was reached. Drilling is to continue. Victoria.—At Romawi, lat. (approx) 37" 50' S., long. (approx.) 147" 45', a dry hole 3246 ft. deep bottomed in the Jurassic and was abandoned. It was drilled by the Governments of the Commonwealth and the State of Victoria. At Lakes Entrance, 1st. (approx.) 37" 50' S.; long. (approx) 748", a small showing of' oil (a few pints a day) was obtained from a well drilled 1275 It., to the Upper Oligocene-Glaucnnitc series, by the Austral Oil Drilling Syndicate, No Liability. Future Drilling Preparations is are being made by companies fur further test drilling in 1939, and the Governments of the Common wealth and the State of Victoria are continuing test holes for information only in the Gippsland district of Victoria. In Papua and New Guinea, no test drilling was done in 1938, but several companies are carrying on geological investigation and it is expected that, some test holes will be drilled during 1939.

Jan 1, 1939

By W. M. Small

From the one producing well in Austria, 7000 bbl. of heavy oil was produced and sold in 1933. This well, owned by the Raky-Danubia, was completed late in 1932 in the formation called Flysch (Upper Cretaceous or lower Eocene) near Zistersdorf north of Vienna. Two wildcats drilling in the vicinity have not yet reached the producing beds. Near Vienna, the European Gas and Electric Co. drilled five shallow wells for gas, three of which were failures. One gas well was completed for 8 million cu. ft. capacity at 260 meters depth and with a pressure of 570 lb. Another is being tested following blowouts. One gas well and one dry hole were completed in the pool in 1932. In Upper Austria, the same company abandoned one wildcat at 679 m. and is drilling at 280 m. on a second. No gas was sold during the year, but a line is being completed to supply fuel to boilers of the Vienna Electric Works. Hungary No deep drilling was done in 1933. Oil and gas concession was granted by Parliament to the European Gas and Electric Co. on Trans-danubia. Active geological and geophysical investigation is in progress. Czechoslovakia In the Gbely and Hodonin shallow fields, some 26 wells were drilled of which three were reported as failures. The total production of the fields was 111,736 bbl. of oil and 40 million cu. ft. of gas used as fuel in the field. At Vacenovice, where there were already two small gas wells, a third producer was completed at 420 m. This pool markets a small amount of gas, which is compressed and used to light railway carriages. Wildcat wells were reported drilling at about 300 m. depth at both Jasina and Telnice. One 700-ni. wildcat near the Hodonin field was abandoned. Another failure was reported completed and abandoned at 820 m. near Holic.

Jan 1, 1934

By Eckley B. Coxe

I wish to call the attention of the Institute to a peculiar variety of anthracite which occurs in the Buck Mountain vein at our collieries at Drifton, and in the same and other veins in different localities in the anthracite coal-fields. It is known among the workmen as iron-gray or cast-iron. It has a dull, greasy appearance, as if a piece of ordinary anthracite had been rubbed with a dirty and greasy rag and allowed to dry. It was formerly considered a very impure coal containing a high percentage of ash, and was picked out of the coal and thrown away. But the following analysis of it and of its ash, made by Mr. J. Blodget Britton, of Philadelphia, shows that such is not the case, the percentage of ash not being much higher than that of the ordinary anthracites as they are prepared for market. ANALYSIS OF COAL. Water,.........4.36 Fixed carbon, by difference,.. 84.90 Volatile combustible matter,. . 3 48 Ash,..........7.26 100.00 The carbon proved to some extent to be of the nature of graphite, and slowly combustible. ANALYSIS OF ASH. Silica,.........25.66 Sulphur,........ .17 Alumina,........27.03 Phosphoric acid,.......21 Ferric oxide,.......42.83 Alkali, undetermined matter and Lime,.........1.56 loss,.........60 Magnesia,........1.83 Manganous oxide,......11 100.00 We recently collected a quantity of the substance and made a fire with it, in an ordinary stove, which was kept up several days. We found that it burned with intense heat, and apparently as freely as our other coal does. Mr. Britton is probably right in his view, that the difference in appearance is not due to impurities in the coal, but to the fact that the carbon is in a more or less graphitic form, as many of the standard coals are no purer. I bring this before the Institute as I know that a large quantity of this valuable fuel is thrown away every year, on account of its supposed impurities.

Jan 1, 1879

By Victor De Ysassi

THE iron mines of Spain are located on the mountain ridge forming the boundary between the, Teruel and Guadalajara provinces, called Sierra Menera. They form a property of 25 mines extending over an area of 1,677 hectares (4,140 acres) situated at a height varying from 1,200 m. (3,940 ft.) to 1,500 m. (4,920 ft.) above sea level. The deposit follows the direction north to south; huge masses of ore are being found both on the slopes and at the summit of the Sierra. The ore occurs among quartzites and magnesite limestone, in some places overlaid by quartzite 15 in. (50 ft.) thick; in some others (and this is more general) the ore is overlaid by earth and boulders of quartzite origin,; this layer is about 8 m. (26 ft.) thick. The ore beds occupy the geological horizon of the Superior Trias or Muschelkask, which are here in direct contact with the Silurian quartzites. The lime-stones have been more or less transformed. There is ample evidence to show that these mines were worked in very ancient times-objects and tools employed in mining by the ancient Romans and Arabs are to be found plentifully in old workings which extend down into the deposits. It has been estimated that more than 10,000,000 tons of ore were mined in the old days in this district and carried to the primitive forges in the vicinity where iron of much renown in Spain was extracted. Remains of more than 20 of these forges are found in the neighborhood of Sierra Menera and are usually situated near waterfalls and forests. Much investigation has been carried on for the purpose of determining the quantity of ore to be found in these mines, but no exact calculations can be made at present. When the investigation is completed it will surely be found that the deposit contains a much larger quantity than the 100,000,000 tons indicated by the present workings.

Jan 2, 1916

By A. C. Lane

Relations de la profondeur de plissement avec la gravita-tion et la hauteur des montagnes dans les Alpes. Par A. Heim (Zurich) 50me Anniversaire, Livre Jubilaire Soc. Geol. De Belgique, Rome, Fascicule 1, 17 to 28. Measurements show a negative anomaly, less densities of .the material below sea level. The author expresses it in terms of the thickness of rocks of an arbitrary density, 2.4, which might be considered wanting. The accordant heights of the summits, the depths of the folds, the deficiency in .gravity, and denudation he finds to be connected. The Alps float on the lightness of the folds of "sal" of weight 2.6 to 2.75 plunged into the heavier "Sima" according to a for-mula: P = h (2.7/2.8-2.7) where - P is the depth of fold-ing below sea level; 2.7 is the weight of the material accu-mulated in folding; 2.8 is the weight of the material dis-placed by it; and h is the mean height of the mountainous regions. For instance, between the valley of Saar and the Val de Bagne in Valais the depth of the folds according to Ar-gand's profiles is between 30 and 40 kilometers. The loss of gravity has been estimated in this region as 1450 X 2.4 = 3480 in units of weight. Obviously errors in the densities would profoundly affect the estimates of the thickness of folding, but his depths of folds are obtained from sections, and from them he works back to the densities. Of course other densities might be placed in the formula. Zur Dichte bestimmung von Tonen. By J. Koenigsberger, Berg u. Hüttenmannisches Jahrbuch, 75, I. Discusses Dr. B. Wilser's investigations as to the best way of obtaining the weight of rocks per unit volume. The use of mercury for rocks affected by water as there recom-mended may easily give too large volumes unless 1 to 3 atm. pressure is used. Thick machine oil is recommended for large lumps of clay.

Jan 4, 1928

By T. Wasson

The same limitations' that characterized 1931 existed in the old fields of Indiana and Illinois during 1932. Prices remained low. The average for the year for Illinois and southwestern Indiana was $1.032 as against $0.852 for 1931 and $1.616 for 1930. In September a curtailment of production of about 25 per cent became effective and was continued to the end of the year. There were no new discoveries and very little wildcatting was done. Considering the age of the wells, and the number still producing, there were few abandonments. The most outstanding thing about the old fields in these states is their long continued productivity. Illinois The fields along the southeast end of the LaSalle anticline had their peak of 33,686,000 bbl. in 1908. In 1932, with a 25 per cent restriction for 355 months, these fields produced 4,661,000 bb1.l There were 52 new completions (most of them in old territory) and of these 33 were dry, 8 were gas, and 11 were oil wells. The new oil wells had a total initial of 102 bbl., or an average of 9.3 bbl. per well. Nineteen of the new producers were in Crawford County. There were about 200 wells abandoned in the old southeast fields in 1932 as compared to 210 in 1931. The greatest number, 86, were in Lawrence County. To the end of 1932, the four major counties—Clark, Crawford, Lawrence and Wabash—had produced almost 394,000,000 bbl. from 92,160 acres. Better than one-half of this was produced in Lawrence County from 26,240 acres. The Dupo area of Sinclair County had no additions to production although four wells were drilled. On the Jacksonville structure in Morgan County, six gas wells with an average depth of 300 ft. were drilled to sands in the base of the Pennsylvanian. They produced an open-flow total initial of 2,000,000 cu. ft. This gas will be developed further to supply a local market.

Jan 1, 1933

By J. J. Jonas, J. L. Uvira

Equipment was constructed which permitted the hot compression of 99.8 pct Armco iron and 2.8 pct Si steel at constant true strain rates of 0.05 to 1 per sec over the temperature range 600" to 1000°C. A maximum true strain of 1.9 could be attained, followed by immediate quenching or by isothermal annealing. True stress-true strain curves were obtained, and the steady-state flout stress, a, strain rate, i, and temperature, T, were found to fit the following expression: The constants A, a, n', and AH were determined for the two ,materials. The activation energies obtained for Arrnco iron and silicon steel are 66 and 80 kcal per mole, respectively, and approximate those for seu- diffusion and for creep. This indicates that hot compression is a diffusion-controlled thermally activated process. THE hot compression of iron and steel is usually carried out in the austenite temperature range,1"7 as this is the one of greatest interest with respect to industrial hot working. However, a disadvantage of testing in the austenite range is that the hot-worked structure is destroyed by the phase transformations taking place during cooling. The present study was therefore carried out in the ferritic temperature range, and the hot-worked substructures were preserved by rapid quenching after deformation. The substructural results will be described in a separate paper, and the present communication is restricted to the strain rate/stress/temperature relationship observed during hot working. The results of hot-compression testing are usually given in the form of true stress/true strain curves, with a different curve for each temperature/strain rate ~ornbination.',~,~ Sometimes simple algebraic equations are fitted to the curves, so that certain extrapolations or interpolations can be performed.1'2'5 These equations are, however, devoid of mechanistic interpretations. The present study was undertaken to show that hot compression can be described by an equation of the type used in creep studies. That is, it will be shown that the temperature dependence of the strain rate in hot working is well-represented by an Arrhenius term, with an activation energy similar to that for creep. Also it will be seen that the stress dependence of the strain rate is similar to that for creep EXPERIMENTAL METHOD AND MATERIALS The investigation was carried out with the following three ferrous materials: 1) Armco iron; 2) Armco iron with 0.26 pct Mn; 3) 2.8 pct Si steel. The first two materials were utilized for investigations performed in the temperature range 600" to 800°C; the last one was used for tests at temperatures from 600" to 1000°C. The materials were of commercial purity,* as shown in Table I. Cylinders of five different sizes were prepared by strain annealing. The resulting mean grain diameter was 3 mm in the 1-in. Armco iron and 2 mm in the other sizes and grades. Different ratios of diameter/height were used to enable the determination of the coefficient of friction. The specimen faces were provided with concentric grooves, which acted as lubricant holders during compression, as recommended by English and ~ackofen' and others.2'9 Powdered glass lubricants were applied to the samples before hot compression to decrease friction and barreling, following the practice of previous investigator~.~~~~~~~~ Different mixtures of glass powder were used for each temperature, after the determination of suitable compositions by experiment.'' Equipment for Hot Compression. Hot-compression tests were carried out on an adapted 150-ton vertical hydraulic extrusion press and also on a modified high-temperature creep machine. The modified extrusion press was used for temperatures up to 800°C. The following items were added to the press: a) a high-temperature furnace with built-in upper and lower platens; and b) a transmission assembly, which permitted the attainment of logarithmically decreasing crosshead speeds. These accessories are described in detail in Ref. 11.

Jan 1, 1969

By D. R. Walker, M. C. Shaw

Dimitri Kececioglu (Allis-Chalmers Manufacturing Co., Milwaukee)—The idea of applying metal cutting theory to comminution and vice versa is very impressive. Among others, the demarcation of wheel-grinding data into two regions, namely Kick's and Rittinger's, draws attention here. A study of Figs. 6 to 9 shows the following: In Fig. 6, 1 point out of 8; in Fig. 7, 4 points out of 26; in Fig. 8 only 1 point out of 13; and in Fig. 9 practically none out of 13 points fall out of curve No. 2. Also when grinding particles smaller than 5x10." in. it is difficult to measure very accurately the grinding forces, chip geometry, and particle size. In view of the above it would be difficult to make a positive and distinct demarcation of the Wheel-grinding data into two regions, namely, Kick's and Rittinger's. The idea of using machine grinding to determine the comminution properties of materials is indeed unique. The following cautions come to mind, however, regarding applicability of machine grinding data to comminution: 1—Grinding gives uniform particle size, whereas comminution gives a variety of particle sizes in the same process. The fact that grinding gives uniform particle size is not necessarily an advantage because in comminution the overall energy under actual comminution is desired and comminution invariably results in the production of a variety of particle sizes. 2—In grinding, a small particle is ground off a comparatively large surface. In comminution small bodies are broken down to smaller bodies. This makes it difficult to establish a concept of reduction ratio in machine grinding. 3—The mechanics of machine grinding involve direct shearing action under very high strain and comparatively high compression at the shear zone, whereas: comminution involves direct dynamic compression and surface friction with comparatively little strain and shear. Consequently the mechanics of machine grinding appear to be different from those involved in comminution. Hence one might arrive at erroneous con- clusions when comminution characteristics are eval-uated from machine grinding results. It is noticed also that functions other 'than Eq. 16 which do not involve the concept of direct proportionality of useful energy input to new surface area created (Eq. 2 and particularly Eq. 12) may be derived to fit the, data of curve No. 2. One such relationship may be u = ct-", where c is a positive constant and n is a positive constant less than unity. This, of course, is made possible because data of a very small range. of particle size are being fitted by the curves of No. 2 and the hereby suggested relationship. A sound comminution theory should be applicable to a relatively large range of particle size. George B. Clark (Department of Mining Engineering, University of Illinois)—While the experimental work of Walker and Shawin this article is of intrinsic value in revealing certain fundamental aspects of machine grinding, milling, and related processes and in adding to the store of information concerning the comminution of solid materials by this particular process, it appears doubtful that the results of their research can be employed to verify either Kick's or Rittinger's theories. Both these laws were originally developed and proposed on the basis of very simple, idealized hypotheses. The creation of parallel idealized physical laboratory conditions which would be required for either their proof or disproof appear to be well beyond the scope of human ingenuity, at least at present. One great weakness of the imputed verification is that the spread of the points plotted on the graphs is not sufficient to permit accurate 'curve fitting. The range of particle sizes included in the belt and wheel grinding is not extensive enough to show any general trends, particularly for the horizontal portion of the curves, said to represent Kick's laws. That the milling; grinding, and turning data obtained by Walker and Shaw for both metals and minerals happen to comply with. certain interpretations of these two theories under certain specialized conditions

Jan 1, 1955

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By R. F. Burdyn

The inadequate use of centrifugation to economically recover solids from weighted drilling fluids reflects the need for better equipment and techniques for this putpose. Laboratory studies in the development of an improved separator are described in which an operating equation is derived and tested. Results show that the concentric cylinder geometry employed effectively separates bnrite from a suspension and that the operating equation provides a good approxinmtion for scale-up. INTRODUCTION Our current drilling technology frequently requires a high-density drilling fluid obtained by addition of barite. In the course of drilling, formation solids which are too fine to be removed either by screening or settling become suspended in the drilling fluid and gradually the volume of solids in the mud increases. The volume fraction of solids must be limited (if a satisfactory set of rheological parameters are to be maintained). A centrifugal separatorprovidesan economical way of accomplishing this. The barite recovery process can be considered as a separation of two solids. One, the light solids, composed of formation and added solids, has a specific gravity of 2.6 to 2.7; the other, barite, has a specific gravity of 4.2 to 4.3. This density difference, plus the fact that the average light-solids particle size is much smaller than the average barite particle size, permits separation by a centrifuge. In drilling fluids some of the coarse particles of the light-solids-range will settle faster than fine particles of the barite-particle range. As a result a complete separation of the two species is not possible. since the object of the process is not merely recovering the maximum amount of barite but includes as well removing the maximum amount of light solids, an optimum barite recovery efficiency exists. From a practical standpoint this optimum cannot be determined in the field for each drilling fluid system, and in practice the separation is less than optimum, with some sacrifice of barite. Drilling technology has included centrifugal separators for barite recovery for more than a decade. Results have been reported by a number of investigators indicating that the process is practical and economica1. l-4 The decision to use a centrifuge is based on economics in which direct cost savings and the indirect benefits in rig time derived from improvement of the drilling fluid are important factors. One would expect that centrifugal separation of barite from drilling fluids would significantly affect barite consumption; however, this is not the case. The Minerals Yearbook shows an annual domestic barite consumption in the drilling industry of nearly 1 million tons.5 By rough estimate there are perhaps 80 separators presently in field use. Assuming half of these in use at any one time, operating an average of four hours per day, at recovery rates averaging 3,000 Ib of barite per hour, total annual recovery is about 90,000 tons. This is less than 10 per cent of he total barite used. I conservatively estimate that barite consumption in drilling operations can be reduced by 30 per cent through greater utilization of centrifugal separators. To encourage more widespread acceptance of centrifugal separators in the drilling industry, improved equipment and techniques would be very desirable. The present paper, covering theory and results obtained from a laboratory model, is the first in a series on he development of an improved mud separator for field use. THE CONCENTRIC CYLINDER GEOMETRY AS A SEPARATING DEVICE Consider the geometry shown in Fig. 1, consisting of two concentric cylinders separated by an annular space. These are arranged so that the outer cylinder is fixed and the inner one can be rotated about its axis on shafts sealed against the ends of the outer cylinder. If the outer cylinder is fitted with openings at either end, the inner

Jan 1, 1966

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),' while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).' These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969