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By L. S. Darken

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By G. R. M. Del Giudice

The term "slime-coating" is not new in the art of flotation; the phenomenon has been observed and described by Taggart;(l)† Taggart, Taylor, and Ince;(2) and by Ince.(3) Notwithstanding that flotation was introduced for the treatment of finely crushed ore, the adverse effects of slimes have been recognized since the earliest days of the process, and the Elmore, Delprat, Potter, and other processes actually specified desliming of the ore prior to treatment. The cause of this trouble has been studied and described by Taggart;(1) Taggart, Taylor, and Ince;(2) Ince;(3) Morrow and Griswold;(4) and by Gaudin and Malozemoff.(5) Old Theory of Slime-coatings At present, so far as published work shows, there seems to be but one theory for the mechanism of slime-coatings. Ince(3) states that they are due to attraction between electrostatic charges of opposite sign on the sulfide and on the slime particles, supporting this theory by migration experiments in the Burton tube. He also used the microscope in conjunction with a glass cell employed by Beans and Eastlack(6) in studying migration, but met with interference from endosmosis. Several attempts have been made in the Department of Mineral Dressing at Columbia University to duplicate Ince's experiments with the Burton tube, but the results have never been convincing. Formation of precipitates which settled through the pulp levels, and evolution of gas at the electrodes, which disturbed the interface between the pulp and the distilled water above it, seriously interfered with observations. However, by use of the migration cell shown in Fig. 1, endosmosis effects and the disturbances due to precipitation and gas evolution were avoided, and distinct and reproducible migrations or absence of migration were observed. The cell was made of bakelite and had platinum electrodes. Objectives were employed which had a working distance of at least three millimeters,1 and the parts of the mounting which came in contact with

Jan 1, 1935

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of 'association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples'-4 or thermogravimetric measurements. 5,8 Darken and Gurry's1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth's neutron-diffraction experiments. Roth's model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1' used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.' Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3' states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By R. G. Wayland

SINCE the installation at Kropfmuehl, Bavaria, of a modern flotation concentrator in 1938, the flake and fine graphite from the Passau area can now be delivered in about any normal specified carbon content of any size range up to a flake averaging about 0.7 mm. The graphite finds a wide German and export market for crucible manufacture, pencil leads, dry cells and other uses. A controversy over the origin of the graphite deposits is being resolved in favor of syngenesis rather than epigenesis. The syngenetic theory is newly supported by the yet unpublished work of Hartmann of the Bavarian Geological Survey. Development work and exploration for graphite in the area may be changed in direction as the syngenetic theory is accepted. Crystalline graphite is produced in the area east of Passau near the junction of Germany, Austria and Czechoslovakia, as shown in Fig. 1. This is the only graphite area of importance in Germany, and Gra-phitwerk Kropfmuehl AG is the only operating firm in the area. The plant and mine are located at Kropfmuehl near Hauzenberg, Kreis Wegscheid, about 10 miles east of Passau. A narrow gage railway from the mine connects with the German Railway at Schaibing Bahnhof. The Pfaffenreuth mines date from about 1730. Until the early 20th century mining operations were carried out in a haphazard fashion. During World War I graphite mining and milling was increased, since it had to cover almost all of the crucible needs of the Central Powers. Between the wars some 11 mines were operated by two large and several small companies, but under the Nazis these were consolidated by 1938 into the Kropfmuehl enterprise. Kropfmuehl built a modern flotation mill to treat its own ores and small amounts of custom ores and tailings from the area. Since Graphitwerk Kropfmuehl AG was an I.G. Farbenindustry subsidiary, it has been under Military Government Property Control and probably will be sold to private German capital. Geology The country rock of the graphite area is part of the "kristallines Grundgebirge," the series of old gneissic and schistose rocks that constitutes the bed rock of most of the Bohemian basin and rims the Sudeten-land. The gneissic rocks of the graphite area are considered to have been metamorphosed during the Carboniferous period. They are bordered on the north by granite stocks and penetrated by numerous smaller granite and pegmatitic intrusive rocks, as shown in Fig. 1. The gneiss is classed as a micaceous, coarse-grained cordierite gneiss by most investigators. It is much metamorphosed by the granite, particularly in the north near the larger granite bodies. Interbedded in the gneiss are the graphite seams and lenses, and also beds and lenses of crystalline limestone containing disseminated graphite in noncommercial quantities. The gneiss, together with the included graphite and limestone seams and lenses, is cut and displaced by a number of granite sills of medium to fine grain and by a large number of diorite lamprophyre dikes and a few syenite-pegmatite dikes. The lamprophyre dikes are of various mineral compositions and textures, but many are banded and richly impregnated with pyrite; while the syenite-pegmatite dikes are coarse-grained with good crystals of titanite, pyroxene, uralite and other green amphiboles. Most investigators and the miners speak only of diorite and granite dikes cutting the graphite seams. The diorite dikes are later than the granite and some of the faulting, as is evident from Figs. 1 and 2. Individual graphite seams and lenses may be mined for thicknesses of several feet up to several scores of feet, and for distances of several hundred feet. The aggregate thickness of a series of some 20 seams of graphite, limestone and interbedded gneiss at Kropfmuehl is stratigraphically about 450 ft. Laterally, the graphite in a seam may pinch out or grade into crystalline limestone. Graphite crystals also are found disseminated in the gneiss itself, although in unmineable concentrations. The faults that cut the graphite seams carry graphite for some feet or tens of feet away from the seams, apparently mechanically. Similarily, the graphite lenses themselves often contain mechanically introduced inclusions of wall rock, probably from flowage during folding. Graphite crystals make up 10 to 30 pct of the fresh, mineable graphite lenses at Kropfmuehl, averaging about 20 to 25 pct after hand-sorting by the miners. In weathered lenses, the graphite concentration is said to be as high as 50 pct. The associated primary and hydrothermal minerals are dom-inantly feldspar and calcite, plus quartz, pyrrhotite, pyrite, biotite and occasional garnet, hornblende, sphalerite and galena. Associated secondary minerals include kaolin, nontronite, mangano-oxide-silicates (mog), adularia and chlorite. The superimposed suite of siliceous cementation minerals present consist largely of opal, chloropal, chalcedony, jasper, and hyalite. The kaolin is of special interest since it too was mined as early as 1730 and was used in the well-known Nymphenburg porcelain from 1756 on. The kaolin is derived from the gneiss and the syenite pegmatites. The crystals of graphite vary in size within a given seam, but in seams more than a mile away from the granite on the north the average crystal-linity is less coarse, lowering the commercial value. The lenses in the Kropfmuehl-Pfaffenreuth area are the most developed, and are the only ones with deep workings now accessible. Other similar crystalline graphite lenses are known from older workings at Habersdorf, Oberoetzdorf, Ficht, Diendorf, and

Jan 1, 1952

LANS are underway for the annual meeting of AIME, to be held in New York, February 17 to 21. The technical program includes meetings of all divisions of all three branches, Mining, Metals, and Petroleum. The bulk of the technical sessions will be held at the Statler Hotel, and the annual banquet will be held at the Waldorf-Astoria, Wednesday evening, February 20. The technical program of the Mining Branch activities is included in this issue. While it is not complete in every detail, it shows general interest groupings as well as subjects to be discussed. The program for each division is shown separately to facilitate following the activities of these special interest groups. Then, after a full scale and possibly somewhat strenuous technical meeting, a post-meeting feature will appeal to many of the members. A restful cruise to Bermuda and Nassau is offered at special rates to AIME members and friends. The schedule is a 3:00 pm departure from New York on the Queen of Bermuda on Saturday, February 23; arrival at Bermuda at 7:00 am Monday, February 25; arrival at Nassau at noon, Wednesday, February 27; and the trip ending again in New York at 9:00 am, Saturday, March 1. Rates begin at $202.10 per person, with higher rates depending upon accomodations desired. The base rate includes outside room with private bath and all meals, as well as Federal, Bermuda and Nassau taxes. Reservations for the trip should be made immediately through Leon V. Arnold, 36 Washington Square West, New York 11, who is in charge of arrangements.

Jan 1, 1952

By James S. Browning

The Bureau of Mines conducted laboratory and small-scale continuous tests of kyanite ore from Georgia and South Carolina to determine the technical feasibility of recovering commercial grade kyanite concentrates by flotation. The research indicated that combinations if sulfuric acid and petroleum sulfonate may be used effectively for flotation of kyanite from quartzite-kyanite ore. This report summarizes the results of these tests, and demonstrates the feasibility of producing commercial-grade concentrates with a high recovery of the contained kyanite. Extensive deposits of kyanite occur in the southeastern United States. The reserves of these deposits, if developed, are adequate to supply the United States with 35-mesh kyanite concentrate for many years at the present rate of consumption. According to Espenshade and Potter,' the kyanite-quartz rock type deposits in this area contain about 100 million tons of ore averaging 10 to 30% kyanite. The tonnage of kyanite-bearing gneiss and schist is much larger than the tonnage of kyanite-quartz rock, but the kyanite gneiss and schist are appreciably lower in grade. The largest deposits of kyanite-quartz rock are in the Farmville district, Virginia, and Kings Mountain district, North Carolina-South Carolina, and at Graves Mountain, Ga. Of the known deposits, only four were being mined for kyanite in 1 967. These deposits are near Farmville and Dillwyn, Va., Clover, S.C., and Washington, Ga.

Jan 1, 1970

By P. H. Fahlström

The Ebliden Company, originally entering the field of mining with the workings of the gold-copper-arsenic deposit at Ebliden, commenced zinc benificiation at Kristineberg in 1940 and lead mining at Laisvall in 1943. During the three last decades a number of mines has been developed for production, Today the Mining Division of BOLIDEN produces ore from 22 mines, operates 7 ore dressing plants and produces: [ ] Over two thirds of the lead contents are treated in the lead smelter of the company at Ri6nnskarsverken. The other part of it is sold abroad. The zinc content of the lead concentrates is recovered from the lead smelter at Ri6nnskarsverken. The zinc concentrates are shipped abroad to European smelters in Norway and Germany. Today BOLIDEN has its plants in the northern and the middle parts of Sweden. Figure 1. Straight lead ore, lead-zinc ores, lead-zinc-copper bearing ores and complex lead-zinc-copper and pyrite ores are treated in local and central plants with a capacity of 8.600 tpd. BOLIDEN also operates the low grade copper ore at Aitik at 7.000 tpd.

Jan 1, 1970

By Alden B. Greninger

The study of mosaic structure of crystals1 has been confined until recently to the field of theoretical physics. Crystallographers, in general, have neglected the subject, although X-ray crystallographers constantly make use of formulas for intensities of X-ray reflection as modified by mosaic structure. Work on mosaic structure has centered chiefly on the task of proving or disproving the secondary-structure theory of Zwicky,² and very little attention has been paid to the visible imperfections of crystals. A. Goetz has been responsible for most of the supposed experimental confirmations of Zwicky's theory.3 On the other hand, Smckal,4 and Orowan,5 among others, maintain that there is neither theoretical nor experimental evidence to substantiate Zwicky's secondary structure. Lately the subject has been intensively investigated by Buerger,6 one of whose recent papers led to a symposium on mosaic structures.'

Jan 1, 1935

By Alden B. Greninger

The study of mosaic structure of crystals1 has been confined until recently to the field of theoretical physics. Crystallographers, in general, have neglected the subject, although X-ray crystallographers constantly make use of formulas for intensities of X-ray reflection as modified by mosaic structure. Work on mosaic structure has centered chiefly on the task of proving or disproving the secondary-structure theory of Zwicky,² and very little attention has been paid to the visible imperfections of crystals. A. Goetz has been responsible for most of the supposed experimental confirmations of Zwicky's theory.3 On the other hand, Smckal,4 and Orowan,5 among others, maintain that there is neither theoretical nor experimental evidence to substantiate Zwicky's secondary structure. Lately the subject has been intensively investigated by Buerger,6 one of whose recent papers led to a symposium on mosaic structures.'

Jan 1, 1935

By John Stewart

The market at present supplied by shipments from the phosphate districts of Quebec, Ontario, and New York State requires high-grade ore, carrying from 75 per cent. to 90 per cent. of phosphate of lime. In sorting out such material by hand, much valuable phosphate is necessarily left in the "culls" or refuse, besides which, much phosphate-rock of low-grade is not now mined at all, because it cannot be made available by the crude method of cobbing and hand-sorting. The utilization of such material, which would, of course, greatly benefit this industry, requires either a mechanical separation or a chemical process which would concentrate the phosphate in a form suitable for agriculture. Considering the rich phosphate now shipped as the first class, we may arrange the lower grades in three classes, as follows: Second Class.—Cull-ore from the first class, and the mass of deposits having, as gangue, pyroxene or hornblende. The following table gives the hardness and specific gravity of the minerals concerned: Hardness Spec. gravity. Apatite,....... . 5 3.1 to 3.25 Crystalline limestone (pink calcite),. 3 to 4 2.5 to 2.9 Pyroxene,..5 to 6 3.23 to 3.5 Hornblende,.5 to 6 2.9 to 3.4 Feldspar (orthoclase),. .. . 6 to 6.5 2.5 to 2.6 It is evident that when pyroxene and hornblende are present in large proportions, this ore cannot be successfully concentrated by crushing and jigging. It may be reduced to fine powder by successive treatment in a rock-breaker and a Sturtevant or Frisbee-Lucop mill, or other suitable apparatus, and in this condition it could be largely used by applying it freely upon exhausted clay soils, such as occur in Quebec and Ontario. The occupants of these once fertile river-lands are, however, hard to move in the direction of such improvements. When water-power is at hand, the cost of crushing

Jan 1, 1893

By H. O. Hofman

THE leading antimony mineral is stibnite. In smelting stibnite ore two processes are available, precipitation and roasting-reduction. The former is suited only for high-grade ores. As low-grade ores are more common than high-grade, roasting-reduction is of greater importance than precipitation. In the roasting process the aim may be to leave the oxidized antimony in the ore, or it may be to volatilize as much of the antimony as possible, collect the volatilized oxide as a rich intermediary product and smelt it for antimony, leaving the gangue poor enough to be considered a waste product. Whichever way the roast is conducted certain difficulties inherent in stibnite are encountered. These are: 1. The low melting point of stibnite which; according to Pelabon,1 is 550°C., according to Wagemann2 540°C., and according to Borgström3 546°C. 2. The ignition temperature: According to Friedrich,4 stibnite, if heated in air, begins to oxidize at 290°C. if the size of a grain is 0.1 mm. in diameter; at 343°, if 0.1 to 0.2 mm.; and 430° if 0.2 mm. 3. The fusibility of a mixture of Sb2S3 and Sb203 which in the form of kermesite (Sb2S3)2.Sb203 melts at 517°C.5 4. The volatility of Sb2S3 and Sb203, for which no numerical data appear to exist, although practical experience has shown that they are volatile at low temperatures.

Jan 1, 1916

By B. N. Bose, M. F. Hawk

SINCE Davenport and Bain' introduced the isothermal transformation technique for the study of austenite decomposition in steels, a new field of investigation has opened up. Extensive research has been carried out on many different steels, but relatively little work has been done on eutectoid transformations in analogous alloy systems. The researches of Smith and Lindlief,² Mack,³ and Klier and Grymko²0 on the beta-phase transformation in copper-aluminum alloys, of Hibbard, Eichelrnan, and Saunders4 and Smith5 on the kappa-phase transformation in copper-silicon alloys, of Chaudron and Forester6 on the decomposition of "FeO," and of Wasserman7 on similarities between the iron-carbon, copper-aluminum, copper-tin, and copper-beryllium systems essentially comprise the field. The iron-nitrogen system, in view of its remarkable similarity to the iron-carbon system, is particularly attractive for the study of eutectoid decomposition. The present investigation is concerned with the study of isothermal transformation, proceeding by the familiar nucleation and growth processes, and of martensitic transformation characteristics of pure iron-nitrogen alloys. The kinetics of transformation and the morphology of the transformation products have been investigated, for these must be the factors determining the properties and behavior of the final product. The Iron-Nitrogen System he binary iron-nitrogen phase diagram has been a matter of considerable disagreement among vari01.1s investigators. However, the phase diagram according to Eisenhut and Kaupp8 and Lehrer10 is now considered essentially correct as reproduced in fig. 1. The important values, 2.35 pct nitrogen and 591°C, for the co-ordinates of the eutectoid point (obtained from this diagram and used in the re- search to be described) were confirmed in a concurrent study of Paranjpe, Cohen, Bever and Floe." The eutectoid decomposition involves the transformation of the ? face-centered cubic interstitial solid solution of nitrogen in iron to the a body-centered cubic interstitial solid solution of nitrogen in iron and the ?' nitride of iron. This nitride is essentially the compound Fe,N; it also possesses a face-centered cubic lattice but a considerably larger one than the ?; the nitrogen atoms in ?' are arranged in an ordered way in the centers of the unit cubes.8,10,11 A martensitic structure has also been reported8,12 in iron-nitrogen alloys and was studied in the research to be described here. Materials and Methods The specimens used in this investigation were prepared by nitriding "pure" iron. This iron was supplied by the Westinghouse Research Laboratories and is the product bearing their trade name "Puron"; it contains about 0.04 wt pct total impurities, the major portion of which is oxygen. Specimens were ribbons several inches long, a tenth of an inch wide, and 0.125 mm thick; this was the

Jan 1, 1951

By Frank A. Wilder

The most important process in a gypsum mill is calcining the crude mineral. There seems, however, to be little progress or change in calcining methods. This would not be surprising if the industry was not, in other ways, developing. The demand for gypsum in its various forms, however, is growing rapidly. The output has more than doubled in six years, while the value of gypsum products, through the introduction of higher priced. specialties like wall board, has nearly trebled in the same period. In other industries, under somewhat similar conditions, calcining in rotating cylinders, either by direct or indirect heat, has replaced the method that still prevails in gypsum mills. Efforts were made to use rotary calciners in manufacturing plaster of Paris in the early days of the industry in America; 25 years ago rotary calciners were in use in Germany. At that time there was great diversity of opinion in regard to their merit. In 1923, the output of calcined gypsum in the United States was 3,101,378 tons. About nine-tenths of this material was calcined in kettles, the remainder in rotary calciners. The ratio was about the same 10 years ago. During these 10 years, rotary calcining made relatively no gains, and there were no important changes in the construction of kettles. In their manipulation, the only change of consequence was in connection with the length of time that the gypsum is left in the kettle. For wall-plaster purposes, all producers who had not previously done so changed from second-settled to first-settled calcined gypsum, thereby reducing production costs and improving the plasticity and sand-carrying capacity of their plaster. Nevertheless, in the few mills in which they were installed, rotary calciners continue to operate, with possibly one or two exceptions, and to be highly successful. In these 10 years, the Cummer type of rotary calciner has disappeared. All rotaries now used are of the cement-mill type with a diameter of 6 or 7 ft. and length of 80 to 120 feet.

Jan 1, 1925

By F. W. Jessen

The Mechanism of solution of salt and mixed halites of sodium and potassium is reviewed. The variation in the rate of salt removal under both laminar and turbulent flow conditions is discussed. Many changes are possible in the development of solution cavities whether used for production of salts or for storage of hydrocarbons. The parameters influencing the type and shape of cavity formed with single well or multiple well systems are examined and information presented regarding field application of techniques developed and the means of controlling overall configuration of solution cavities.

Jan 1, 1972

By C. S. Cole

CO-CHAIRMAN CARTER S. Cole l-The stimulus of war definitely increases interest in the subject we are discussing at this Symposium. There have been, in the past, other symposia on this subject and there probably will be still others in the future, but I feel sure that this one will go down as one of the most important that have ever been held on the subject. In 1918 A.S.T.M. held a Symposium on Stress- Corrosion Cracking that was confined entirely to brass, because at that time few people were interested in the phenomenon as it applied to other metals. Again under the stimulus of war, we are gathered to discuss the subject, but this time brass alone is but part of our interest. It is interesting to note more papers on brass will be presented than there were in the 1918 session, but these brass papers, you will also note, comprise less than half our program. Aluminum, magnesium and

Jan 1, 1945

By James O. Elton

This paper covers, besides laboratory work, a study of actual operation at the Washoe Smelter over a considerable period of time, together with the results of a visit to the Midvale plant of the United States Smelting & Refining Co., near Salt Lake. For the latter privilege, as well as permission to publish the resulting data herein given, I am indebted to George W. Heintz, General Manager of the Midvale plant, and here take pleasure in expressing my appreciation for the many courtesies extended to me by Mr. Heintz and members of the technical staff at the smelter. Almost all of the world's supply of arsenic is recovered as a byproduct in the smelting of other metals. It is seen 'on the market in various forms, the most common being arsenic trioxide, the " white arsenic " of commerce, which is sold as a heavy white powder, or in white, glassy, translucent masses. The trioxide is used in the manufacture of pigment, glass, and insecticides. About 50 per cent. of the domestic consumption is supplied by imports. Statistics of Arsenic Trioxide in United States.' Production. Consumption. Price Per Pound. Year. Tons. Tons. Cents. 1907..........1.010 5.471 5 1908,.........1,302 6,098 33/4 1909,.........1,007 4,600 2 7/8 1910,.........1,526 5,428 2 1/2 1911,.........3,081 6,539 2 1912,2........ 2,926 Closed at 4 7/8 Arsenic occurs in combitlation with sulphur and the metals in a large number of minerals. It is present in small amounts in many ores. In the roasting and smelting furnaces many of its compounds break down, liberating arsenic trioxide, which is volatilized and carried by the gases into the flue system, where a part is condensed and settles with the flue dust.

Jan 1, 1914

No true conception of the Park City mining district can be obtained without first giving consideration to the part it has played as a consistent producer of mineral wealth. Its position in this regard is almost unique in the annals of a lead silver camp. For over fifty years it has been a continuous producer of lead and silver and for twenty years it has added to the world's supply of zinc. Few camps with its productive history are so little known to the mining fraternity for the reason that its life has never been punctuated by periods of "boom" which serve to attract general attention, neither has it been the field of operation for promoters who temporarily focus attention upon their scene of action. Its history is one of legitimate mining operations. These were at first carried on by a number of smaller companies. A period of consolidation followed and at the present time the entire production of the camp is in the hands of two major companies and one smaller company. These are flanked by a number of prospecting properties, which are at this time actively engaged in the search for ores and later events will doubtless put some of them in the producing class.

Jan 1, 1925

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine' who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H'-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson'28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By W. R. Seyfried

THE problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations. An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper. The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reagent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp. became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant. By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1472°F), (b) The roasted ore would then be leached with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1947

By Thomas G. Murdock

EthIopia, the first country to be liberated from Axis domination, has recovered remarkably from the ravages of occupation and war. Mineral production has contributed significantly towards this recovery, as it has provided a means of obtaining foreign exchange and has given employment to hundreds of workmen whose maintenance otherwise would have presented a problem. Although primarily an agricultural country, never with a large mineral production, Ethiopia has within its borders a variety of minerals, both precious metals and nonmetallics. Some of these are important to the country as a national asset and others contribute greatly to local economy and can be expected to do so even to a greater extent in the future1 (Fig I). Physiography and Geology The Empire of Ethiopia is essentially a mountainous and volcanic country, in northeast Africa, situated principally between latitude 4° and 15°N and longitude 34° and 44°E. It is bounded on the north by Eritrea, on the northeast by French Somaliland, on the southeast by Italian Somaliland, on the south by Kenya Colony, and on the west by Anglo-Egyptian Sudan. These European possessions thus completely surround the country. Its access to the Red Sea is through Eritrea; to the Gulf of Aden, through French or British Somali- land ; and, to the Indian Ocean, via Italian Somaliland. These routes range in length from 40 to 250 miles. Ethiopia has an area of approximately 350,000 square miles, with a width from north to south of 625 miles, and a maximum length from east to west, along latitude 8°N, of about 875 miles. Physiographically the country is characterized by two very extensive sub-tabular plateaus: the Ethiopian Plateau to the northwest and the Somaliland Plateau to the southeast, separated by a long tectonic graben—the Rift Valley of the Galla Lakes and Danakil. The Ethiopian Plateau, deeply cut and notched by the drainage, slopes in a general northwest direction toward the Sudanese Plains and the valley of the Nile; the Somaliland Plateau slopes to the southeast, toward the Indian Ocean. The valley of the Galla Lakes and its extension to the northeast—the Awash River Valley, separates the plateaus, from Lake Rudolph to Danakil. This depression which constitutes a continuation or ramification of the Great Rift Valley of Central Africa joins in turn the trough of the Gulf of Aden and the Danakil-Eritrean Rift, continuations of the Red Sea and the Jordan Valley. The general basement of Ethiopia is made up of very old rocks, usually considered as Archaen.2 These rocks are represented by the metamorphic crystallines, such as gneisses, different kinds of schists, included lenses of crystalline limestone, and massive intrusives such as granites, diorites, and syenites, all cut by

Jan 1, 1949