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By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of liquid Mg-Ge alloys have been determined between 1000°and 1500°K by an isopiestic method. Germanium specimens, heated in a temperature gradient and contained in covered graphite crucibles of special geometry, were equilibrated with magrtesium vapor in closed titanium tubes. The crucible design allowed free access of magnesium vapor to the samples during the equilibration to form alloys of magnesium and germanium, but prevented magnesium losses from the crucibles on quenching the titaniuin tubes to terminate the experimental runs, thus preserving the equilibrium alloy compositions. The activities and partial molar enthalpies of magnesium and the integral thermodynamic properties of the system were calculated from the experimental data. THE Mg-Ge phase diagram' shows one congruent melting compound, Mg2Ge, of essentially stoichio-metric composition, two eutectics, and very limited terminal solid solubilities. Very little information is available on the thermodynamic properties of the Mg-Ge system. The free energy of formation of Mg,Ge was recently deter-mined2 by a Knudsen cell technique in the temperature range 610° to 760°C. The standard enthalpy of formation of Mg,Ge was measured calorimetrically by Bever and coworkers.3 The present study was undertaken as part of a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,4 Mg-Sn,5 Mg-Ge, and Mg-Si. An isopiestic technique was used which was developed by the authors5 for investigating the thermodynamic properties of liquid Mg-Sn alloys. Specimens of the nonvolatile component, contained in covered graphite crucibles, are heated in a temperature gradient in an evacuated and sealed titanium reaction tube, and equilibrated with magnesium vapor of known pressure. The method employs crucibles of special geometry which preserve the high-temperature equilibrium composition of liquid alloys having a highly volatile component such as magnesium on termination of the experimental runs by quenching the crucibles to room temperature. EXPERIMENTAL PROCEDURE First reduction germanium of 99.999+ pct purity (Eagle-Pitcher Co., Cincinnati, Ohio) and 99.99+ pct magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) were used. The graphite crucibles were machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non-reactivity of graphite with germanium at the temperatures used in this study had been previously established by Scace and Sleck.6 The experimental procedure has been previously described in detail.5 The selection of a particular crucible geometry for a run was determined by a combination of imposed experimental conditions, the principle being that more tightly covered crucibles were required to preserve alloy compositions during quenching when higher magnesium pressures and higher specimen temperatures were used. Depending upon the composition range of the equilibrated alloys the source of the magnesium vapor was either pure magnesium or a two-phase mixture of Mg2Ge + Ge-rich liquid of known magnesium pressure. The experimental runs can be divided into the following three groups on the basis of crucible geometry and magnesium source material. Crucibles with Small Holes and Pure Magnesium Reservoirs. The crucible dimensions were identical to those of the Mg-Sn investigation5 except that the hole diameters were reduced to 0.010 in. because of the higher temperatures and higher magnesium pressures involved in the Mg-Ge system. During an equilibration run, magnesium vapor diffused from the reservoir to each specimen through the small holes, one drilled through the crucible lid and two others drilled through graphite baffles positioned vertically inside the crucible between the lid hole and the specimen. Since the magnesium pressure was high, i.e., in the range 117 to 277 Torr, during the equilibration time of approximately 24 hr, equilibration was not impeded by these holes. A specimen composition at equilibrium was fixed by the relative temperatures of the specimen and the reservoir, and by the thermodynamic properties of the system. Upon brine quenching the titanium reaction tube to end a run the vapor pressure of magnesium above the liquid alloys decreased exponentially with decreasing temperature, and the small cross-sectional areas of the holes (4.9 x 10"* sq cm) drastically reduced magnesium losses from the crucibles. Because of its low vapor pressure, germanium losses from crucibles during a run were at most 0.2 mg for pure germanium and correspondingly less for the alloys. This crucible geometry satisfactorily retained the equilibrium alloy compositions on quenching for magnesium-rich (from 3 to 33 at. pct Ge) alloys provided their temperatures were below the melting

Jan 1, 1967

By Subhas G. Malghan

Feldspathic deposits occur widely throughout the United States, but North Carolina, California, Connecticut, and South Carolina accounted for over 80% of the total domestic feldspar output for the year 1973.1 Pegmatites and granites constitute the major feldspar reserves of the United States, 2 and in addition, feldspar is produced as a byproduct by firms whose major products are spodumene and mica. 3 Feldspar flotation is practiced in the United States, Mexico, Finland, Norway, West Germany, Japan, and the USSR. According to the US Bureau of Mines estimates, the production of feldspar in the United States and rest of the world were 704,000 and 2,514,000 t, respectively. Feldspar is principally used as a flux in making glass, pottery, porcelain, enamel, tile, and other ceramic products. In recent years, the domestic feldspar industry is faced with a number of problems. As a result of increased cost of energy and the introduction in 1972 of new legislative programs relating to air, water, and noise pollution, land-use restrictions, and mined-land rehabilitation, the production costs have increased. Apart from the increased cost of operation, an operational problem exists with the feldspar producers in North Carolina, especially those in the Spruce Pine area. This problem is concerned with the use of hydrofluoric acid in the feldspar flotation. Feldspar producers in Spruce Pine, NC, have been discharging process waste water into the North Toe River. The mill waste water contains active fluoride ions. Fluoride in excessive concentrations is undesirable in waters used for drinking. It is stated that water containing 0.9-1.0 ppm fluoride will seldom cause mottled enamel on children's teeth; and for adults, concentrations less than 3-4 are not likely to cause endemic cumulative fluorosis and skeletal effect. Although the literature on this subject is rather confusing and inconclusive, the inference that concentrations over 4 ppm may affect bone structure is clear. According to the recent Federal Register,4 maximum fluoride level of 1.4 ppm at 79°-98°F is considered to be adequate and safe for the protection of health of the consumers. The EPA and state environmental agencies have accelerated their drive to reduce water pollution on a faster schedule. By 1977, the EPA specifications for maximum contaminant level of fluoride ions in the discharge waters of feldspar milling operatins is expected to be reduced to 2.0 ppm. The other problems of using hydrofluoric acid are the following: toxicity, hazards of handling and storage, and high cost as compared to other inorganic acids (almost 16 times the cost of sulfuric acid). In order to reduce fluoride levels in mill discharge waters, mining companies have taken the following steps: I) Recirculating a part of their mill water. Even though recirculation of mill water seems to be a novel method of reducing fluoride contamination of the discharge water, there are certain operational and handling problems. 2) Conducting research on the treatment of fluorides in mill waste water. The technology of treatment of fluoride ions has received considerable interest in the recent years. A recent research report5 estimates that the cost of fluoride ion removal to meet the present specifications in the feldspar industry is approximately $0.25/t of ore processed, and about $0.50/t of feldspar produced. At the request of the feldspar producing industries in North Carolina, the North Carolina State University (NCSU) Minerals Research Laboratory has taken up a research program directed towards overcoming the fluoride ion pollution problem. After a close study of the operational, technical, and economic aspects of feldspar flotation, it was decided to attempt to replace the conventional hydrofluoric acid process. Conventional Feldspar Flotatin Using Hydrofluoric Acid Since the inception of the feldspar flotation process using hydrofluoric acid by O'Meara2,6 the process has achieved a great commercial success. In the conventional flotation separation of feldspar-quartz, hydrofluoric acid is used to suppress quartz and activate feldspar, and a long chain amine salt (acetate or chloride) is used as a collector. The bulk of amine collectors used in current feldspar operations are applied as the water-soluble acetates of the free-base amines. These products are pastes or waxy solids which are available in a range of acetic acid neutralization levels generally 50 to 100% neutralized. In spite of the problems mentioned in connection with the use of hydrofluoric acid, this process is extremely stable with respect to changes in the process variables. With the exception of a few operations, alaskite and pegmatite are the major sources of feldspar.7 In the flotation treatment of a pegmatite that contains iron-bearing minerals (heavy minerals), mica, feldspar, and silica, a logical order of removal presents itself considering the following:8 1) Mica is readily floated by an amine collector in a pulp pH 3.5. Some iron-bearing minerals will usually respond to amine collector in acid circuit with the mica concentrate. 2) Since iron minerals tend to occur invariably in the feldspar concentrate, it is desirable to remove most of these prior to feldspar flotation. A fatty acid or a petroleum sulfonate collector used in this flotation step in acid circuit will float iron-bearing minerals. 3) Using hydrofluoric acid to maintain pH of 2.5, an amine collector employed in a final step will float feldspar away from silica, usually leaving the latter in the tailing as a high-grade silica concentrate. The problems connected with the flotation separation of feldspar-quartz arise due to the similarities in their chemical structure. Therefore, any reagent system that is likely to succeed in feldspar-quartz separation should have adsorption affinity towards one of the minerals and depression effect towards the other mineral.

Jan 1, 1979

By R. H. Swallow, George Hess

Aerial photography was once a crude, uncertain tool. Today it is a precision mapping instrument which saves important time and money for strip mining and other industry. Aerial photography began in the boxkite days of aviation. The Army first used it for rough reconnaissance photographs. Then, in the early Twenties, industry began to use aerial photographs of their plants and facilities for advertising or annual reports. The quality of these pictures was not very good by today's standards, but this work began the development of better cameras, better lenses, better photographic techniques.

Jan 1, 1949

PUBLIC hearings began before the Committee for Reciprocity Information on May 24, 1950, for the purpose of unearthing data and opinion that will be helpful in the forthcoming reciprocal tariff and other trade-barrier negotiations at Torquay, England, on September 28th of this year. The conference this fall will constitute the "third round" of tariff negotiations under the General Agreement on Tariffs and Trade concluded at Geneva in 1947. The United States plans to negotiate with 17 other countries on possible tariff modifications on various articles all the way from baby carriages and bottle caps to lead and zinc-bearing ores. On May 31, June 1 and June 2, spokesmen appeared before the Committee for Reciprocity Information on behalf of the domestic lead and zinc mining industries. Producers of these metals protested the inclusion of paragraphs 391 (lead-bearing ores, dust and mattes), 392 (lead bullion, lead in pigs and bars, and scrap lead), 393 (zinc-bearing ores of all kinds), and 394 (zinc in blocks, pigs or slabs, and zinc dust) of the Tariff Act of 1930, as amended in the list of articles to be considered for possible tariff concessions at Torquay. It was pointed out that although operating costs have more than doubled since 1939 tariffs on these metals were actually higher in that year than at present. This, coupled with the detrimental effects of the recent series of devaluations, has sounded the death knell for a substantial number of domestic lead and zinc mines-a most undesirable development in the face of the ominous international situation, according to these spokesmen. It was urged that higher rather than lower tariff rates are needed on these metals. The opinion was expressed that it was inconsistent to foster a high living standard in our western areas and then, once it is attained, to undermine that condition by minimizing the protection that was partly responsible for it. The main theme of some arguments implied that although every effort should be made to close the "dollar gap" abroad, serious consideration must be given the methods employed lest our national security position be jeopardized in the process. The House Committee on Foreign Affairs completed hearings on H. J. Res. 236, to provide for United States membership and participation in the International Trade Organization. Hearings began on April 19th and ran for over five weeks. Many witnesses from industry and government presented voluminous testimony, which will not be available for public distribution for several weeks. However, it is no secret that the most controversial provisions of the Draft Charter of the ITO are: (1) Article 17 (Chapter IV on Commercial Policy) which would obligate members to negotiate for the reduction of tariffs and the elimination of trade preferences; (2) Article 20 which would prohibit the use of quantitative restrictions for protective purposes; (3) Article 16 which promulgates rules to implement the principle of non-discrimination in international trade; and (4) provisions permitting the use of protective measures for promoting economic development, particularly in backward areas, even though such provisions are inconsistent with those of the three articles cited above. United States membership in the International Trade Organization is essential to the successful operation of that body in view of this country's position as the economic giant in the present international trade pattern. Many countries are reluctant to take any action toward the ratification of the charter until it is known what course America will pursue. However desirable or undesirable the ideal of free multilateral trade may be it is unlikely that this Government's participation in the ITO will materialize soon. Advices in Washington indicate that H. J. Res. 236 will not be enacted during the present session of Congress. The legislative pattern designed to secure Congressional approval of the ITO is similar to that of the St. Lawrence Seaway project. The Seaway project was pending in treaty form for several years before the Foreign Relations Committee of the Senate and when the Administration decided to incorporate this project into bill form it was found that, while it passed the House promptly, the Senate decided to pigeonhole it because of the obvious intent to circumvent the constitutional prerogative of the Senate to advise and consent to the ratification of treaties. The ITO bill may be slated for a similar fate. It is deemed essential by western Senators and Congressmen that the present session of Congress enact some form of mining legislation before its adjournment, now set for July 31st. These legislators from prominent ore-producing states do not desire to return to their home areas in the fall emptyhanded. Aside from that, it is entirely superfluous to reiterate the necessity for maintaining a healthy domestic mining industry as a bulwark against a sharp rise in the temperature of the "cold war". Now that S. 2105 has failed a new bill is taking shape in the Senate Interior and Insular Affairs Committee. It is similar in language to H. R. 8221 (to encourage the conservation and development of the mineral resources of the United States) reported by the House Public Lands Committee on May 3, 1950, but so far has failed to receive approval of the House Committee on Rules. There are some qualified observers in high circles in Washington as well as in the mining industry who favor a tax incentive program to stimulate investment in mining enterprises, as opposed to a conservation and exploration program. The Bureau of Mines and the Treasury Department have undertaken a joint study to determine the need for modification of the tax laws as they apply to mining. The study is scheduled for completion before the end of the year, and appears to be supplementary to the investigation initiated by the National Minerals Advisory Council which culminated in the submittal of recommendations to the Secretary of the Interior in December 1949. The "cold war" is largely responsible for the increased demand for metals. Stock-pile purchases and heavy industrial demand due to military needs distort markets and disrupt normal price trends. Such activity has an unhealthy influence on metal production, luring some producers into a state of dependency on the continuation of this condition. When stock-pile objectives are met sometime in the future purchases must then come to a halt unless international "fireworks" are touched off. It can only be hoped that technological improvements and further mechanization of mines coupled with the stimulus of a rising population will offset the anticipated drop in industrial demand and cessation of stockpile purchases when the international crisis abates.

Jan 7, 1950

APRIL 10-Officially, spring comes to the Great Lakes on March 21 as it does elsewhere in the country but in the Superior district continued snow and freezing until late in March have caused citizens in Duluth to place their bets on April 15 for the first ore vessels if the ice breakup is left to Mother Nature. North and west of Duluth and near the eastern end of the Mesabilies the little town of Aurora, population 1100. As the little v-nosed snowplow, pride of the community, shuttled back and forth clearing Aurora's few sidewalks, the crowd in Bradich's Cafe were more interested in the impending high school state championship basketball tournament in Minneapolis than in the outcome of Erie Mining Company's petition for water rights for their proposed 10 million ton taconite concentrating plant. Such a plant would employ 4500 workmen, and at the prevailing ratio of 10 people for every mine worker in Minnesota, this would mean a 45,000 increase in population for Aurora and the vicinity in the next few years. Downstate fishermen are alarmed at the flurry of activity by the mining companies in pushing plans for large scale recovery of iron from taconite. Inconvenience to these gentlemen will be inconsequential when compared with the vast increase in payrolls for range communities. Oliver is pushing the construction of a fine ore agglomeration plant at Virginia which will give them valuable experience for projected taconite processing. Oglebay, Norton & Co. is ready to go at Beaver Bay, north of Duluth, as the right of way for a railroad from Babitt to Beaver Bay is secured as well as permission to dispose of tailing into Lake Superior at the site of the proposed concentrating plant. This company is also doing research in agglomeration at Ashland, Ky., in cooperation with other interests. The financing is yet to be worked out. Of the four possibilities for agglomerating taconite concentrate-sintering, pellitizing, nodulizing and briquetting-the prospects for pelletizing appear the most favorable., It seems likely that 60 cents per ton can be saved by this process over sintering because only 1 to 2 pct of coal is required as compared with 7 pct for sintering. One reason for the lower coal consumption is that the chemical transition of magnetite to hematite which transpires in the pelletizing process is exothermic.

Jan 5, 1950

By R. J. Corfield

MODERNIZATION of the entire electrical system and improvement of Rotation process efficiency is the twofold goal of the improvement program underway at the Arthur and Magna concentrators of the Utah Copper Div., Kennecott Copper Corp. Copper ore from the Bingham pit goes to these two concentrators where an interlocking program calls for complete electrical modernization and increased flotation process efficiency through additional capacity and flow scheme revisions. Flotation plants at the two mills are essentially duplicates, and while this article deals with the changes at the Arthur mill similiar improvements are being made at the Magna mill.

Jan 3, 1953

By W. B. Heroy

ONLY through the mineral fuels can large amounts of energy be transported to great dlstances and stored for long periods for future use. Coal has the advantages over oil of greater safety of handling and smaller losses in storage. But oil is, in the present stage of technical advancement, the more economical source of liquid fuel for internal-combustion motors. No method for direct use of coal in such motors has been developed that can compete with petroleum products. The automoblle engine and the airplane motor are designed to make the most effective use of gasoline.

Jan 1, 1944

By A. L. Moore

KAISER Bauxite Co., a subsidiary of Kaiser Aluminum & Chemical Corp., has been mining and shipping Jamaican bauxite for over a year. On Feb. 10, 1953 the first boat load of bauxite left Port Kaiser, Jamaica, for the company's alumina plant at Baton Rouge, La. To provide its own source of the aluminum ore, a Kaiser Aluminum & Chemical Corp. exploration party started initial reconnaissance in 1947. This work, and subsequent exploration, led to the acquisition of reserves sufficient to warrant a full-scale mining operation for several decades.

Jan 3, 1954

By R. S. McClellan

Western Talc Company, Inc., with headquarters in Los Angeles, Calif., has just completed an extensive modernization and expansion program at its talc mine near Tecopa, Calif., and at its talc and clay mills at Dunn Siding, Calif., the nearest rail shipping point to the mine. The basic objective of the program was to provide facilities necessary to produce 300 tpd of a wide range of ground talc and clay grades for the ceramic, paint, paper, rubber and other industries. In the planning of the program every effort was made to provide a system which would permit a high degree of quality control and uniformity of the finished products, along with efficient operation. Several years ago, R. T. Vanderbilt Co., Inc. purchased Western Talc Co. after a comprehensive investigation of its properties, including an extensive diamond drilling campaign. Western Talc's properties embraced a number of claims in the Resting Springs mining district in the northern part of San Bernardino Co. and the southern part of Inyo Co., Calif., some seven miles southeast of the town of Tecopa. Operations by the original company were started on a small scale in 1913 and production from that date to the time of purchase of the company by Vanderbilt is estimated at 250,000 tons. The major part of this output was sold to the ceramic wall tile industry.

Jan 3, 1968

By Gerard C. Gambs

The electric utility industry is the largest customer of the U.S. coal industry, consuming nearly 50% of present coal production. By 1980, the electric utilities are expected to burn over 500 million tpy of coal or 75% of total coal production. When coal is burned in electric utility plants, ash is produced in one of several forms. These include fly ash, bottom ash and bottom slag. At the present time, approximately 20 million tons of these ashes are produced and must be disposed of by the utilities at a cost of 50[c] to $2 per ton. In 15 years, more than double this quantity will be produced. Only a small quantity of this ash is put to any practical use. Much remains to be done about expanding uses for fly ash and bottom slag.

Jan 1, 1967

By Philip D. Wilson

WHEN the United Nations win the war and the decision has been made to control future armament in the Axis countries, plans for the extent and operation of such control must have been prepared, to be ready to put into immediate execution. Such control to be effective must be premised upon complete military occupation of the two countries for a substantial period, with an arrangement at the end of such occupation for continued supervision of these industries into an indefinite future.

Jan 1, 1944

By Robert Laurich

Chuquicamata pit was opened in 1915 with steam shovels and steam locomotives brought down from the Panama Canal excavation project. With expansions in the early years, more steam locomo¬tives were brought into the mine. IMPROVED LOCOMOTIVES During the period 1927 to 1937, electric locomo¬tives were purchased and main line and bench tracks were electrified. Third rail was installed up to the working areas. At first, the locomotives were equipped with batteries for service at the shovels, but charge life was too short and they were con¬verted to use the third rail and a reel with 3000 ft of trailing cable for service in the loading area.

Jan 11, 1959

By Russell Webster

In having maintained production for more than 40 years Arizona's Magma mine is unique in a mineral district that includes several major copper mines. Other past and present producers in this area are Miami and Inspiration at Miami, the Old Dominion in Globe, the Ray mine in Ray, and to the south the new San Manuel mine near Tucson. Magma's production of copper, silver, gold, and some zinc has come from nearly parallel east-west striking mineralized faults, one called the Main or Magma vein and the other the Koerner vein, about 1100 ft to the south. This vein system has been prospected and partially mined for some 9000 ft horizontally and 4800 ft vertically. In ascending order from the deepest exploration level, the Main vein cuts Pre-Cambrian schist, Pre-Cambrian Apache Group, Post-Devonian diabase, and Devonian, Mississippian, and Pennsylvania limestones. Until 1950 very little ore was obtained from replacement mineralization.

Jan 10, 1958

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By P. J. Dean

This Paper contains a comprehensive survey of the known electron-hole radiative recombination mechanisms in the family of III-V compounds. Because of space limitations, the luminescence properties of each III- V compound are not reviewed separately and exhaustively. Instead, the different known types of recombination processes are discussed in turn and exemplified with reference to the III- V compound in which they were first recognized, or are best understood. Electron-hole recombinations usually occur predominantly at impurities or lattice defects either introduced de1iberately or inadvertently present, but radiative intrinsic interband electron-hole recombinations, which occur in perfect crystals, have been observed. Recombination processes which involve the participation of impurities or lattice defects ("extrinsic" recombinations) considered include transitions in which a) free carriers recombine with carriers trapped at impurities ("free to bound" transitions) , b) electrons bound at donor impurities recombine with holes trapped at acceptor impurities ("donor-acceptor pair" recombinations), C) excitons bound to charged or neutral donor or acceptor impurities recombine radiatively (both "resonance" and "two-electron" "bound exci-ton" transitions have been observed), d) excitons bound to neutral donor or acceptor impurities recombine non-radiatively (an example of an "Auger" recombination), and e) excitons bound to impurities with the same number of valence electrons as the host atom which they replace ("isoelectronic " traps) recombine radiatively. In addition, Auger recombination processes involving one or more free carriers have been observed. These extrinsic processes all involve impurities which are present as point defects. Some apparently well-authenticated examples of the recombination of excitons bound to complex impurity-lattice defect centers including nearest-neighbor donor-acceptor pairs are also discussed. Identificalions of the transitions involved in stimulated emission from the direct gap III-V compounds are briefly reviewed. Although the examples of these recombination mechanisms are selected from the III-IV compounds ia this review, these processes have quite general relevance in semiconducting crystalline solids; irrdeed most of them have also been identified in the 11- VI compounds and elernental semzconductors. THE development of crystal growth and purification techniques in recent years and concurrent advances in the understanding of physical processes in solids has accelerated the development of a wide variety of solid-state electronic devices of proven utility. These de- vices are generally used for switching or amplifying operations in electrical circuits. Most solid-state circuit elements are very photosensitive. This photo-sensitivity is generally undesirable and the single-crystal chip forming the active portion of the solid-state device is mounted in an opaque container. The photosensitivity is made use of in phototransis-tors and photodiodes, which are among the most sensitive detectors of electromagnetic radiation particularly in the near infrared.' In these devices, light is converted into electrical power. The solid-state lamp utilizes the inverse effect, namely the conversion of electrical power into light. There is an increasing tendency to use single-crystal diodes rather than the earlier electroluminescent cells in which the active material is present as a powder embedded in a suitable dielectric.' The radiation is emitted at a rate far in excess of the thermal equilibrium rate for the frequencies and temperatures involved; i.e., luminescence occurs. The development of practically efficient solid-state lamps is at an early stage compared with solid- state circuit elements or even photodetectors. Considerable progress has been made in recent years, however.3 The present review is devoted to a survey of the radiative recombination processes in the semiconducting compound crystalline solids formed from elements in groups I11 and V in the periodic table. These materials exhibit the full range of known recombination processes in solids. In fact many of these processes were discovered in 111-V semiconductors. Nonradiative recombination processes, which control the lutninescence efficiency, are also discussed. Luminescence is efficiently excited in semiconductors through processes which produce large excess concentrations of free electrons and holes in the energy bands of the crystal. Transitions induced by lattice defects or impurities usually predominate in the recombination process. By contrast, luminescence in the conventional fluorescent lamp is excited by optical absorption at the luminescent impurity center itself (the activator) and/or at a second type of impurity center (the sensitizer). This latter type of photoluminescence process, occurring in doped ionic crystals with wide band gaps, is outside the scope of this review.4 I) ENERGY BAND DESCRIPTION OF ELECTRON STATES IN CRYSTALS The energy band description of the energy states available to an electron in a crystal forms the basis of our understanding of the empirical division of crystalline solids into metals, semiconductors, and insulators in accordance with their electrical and optical properties.' Nonmetallic crystals have a finite energy gap between the highest energy band which is

Jan 1, 1969

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,' it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:' log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0' systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick's first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By AIME AIME

IT IS impossible in this short sketch to give a detailed description of each part of the plant at Bethlehem, therefore, only such facts will be touched on as are necessary to give a general idea of the works. The extent of the plant, and the fact that the units making up the various departments are located in different parts of the works, make it impracticable to mention the departments in any regular order with regard to their location. They are, therefore, mentioned approximately in the order of their relation to each other with reference to their functions in the making of the various products.

Jan 1, 1924

By C. H. Mathewson, P.W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)' by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By C. H. Mathewson, P. W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)' by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By P. W. Bakarian, C. H. Mathewson

THE greater part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation, in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)1 by geometrical analysis identified the {102} ? plane in magnesium as the twinning plane, Schiebold and Siebel (1931)2 confirmed this twinning plane, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also reported twin formation in a secondary role on the {101} plane. Schmid (1931)3 summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-i.e., the critical resolved shear stress-were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C., at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the original specimens of circular section had been

Jan 1, 1943