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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

THE John Fritz Medal Board of Award, at its regu¬lar annual meeting Oct. 19, awarded its gold medal to Herbert Clark Hoover. Thus ended a process of selection begun a few years ago. The award was tentatively made a year ago by the Board, which is composed of sixteen recent past-presidents of the four national societies of Civil, Mining and Metallurgical, Mechanical, and Electrical Engineers, having together a membership of nearly 60,000. The sixteen members of the Board are: American Society of Civil Engineers : C. E. Grunsky, Robert Ridgway, George S. Davison and John F. Stevens ; American Institute of Mining and Metallurgical Engineers: William Kelly, J. V. W. Reynders, Samuel A. Taylor and E. DeGolyer; American Society of Mechanical Engineers: Fred R. Low, D. S. Jacobus, Dexter S. Kimball and Charles M. Schwab; American Institute of Electrical Engineers: Farley Osgood, M. I. Pupin, C. C. Chesney and Bancroft Gherardi.

Jan 1, 1928

By Tran K. Van, Francois E. Heuzé, Richard E. Goodman

Sound design of structures founded in or upon rock requires that the deformability of each rock member involved be characterized. This can be done by means of loading tests (plate bearing, flat jacks, borehole jacks, pressure chambers, etc.) or through convergence measurements (tunnel convergence, roof sag, etc.) in exploratory works. Analysis of data will be qualitative (degree of nonlinearity, creep behavior, scattering of results over a number of sites, etc.) and quantitative (modulus of elasticity or deformation). Some of these tests involve a very bulky apparatus and are expensive to perform. On the other hand, for the purpose of mapping and describing the various rock members which occur within a given site, many feet of diamond drill holes are frequently completed. Even with the optimum equipment and expert drillers, however, quantitative characterization of the rock units on the basis of tests on returned samples is apt to be misleading; the softer and weaker components of the rock tend to be lost and the fabric of the rock block- fracture system in situ is not sampled. Laboratory moduli of elasticity have proved to be consistently higher than in-situ values selected for engineering purposes. This led to the design of instruments which would operate in boreholes, combining the advantages of a reduced size and a deeper investigation, from the surface to several tens of feet. BOREHOLE DEFORMABILITY MEASURING INSTRUMENTS In the last 10 to 15 years, a number of testing devices have been con- structed which can be inserted into a borehole to apply a load and mea-

Jan 1, 1972

By W. Rostoker, R. P. Elliott, B. W. Levincer

Phase equilibria in the Ti-Cr-Mo system have been investigated for alloys containing 100 to 40 pct Ti in the temperature range 550° to 1300°C. Five experimental isothermal sections and a surface of incipient melting are presented in addition to a summary projection of the space. Seven vertical sections have been constructed from the isothermal sections. A STUDY of the system Ti-Cr-Mo was undertaken as part of a program sponsored by Watertown Arsenal toward the development of titanium-base phase equilibrium diagrams of potential technical importance to alloy development. The scope of the investigation included the composition range contained by the titanium corner and the line of 64 pct Ti (all compositions are by weight) and the temperature range 550" to 1100°C. A surface of incipient melting was constructed from measurements on a large number of alloys. The system Ti-Cr has been established.&apos;-? The phase diagram is characterized by a wide miscibility field of the solid solution at elevated temperatures and a eutectoid reaction of the type: (15 pct Cr) + TiCr, (685C). The a solid solution has a very limited capacity for solution of chromium (< 0.5 pct Cr). The intermediate phase TiCr2 has at best a very narrow composition range. It has been shown that two allotropic modifications of this phase exist. However, this behavior does not appear to be perceptibly reflected in the form of phase boundaries of the type + TiCr,. In the system Ti-Mo,9-10 the phase is stabilized to successively lower temperatures with increasing molybdenum content. There are no known intermediate phases. The a solid solution is limited to less than 0.5 pct Mo. Because of the very extensive range of the phase, the ternary system was ideally suited to the determination of the phase boundaries by the parametric method of Andersen and Jette." A parametric surface was constructed to provide the necessary basis for the application of this method. Preparation and Treatment of Alloys More than 60 alloy compositions were prepared for the study of this system. Alloy buttons of 10 grams were arc-melted in a nonconsumable electrode furnace using inert atmosphere protection and a water-cooled copper crucible. The construction and operation of this type of melting unit have been adequately described elsewhere.&apos;&apos; To insure complete solution of alloy additions, the buttons were remelted alternately on top or bottom as many as five times. This was accomplished by a suitable mechanism for "flipping" over the ingots. Iodide titanium (99.97 pct Ti) was used as the alloy base. An especially high quality chromium (99.9 pct Cr) was obtained from the National Research Corp. Molybdenum sheet (0.005 in.) of 99.9 pct purity was used.

Jan 1, 1954

By John R. Low

A number of cases of low-temperature, intergranu2ar brittle fracture of metals containing small amounts of certain impurities, have now been identified. Some degree of understanding of this phenomenon exists for the simpler binary systems of a metal and a single impurity, but the profound effects of other impurities and alloying elements in modifying this type of behavior remain unexplained. Current research in this area is reviewed and some of the newer techniques of investigation which should make possible a more quantitative study of the structure and composition of grain boundaries in impure metals are described. To indicate the subject matter of this lecture, we may begin by reviewing the experimental observations concerning low-temperature intergranular brittleness in impure metals, particularly those examples in which the embrittlement appears to result from what has been called "equilibrium grain boundary segregation."&apos; These are the systems in which it has been impossible, at least up to now, to detect the presence of any second phase film at the brittle interfaces. When second phase films are present they are usually readily detectable by fractographic methods, often appearing as epitaxial films in geometric or dendritic patterns. An example is shown in Fig. 1 for the case grain boundary carbides in a sensitized stainless steel which failed by intergranular brittle fracture at 78?k2 In contrast to this type of embrittlement there are numerous examples of low-temperature intergranular embrittlement in which the fractographs are essentially featureless, for example, that of an oxygen-embrittled iron shown in Fig. 2. The only second phase particles visible are the small, widely separated, round oxide particles typical of the bulk material. The fracture surface is extremely smooth and the fracture path appears to follow the intergranular interface without deviation. This type of fractograph also implies that crack propagation has occurred without plastic deformation at the crack tip, since localized slip or twinning ahead of the crack would be expected to distort the interface and be readily visible in the fractograph. Such indications are occasionally seen in these fractographs, but are not characteristic. A second example of this type of fractograph is shown in Fig. 3, which is from a temper-embrittled, carbon-free, Fe-Cr-Ni alloy containing Sb, broken at 1OO?C.3 The similarity to the oxygen embrittled iron case will be apparent. In the case of the temper embrittled Cr-Ni ferrite containing antimony, it is possible to remove the embrittlement by suitable thermal treatment. The grain boundaries may then be examined by thin film transmission in the electron microscope for the material in both the nonembrittled condition and in the embrittled condition. Two boundaries are shown in dark-field transmission in Fig. 4, one in the nonembrittled

Jan 1, 1970

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult&apos;s law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.&apos; This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3&apos;4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner&apos;&apos; and has been used to determine the thermodynamic data for Cu-Ni alloys.&apos; THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday&apos;s constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.&apos; The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By A. A. Burr, D. G. Ebeling

The effects of casting texture, grain orientation and grain size upon the performance of Alnico permanent magnets is described. Single-crystal specimens were produced by special sintering and grain coarsening techniques to study the effect of crystal orientation. In addition to texture and orientation effects, an analysis of the results indicates that the permanent magnet performance is impaired by a refinement of the grain size. AN excellent historical review of the development of Alnico permanent magnets has been prepared by Bozorth.1 The desirable permanent magnet characteristics of Fe-Ni-A1 alloys were discovered in 1932 by Mishima.2,3 The work of Ruder&apos; showed that the alloys were age-hardenable, and Betteridge5 defined the best composition and heat treatment for the magnetically isotropic alloy known as "Alnico 3." Horsburgh and Tetley0 increased the energy product by the addition of cobalt and copper, "Alnico 2," and Oliver and Sheddon7 demonstrated that cooling in a magnetic field improved the residual induction of this alloy. Jonas8,9 then disclosed the great practical benefits of heat treating an alloy of higher cobalt content in a magnetic field and the resulting alloy, "Alnico 5," has become the standard of the industry. This paper describes the fundamental aspects of a procedure which can be used to further improve the properties of these anisotropic permanent magnet alloys. A study of the casting techniques used in the production of anisotropic Alnico permanent magnets indicated that the magnetic quality was affected by the as-cast macrostructure. Improved performance was observed in magnets containing a high percentage of columnar grains whose long axes were parallel to the magnetic axis of the casting. McCaig10 studied the effect of such columnar grain structures upon the magnetostriction characteristics of similar alloys, however no data was presented showing the effects on other magnetic properties. The following paragraphs describe two experiments which were conducted to determine the effect of various grain orientations upon the energy product. Special composite molds were prepared of highly conductive and highly refractive components to remove the heat of solidification from the casting in a controlled manner. Representative macrostructures produced by these techniques are shown in Fig. 1, along with the relative volumes of favorably oriented columnar grains. The alloy, Alnico 5, has the highest permanent magnet performance of any commercial magnet material. It has the nominal weight composition of 8 pct Al, 14 pct Ni, 24 pct Co, 3 pct Cu, and 51 pct Fe. A heat of this material was cast into molds producing the type A and B grain structures shown in Fig. 1 and pairs of the resulting magnets were placed in heat-treating boats so as to eliminate any biasing effects of boat position. After a standard heat treatment the type A magnets, with 16 pct of the volume composed of favorably aligned grains, had a maximum energy value of 3,940,000 gauss-oersteds, while the type B magnets with 73 pct aligned grains averaged 5,090,000. This large im-

Jan 1, 1954

By HENRY M. PARKS

THE total production of all metals in Oregon to date is estimated at $160,000,000; ~115,000,000 from eastern Oregon and $45,000,000 from the western part of the state. In 1916 the metal production of the state was approximately $4,000,000, while the present annual production has dwindled to a little less than $1,000,000. Western Oregon The state of Oregon contains several metal-bearing areas, widely scattered in different regions. More than half of its coast is fringed with a belt of auriferous sands which sometimes are rich in fine gold. A second mining field, the chief producing one of western Oregon, is situated in the southwestern part of the, state and includes Jackson, Josephine, Douglas, Coos and Curry counties. It may be considered as the northern extension of the gold and copper belt of California. A third region in western Oregon is that on the western slope of the great Cascade range in the Bohemia, Blue River, Quartzville, North Santiam and Ogle Creek districts-from the Siskiyous on the south almost to the base of Mt. Hood near the Columbia River on the north.

Jan 1, 1925

The Pueblo Viejo Mine, a 7, 250 mtpd (8,000 stpd) gold-silver cyanidation plant built by Rosario Dominicana S. A., was described in Volume I of this monograph. At the time of writing that volume, Pueblo Viejo had not yet gone on-stream and operating data or costs could not be presented. Since that time this information has been obtained and several interesting modifications and an expansion have been made to the plant. Because Pueblo Viejo is the largest open-pit gold mine in the world and one of the world&apos;s leading gold-silver operations with production of approximately 31 kg (1,000 oz) gold and 125 to 155 kg (4,000 to 5, 000 oz) silver per day, the authors have updated the previous data and flow sheet. The Dominican Government, which held a 4670 interest in Rosario Dominicana S. A., completed purchase of the mine to gain full control in 1979. Rosario Resources will continue to manage the mine, at least until the end of 1980. Gold was produced at Pueblo Viejo almost 500 years ago with initial production in the year 1505. Rosario Resources became interested in the property in 1969 and found surface oxidation had rendered the upper portion of the ore body amenable to direct cyanide treatment. The treatment of the underlying gold-bearing sulfide zone is still undergoing metallurgical studies. The ore is considered to be a laterite; and because there appeared to be few boulders in the ore zone, only a 400 m (16 in. ) square grizzly was initially installed ahead of the mills when the plant went on-stream in late 1974 at a design capacity of 7,250 mtpd (8,000 stpd). Operation also proved the ore to be harder than was originally anticipated. During 1967 a 1. 25 m by 1. 5 m (48 in. by 60 in. ) jaw crusher was installed to -feed the 1, 000 mt (1, 100 st) mill bin. Minus 200 mm (8 in.) crushed ore is fed directly to two 5.5 m by 1. 8 m (18 ft by 6 ft) semi-autogenous mills re-powered with 750 km (1,000 hp) motors and 50 mm (2 in.) grates. Each mill product is screened at 13 mm (1 /2 in.) by a vibrating screen. Screen oversize from each mill is combined on a single return belt equipped with a magnetic head pulley for grinding ball removal. The non-magnetic oversize is then split into two fractions for return to the primary mills. Originally, a minus 6 mm (1/4 in ) product was made on each screen and fed to a 300 kw (400 hp) 2.6 m by 3. 7 m (8-1/2 ft by 12 ft) regrind mill. During a plant expansion in 1978, an intermediate mill of 746 kw (1,000 hp) was installed to operate in open circuit on the combined primary mill

Jan 1, 1981

By M. TAYLOR

AT Grand Saline, some 65 miles east of Dallas, the Morton Salt Co. of Chicago has for some years operated a brine pumping and evaporation plant on a salt dome. They recently drilled trial holes to obtain data on the dome, preparatory to opening, a new mine, with the following results: The dome is in the form of a truncated cone, with an average of 210 ft. of cover. The top of the dome is approximately one mile in diameter, with the town of Grand Saline lying over the northern rim, and the sides slope off at an angle of 50" to 80" from the horizontal. The deepest holes were drilled to 900 ft. without penetrating beyond the salt, and indications are that the salt deposit is several thousand feet thick. As the deposit increases in area with the depth, there is undoubtedly enough salt to supply a mining operation for an almost unlimited period of years.

Jan 1, 1930

By Louise Barton Freeman, Coleman D. Hunter

The total production of oil in Kentucky during the year 1943 reached 7,010,776 bbl., which is more than at any time since 1930. Of this total, 5,287,659 bbl. was produced from the counties west of the Cincinnati arch, 692,359 bbl. from the 18 new pools opened during the year, and 3,260,765 from the Smith Mills pool, which was discovered in August of 1942. This is an important increase in western Kentucky in spite of the low price of crude, and demonstrates effectively the desire of the industry to cooperate in meeting the increased demands made by the war. Western Kentucky Two deep tests were drilled in the Kentucky portion of the Mississippi Embayment this year. Both were drilled to test the St. Peter. One well, drilled in Marshall County by the Adams Oil and Gas Co., did not encounter any St. Peter sandstone but drilled 650 ft. of formation below the position of the St. Peter and above the true Knox dolomite. The other well, in Ballard County, was reported to have tested the St. Peter and to have been temporarily abandoned at 3069 ft. At this depth the well probably was stopped in about the same formation as the Marshall County well. No accurate information is available on the Ballard County well. Several new producing areas were added to the list of fields in the western Kentucky coal basin, in Daviess, Henderson, McLean, Ohio, Union and Webster Counties. The Smith Mills pool was enlarged and production was found in the McClosky (Ste. Genevieve) in addition to the Cypress sandstone from which much of the earlier production had been obtained. There was some interest during the year in testing the Devonian and Silurian formations in the area south and east of the western Kentucky coal basin. In the fall of 1943, a 15 to 20-bbl. well was drilled in Allen County and two more wells are now being drilled. The production was obtained from within a few feet of the base of the Chattanooga black shale, probably in the upper Silurian. One well in Simpson County was drilled completely through the Silurian section before it was abandoned. Several wells were drilled in Logan, Todd and Christian Counties to test the Devonian where it is thinned by removal of the upper formations before deposition of the Chattanooga shale. None of these wells was successful but several other locations are now being tested. The Silurian thins in like manner on the eastern flank of the coal basin as the crest of the Cincinnati arch is approached, and it is along this thinning edge that such fields as the LeGrande, Logsdon Valley, Magnolia, Bowling Green and the Barren County pools were developed. A number of wells were drilled around these old pools in an effort to extend them, some of which were successful. The wells listed this year in Larue, Hardin, Barren, Hart and Warren Counties were drilled in the search for other such fields.

Jan 1, 1944

By Louise Barton Freeman, Coleman D. Hunter

The total production of oil in Kentucky during the year 1943 reached 7,010,776 bbl., which is more than at any time since 1930. Of this total, 5,287,659 bbl. was produced from the counties west of the Cincinnati arch, 692,359 bbl. from the 18 new pools opened during the year, and 3,260,765 from the Smith Mills pool, which was discovered in August of 1942. This is an important increase in western Kentucky in spite of the low price of crude, and demonstrates effectively the desire of the industry to cooperate in meeting the increased demands made by the war. Western Kentucky Two deep tests were drilled in the Kentucky portion of the Mississippi Embayment this year. Both were drilled to test the St. Peter. One well, drilled in Marshall County by the Adams Oil and Gas Co., did not encounter any St. Peter sandstone but drilled 650 ft. of formation below the position of the St. Peter and above the true Knox dolomite. The other well, in Ballard County, was reported to have tested the St. Peter and to have been temporarily abandoned at 3069 ft. At this depth the well probably was stopped in about the same formation as the Marshall County well. No accurate information is available on the Ballard County well. Several new producing areas were added to the list of fields in the western Kentucky coal basin, in Daviess, Henderson, McLean, Ohio, Union and Webster Counties. The Smith Mills pool was enlarged and production was found in the McClosky (Ste. Genevieve) in addition to the Cypress sandstone from which much of the earlier production had been obtained. There was some interest during the year in testing the Devonian and Silurian formations in the area south and east of the western Kentucky coal basin. In the fall of 1943, a 15 to 20-bbl. well was drilled in Allen County and two more wells are now being drilled. The production was obtained from within a few feet of the base of the Chattanooga black shale, probably in the upper Silurian. One well in Simpson County was drilled completely through the Silurian section before it was abandoned. Several wells were drilled in Logan, Todd and Christian Counties to test the Devonian where it is thinned by removal of the upper formations before deposition of the Chattanooga shale. None of these wells was successful but several other locations are now being tested. The Silurian thins in like manner on the eastern flank of the coal basin as the crest of the Cincinnati arch is approached, and it is along this thinning edge that such fields as the LeGrande, Logsdon Valley, Magnolia, Bowling Green and the Barren County pools were developed. A number of wells were drilled around these old pools in an effort to extend them, some of which were successful. The wells listed this year in Larue, Hardin, Barren, Hart and Warren Counties were drilled in the search for other such fields.

Jan 1, 1944

By William G. Kegel

Apart from a usable product and good mining conditions, the greatest asset for a profitable coal mining organization is an effective mine maintenance program. The first step in achieving this is to have good mechanics-or men who want to be mechanics and are interested in knowing, more about the design and control of the machines in their charge. A good mechanic&apos;s knowledge and ability result from ambition, curiosity, and determination. Starting with these qualities, the aspiring mechanic can launch his career by learning all he can about mechanics, electricity, and hydraulics. Though the path is rough, the end result is rewarding. Mining machinery probably receives as much, if not more, abuse as any other heavy equipment in use today. Considering the conditions under which much of the repair work must be done, it is essential that the mine operator has the best men and tools to perform the work. Mining machines, from their inception, have utilized the electric motor; and down through the years of mechanization, this power source has undergone many changes to better adapt it to the job. The first motors used were direct-current (d-c) motors since d-c power was the most economical power source for mining at the time of early mechanization. These motors were large open-type machines which are seldom used in modern mining. Because of the mine environment, the d-c motor has been reduced in size to better suit the application in mining machines and is now manufactured with dust-tight or explosion-proof enclosures. The d-c motor is constructed with either (or both) series and shunt fields located on the stationary part of the motor (stator) and an armature coil wound on the rotating part of the motor (rotor). Power is supplied to the armature by brushes which are held stationary and make sliding contact with the armature. The brushes requires regular and careful maintenance because worn or defective brushes will cause heat or arcing which can destroy the motor. D-c motors can be used as d-c generators when mechanical power is supplied to them by the rotating

Jan 1, 1981

IN international affairs, the great event of June was the meeting of representative bankers at Paris -for consideration of the arrangement of a large loan to Germany. The conference dissolved in futility. Following this abortive conference, the delegates to the parley at the Hague assembled there on June 15. America is not represented at the Hague, any more than at Genoa. The British view the conference seriously and have Leslie Urquhart, the highest authority on Russia, attending in an official capacity. The Irish had their election and voted by strong majority in favor of the treaty with Great Britain, which was happy, but the general situation in Ireland is miserable. In China there were spectacular military and political events. Economically, Japan was in trouble. Conditions are becoming better in India, although no yet settled. Egypt has troubles still. Australia has a better chance for welfare, following the overthrow of its labor govern-ment early in April last. In Europe it is hard to discern any improvement except in Great Britain. Business in Great Britain has been slowly widening. The future of Great Britain, which is chiefly an in-dustrial country, depends on finding employment for its, 1,750,000 idle men. Personalities figured largely in June. Lenin&apos;s health was represented as having failed so that the govern-ment of Russia has had to be-turned over to a trium-virate. All of this has been denied. It is clear that some. mighty events are transpiring there. The assassination of Doctor Rathenau in Germany is probably also an occurrence of portent. The murder of Field Marshal Wilson, in London, tended to in-crease anger in England against the Irish. In the United. States the attention of Congress was concentrated on the soldier bonus, the tariff bill and the subsidy for shipping. All of these projects are economically bad and are of the same nature, viz., the allotment of a bounty to some classes of people, without consideration to the general national interest and welfare.

Jan 7, 1922

By J. J. Becker

Changes in magnetic properties with particle size are used to study the precipitation process in a Cu-Co alloy. In particular, the effect of a field during aging in producing anisotropy is shown to occur entirely during the growth of the particles, after precipitation is complete. HEAT-treatment in a magnetic field is done commercially to improve the magnetic properties of a number of materials. These can be divided into solid-solution alloys and precipitation alloys. The Permalloys are representative of the first type, and magnetic annealing greatly increases their maximum permeability. On the other hand, in precipitation alloys such Alnico 5 the important result is an increase in maximum energy product. The effect of the field in all cases is to bring about an additional magnetic anisotropy, uniaxial in nature, which makes the hysteresis loop more upright when measured in the direction in which the field was applied. The structural origin of the anisotropy brought about by magnetic annealing is not well understood. In the solid solution alloys, one possible explanation is based on ordering.&apos; Another possibility is the orientation of like-atom pairs.&apos; The precipitation systems known to respond to magnetic heat treatment are Alnico 2, in which the effect was first discovered," Alnico 5, cobalt ferrite (oxide),&apos; and Cu-Co alloys.3 n these materials, the field affects the precipitation process itself in some way. Although there has been much work on Alnico 5. its nature is still incompletely understood. According to Geisler,&apos; the precipitation reaction is of the

Jan 1, 1959

By K. Mukai, M. Ishihara

This report is a brief discussion of the impurity levels both in primary aluminum and super-purily alnminim in connection with raw materials and proc-essing methods. Particularly, truce amounls of im-purities were analyzed by introducing nittss-speclro-gruphy and nenlron-aclivalian analysis techniques. Vanadium and gallium content in primary aluminum metal corresponded to theor amounls in anode coke. but the nickel content in primary aluminum was hide-pendent oj its amount in the anode cake. Sulfur in the anode colic might result in an increase of the iron content in the molten metal in the reduction cell. The content of sodium and calcium increased with increasing bath ratio. In the holding furnacc sodium content decreased rapidly, and nonmetallic inclusions merit separated front the mollen metal. Three-layer elctrolysis was effectire in eliminating many impuri-ties with the exception of copper, aluminum oxide. aluminum nitride, and some rare-earth elements. THE amount of impurities and nonmetallic inclusions in aluminum metal depends on impurities in the raw materials and various production processes. This paper presents an investigation of the behavior of impurities and nonmetallic inclusions in aluminum during the electrolysis process, the period in the holding furnace, and the process of three-layer electrolysis. Chemical analysis and emission spectrometric analysis have generally been used as methods to determine small amounts of impurities in both primary aluminum and super-purity aluminum; however. mass spectrography and neutron-activation analysis have been recently introduced into this field, and trace amounts of impurities can accurately be determined by these latter methods. EXPERIMENTAL WORK Common impurities were determined by means of absorptiometric. polarographic, flame-photometric. and emission-spectrometric methods. However, in the determination of trace amounts of impurities and non-metallic inclusions, the following methods were applied. In the analyses of trace impurities by mass-spec- trographic analysis, samples were exposed in the vacuum spark of double-focus ing Mattauch-Herzog type mass spectrograph (Japan Electron Optics Laboratory, Ltd.). Ilford Q2 photographic plates were used as ion detectors. Fe was used as the internal standard, and the atomic concentration of each element was calculated by the following expression and converted into the weight concentration: where E, and Ei are the exposures (coulomb) when isotopes of the internal standard and impurity elements (on which the estimate is based) show the same density, X is the percent (atomic) concentration of the standard, IF and Ii are the percent abundances of the isotopes of the standard the impurity elements (on which the estimate is based), and Ms and hfi are the mass of the isotopes of the standard and impurity elements (on which the estimate is based). The coefficient of variation in this method is about 40 pct in the range of 0.1 to 1 ppm. In neutron-activation analysis, irradiations were done in the nuclear reactors TRIGA-I1 (neutron flux: 4.7 x 10 11 n per sq cm per sec; Rikkyo University) or JRR-2 (neutron flux: 2 x 1013 n per sq cm per sec: Japan Atomic Energy Research Institute). After the chemical separation, a NaI (3 by 3 in.) scintillator connected to a 256-channel y-ray spectrometer (R.C.L.) was used for counting and recording various activated impurities. The coefficient of variation in this method is about 20 pct. In the analyses of nonmetallic inclusions, aluminum-oxide determination was carried out according to Fischer&apos;s method, 3 as follows. A slice of sample was cut off and the surface was cleaned. It was dissolved in bromine-methanol. The solution was filtered and the residue was washed. The residue was fused with potassium bisulfate flux. Then it was dissolved in weak acid, and oxine solution was added. The aluminum oxinate was extracted with benzene. Finally, aluminum was determined absorptio-metrically. Aluminum nitride determination was carried out as follows. A slice of sample was cut off and the surface was cleaned. It was put in the distillation apparatus and decomposed with sodium hydroxide solution. The solution was distilled. Then ammonia was absorbed and

Jan 1, 1967

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF&apos;-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By D. G. Russell

Two techniques have been developed with which the applicability of pressure build-up analyses can be extended to include pressure data which previously have been considered virtually unusable. One of the interpretation methods makes possible the analysis of pressure build-up performance during the wellbore fill-up or after production period which occurs soon after a well is closed in. The other technique is an extension of a method for analyzing pressure build-up performance during the late-time portion of the pressure build-up which occurs after boundary eflects first begin to alter the shape of a conventional pressure build-up curve. With both of these methods it is possible to obtain estitnates of the kh product, the skin factor and the reservoir pressure. In addition, with the late-time analysis technique it is possible to obtain an estimate of the contributory drainage volume of the well being tested. This means that in some cases a check on reservoir limit test and (or) material-balance calculations can now be obtained from pressure build-ups. Both methods are slightly more time-consuming than conventional pressure build-up analysis methods because trial-and-error plots of pressure data must be made. The late-time method for analysis of pressure build-ups is in principle applicable to the late-time portion of a two-rate flow test or a pressure drawdown test. The interpretation formulas and procedures for these types of tests are also outlined. In these cases, as with pressure build-ups, it is significant that an estimate of the contributory pore volume is also obtained. On the basis of limited experience with the new techniques, it appears that satisfactory estimates of the kh product, skin factor, reservoir pressure and, for late-time analysis, contributory drainage volume can be obtained. INTRODUCTION The analysis of bottom-hole pressure build-up behavior in closed-in wells has been a a subject of interest in petroleum engineering circles for many years. In fact, few other subjects have received as much attention as pressure buildup analysis methods have. The cause for this interest is essentially twofold in nature. First, the pressure behavior of a well can normally be measured with a reasonably high degree of accuracy so that good data for analysis can be obtained. Secondly, over a fairly wide range of operating conditions, valuable information as to the quality of the reservoir rock and completion efficiency of the well can be obtained at a nominal cost. In recent years, numerous papers have been prepared on the effects of various operating conditions and reservoir heterogeneities on pressure buildup behavior. Very little work has been done, however, on extension of pressure build-up analysis methods to those pressure data which are not amenable to analysis by the present methods. The theory upon which the analysis of shut-in bottom-hole pressure build-up data is based is derived from the solution of the radial flow equation for a slightly compressible fluid for constant-rate conditions. It requires that the well be closed in for a sufficient period of time to obtain a clearly defined linear portion on the plot of observed bottom-hole pressure vs log (t + ?t)/ ?t (where At is shut-in time, and t is producing time to the instant of shut-in). From the slope of the plot and other normally obtainable data, the formation permeability, the well damage or skin factor, and the reservoir pressure at infinite shut-in time (if the reservoir were infinite) can be estimated. The successful application of this procedure depends on being able to recognize the straight-line section on the basic pressure build-up plot. The presently used pressure build-up interpretation theory also assumes that a well is closed in at the sand face and that no production into the well occurs after shut-in. In practice, of course, the well is closed in at the surface, and inflow into the well continues until the well fills sufficiently to transmit the effect of closing-in to the formation. This adjustment period is commonly referred to as the "afterproduction" or "fill-up" portion of the pressure build-up. During the period that the well fill-up effect is most pronounced, the basic pressure build-up plot is nonlinear. At later shut-in times after the effects of a drainage boundary have been felt at the well, deviation from the straight-line behavior of the pressure build-up plot also results. In many cases either of these effects or a combination of both can make the straight-line portion on the pressure build-up plot difficult to recognize. Obviously, an extension of pressure build-up analysis methods to include the afterproduction period and the period in which boundary effects are being felt would be desirable and might render valuable pressure data which for years have been considered virtually unusable. The principal reference of note concerning pressure buildup analysis during the afterproduction period is a paper by Gladfelter, Tracy and Wilsey.1 In the approach of these authors it is necessary to measure the rate of influx into the well during the afterproduction period. This is done through sonic measurements or through measurement of tubing-head and casing-head pressures simultaneously with

Jan 1, 1967

By M. B. Bever, A. K. Jena

THE heats of formation ?H at 273°K of the compound AgMg as a function of composition have been measured by solution calorimetry.1 The value at the stoichiometric composition is -4.41 kcal per g-atom. From electromotive force measurements2&apos;3 the heat of formation at 773°K of stoichiometric AgMg has been determined as -5.19 kcal per g-atom.4 The combination of these two values results in an unusually high negative temperature coefficient of the heat of formation d?H/dT = ?Cp = -1.6 cal per g-atom-OK. By contrast, published heat contents of the compound AgMg and the component elements above room temperature5 indicate that the temperature coefficient of the heat of formation of AgMg is nearly zero. In this communication calorimetrically measured heats of formation of A.K.JENA,Junior- MemberAIME,andM.B. BEVER,Member AIME, are Staff Member, Division of Sponsored Research, and Professor of Metallurgy, respectively, Massachusetts Institute of Technology, Cambridge, Mass. Manuscript submitted July 1, 1968. IMD AgMg below room temperature are reported and the temperature dependence of the heat of formation is discussed. The heat effects of additions of samples of the compound AgMg containing 50.1 at. pct Mg to liquid tin-rich solutions at 623°K were measured in a solution Calorimeter.6 The heat effects of additions plotted against the average of the atom fractions of solutes in the solution before and after each addition were a linear function of composition from which the heat effect at infinite dilution was obtained, Table I. The calorimeter was calibrated by additions of tin; the heat content (H623°K - H273°K) of tin was taken as 4.08 kcal per g-atom.4 The heat effect at infinite dilution of an addition of where heat of formation of AgMg at T°K, T = temperature from which samples are added (78°, 195°. and 273°K), Xi = atom fraction of i in AgMg, ?Hi = relative partial gram-atomic enthalpy of i in tin-rich solution.

Jan 1, 1969

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu&apos; of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith&apos; deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-&apos; make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.&apos; It has received confirmation in the recent work of Dench and Kubaschewski,&apos; and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968