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By Arnulf Muan, Carlos Landolt

Equilibria involving Cu-Pt alloys, copper oxides, and atmospheres of known ox2gen pressures have been determined at 1000' and 1200 C. The data obtained have been used to calculate activity-composition relations in the alloys. A moderate negative deviation from ideality is found. At high copper concentrations, the results of the present study are in good agreement with those of previous investigators, whereas at low copper concentrations the activities obtained in this investigation are slightly higher than those reported previously. The present study is part of a research program dealing with the determination of phase relations and thermodynamic properties of copper-containing systems at high temperatures. The information available for such systems is very scanty, particularly for copper oxides and their combinations with other oxide components. Platinum is commonly used as a container in studies of oxide equilibria. To evaluate quantitatively the extent of reaction between the oxide and the container, a knowledge of activity-composition relations in Cu-Pt alloys is necessary. Such data are not available for Cu-Pt alloys in the temperature range of particular interest in the present research program, and particularly for alloys low in copper. Studies of various aspects of the systems Cu-Pt and Cu-0 have been reported in previous literature. The system Cu-Pt is known1 to form a continuous solid-solution series above 812.C, whereas ordered phases are present in certain composition ranges at lower temperatures. Thermodynamic data for the system have been reviewed by Hultgren et al.,' who presented free energies of mixing at 65Oo C, mainly derived from electromotive force cell measurements by Weibke and Matthes.3 Enthalpies of mixing at 640°C have been obtained by Oriani and Murphy4 with liquid tin calorime-try. Their results differ considerably from those derived from the temperature dependence of the data of Weibke and Matthes. Thermodynamic data for the disordered alloys have been obtained by Assayag,5 and more recently by Schmahl and Minzl,6 by Myles and Darby,7 and by McCormack, Myers, and Saxer.8 The two latter sets of data7'' became available after the present study was completed. In the system Cu-0+ two oxides are stable at high temperatures, CuO and CuzO+ each having only minor deviations from stoichiometry. Equilibria in the liquidus temperature region of the system Cu2O-CuO have been studied by Roberts and systemsmyth,9'10CuzO-CuO by Vogel and ocher,I1 by Osterwald,12 and recently the the present authors.13 The system is of the eutectic type with a eutectic temperature of 1083.C The composition of the eutectic liquid corresponds to Xcu0 = °.44, and the oxygen pressure of the coexisting gas phase is Po2 = 0.55 atm.13 Equilibrium oxygen pressures for coexistence of solid CuO and solid Cu2O have been determined by Schmahl and Muller,l4 by Gadalla, Ford, and white,l5 by Bidwell,16 and recently by the present authors.13 There is reasonably good agreement among the various sets of data. Free energies of formation of Cu2O(s) from the elements have been derived by Tretyakov,17 by Bidwell,16 by Kiukkola and wagner,18 by Pal'guev and Neuimin," and by Steele and Alcock,20 There is particularly good agreement among the latter three1'-20 sets of data. THEORETICAL BASIS Consider a subsolidus isothermal section of the system Cu-Pt-0, as shown in Fig. 1. Two phase as-

Jan 1, 1970

By G. V. Jere, V. Krishnan, C. C. Patel

Standard free energy and standard enthalpy changes as a function of temperature have been calculated for the chlorination reactions of different oxides constituting columbite and tantalite. The tallies of standard lee-energy change (F) indicate the possibility of pvefeential chlorination of different oxides but the ease 0.f chlorination of columbium pentoxide at about 250°C and the chlorinating tendency of columbium pentachloride in promoting the chlorination of tantalum and other metal oxides, p7-evetzt the separation of columbiu?n and tantalum from other oxides and pom each othel.. It is likely that low temperatuves of chlorination and continuous 1err2oval of columbium pentachloride from the ..eaction zone may help partial separation of columbium from tantalum as well as from titanium. The standavd enthaply change (AH?) values shotr that 1ou.-temperature chlorination around 300" to 500°C is likely to sustain the chlorination , without external heating. COLUMBIUM (niobium) and tantalum metals, their alloys and interstitial compounds are finding extensive uses in nuclear reactors and high-temperature equipment.la-3 These metals also find uses in chemical process plants, electrical rectifiers and capacitors and as "getters" in electronic tubes.la With the development of Kroll process of reduction of volatilized titanium tetrachloride by magnesium for the production of titanium metal, chlorine metallurgy is receiving greater attention. Chlorine metallurgy has several advantages, the foremost amongst them are: the ease of chloride formation, separation of the different constituents of minerals by selective chlorination, and the reduction of the chlorides in vapor phase to the respective metals. Recently, Si-bert, Kolk, and Steinberg4 have considered a number of methods for the preparation of columbium metal and the most promising is found to be the halide reduction. Since the minerals columbite and tantalite are comparatively abundant in nature, the future of the metallurgical processes depends on the utilization of these minerals for the production of columbium and tantalum chlorides by chlorination. In this paper, an attempt has been made to interpret thermodynamically the chlorination of individual oxides constituting columbite and tantalite, with the help of the recent thermodynamic data.5-8 For this purpose, standard free energy and standard enthalpy changes of the chlorination reactions of the oxides with chlorine, both in absence and presence of carbon as the reductant, have been calculated as a function of temperature and represented graphically. Similar calculations for the reactions employing carbon tetrachloride and carbonyl chloride as chlorinating agents have also been incorporated in this paper. REPORTED WORK ON CHLORINATION Cuvelliezg has patented a process for the separation of columbium and tantalum from their concentrate, wherein 75 pct Cb05 is claimed to be chlorinated at 1050°C in the course of 7 hr using chlorine or chlorine containing nonreducing gases, the products of reaction being CbC1, or CbOC1,. At this temperature, Ta,05 is claimed to remain unaffected. It is further claimed1° that at higher temperatures, the proportion of Ta205 chlorinated increases while that of Cb205 diminishes. During the studies on the action of chlorine on individual metal oxides, Kangro and Jahn" have observed that Ta,05 is not chlorinated even at 1200" in the stream of chlorine, while 75 pct of Cb,05 is converted into CbOC1, around 900 to 1100°C. The chlorination of Cb205 by chlorine in the presence of carbon, investigated by Lind and Ingle,' and

Jan 1, 1962

By A. C. Fieldner

COKE and by-products have prime importance in the war program. The past year was marked by the construction of new and the rehabilitation of old by-product and beehive ovens and by the increase of production from existing plants to practically 100 per cent capacity. W. T. Brown's paper, "Plan to Improve Blast-Furnace Coke," presented at the Fuels Conference in St. Louis, Sept. 30, showed how the blending of low- and high-volatile coal improved the physical properties of coke and that improvement of the quality and uniformity of coke favored an increase of blast-furnace capacity- a vital need in the war program. Others in the industry have likewise increased production of coke or recovery of by- products by various innovations or changes in operation. Recognition of the value of pooling these developments for the benefit of the entire industry led to organization of a survey of coke- oven plants and blast furnaces by the Bureau of Mines in co-operation with the Solid Fuels Co-ordinator with a view to improving metallurgical coke production and recovery of by-products. This survey is being conducted with the help of an advisory committee consisting of representatives of the Bureau of Mines, the Solid Fuels Co-ordinator, the War Production Board, and the blast-furnace, coke-oven, and coal-mining industries.

Jan 1, 1943

By AIME AIME

NEW YORKERS look forward to the third week of February as the time of the year when they can count on seeing their friends-from far and near gathered in the city for the four-day annual session of the Institute.., Indeed, the metropolitan district is so large that in engineer who lives in New, Jersey and has his office on the lower end of Manhattan island may easily pass a whole year without seeing an acquaintance who lives in Westchester and has an office near Forty-second Street. If the Institute served no other function than to provide a place where friendship may be renewed, ideas exchanged, and new acquaintances made it would still be worth while. But when about 30 technical sessions at which about 160 papers are read and discussed are compressed into four days the annual meeting is also entitled to high rank as an intensive course of post-graduate instruction in the newest development in mining and metallurgical technology. Last, but not least, it is the occasion of a good time for one and all, even if they do get more than a little behind on sleep before the end of the fourth day. Nine o'clock is the time set on Monday morning for the beginning of registration, but a half-hour before that a number have always 'put in an appearance, and this is fortunate, because by 10 o'clock four sessions had begun, those on mining methods, geophysics, a round table on the valuation of coal, and the session of the Local Section delegates. Three committees of the A. S. T. M. were also in simultaneous session, so the meeting may be fairly said to have started "in high."

Jan 1, 1931

By AIME AIME

STEADY advance has been made in the art of lead smelting and refining during the year. The bringing of natural gas to the Salt Lake valley has led to its adaptation to lead smelting operations. The Tooele plant of the Anaconda Copper Mining Co. has put into practice the high blast pressure and constant volume for lead blast furnaces, which we understand was first advanced by John F. Austin. It would appear that within limits, capacity is nearly proportional to the volume of air. If the charge is dense, a constant pressure, as in the old practice. did not get much air through the charge and the furnace slowed up. The constant volume idea makes the charge smelt at the same rate as if the charge were porous. The cost of a little additional power insures capacity operation at all times.

Jan 1, 1932

By W. E. D. Stokes

The faster that aircraft fly the sooner some new and stronger material must be found to take the place of the present aluminum alloy used in all-metal planes. Experts of the National Advisory Committee for Aeronautics. in studying hi-speed aircraft, are convinced that the present all-metal plane, of semi-monocoque, aluminum alloy construction, is not the ultimate in aircraft design. Magnesium alloys and steel are under consideration.

Jan 1, 1942

By Robert E. Tally

A recorded in the account of the Annual Meeting, on another page, the report of the tellers showed that all men nominated by the committee, which included Messrs. Wilber Judson, E. DeGolyer, W. A. Weldin, J. A. Norden, J. D. MacKenzie, Wilfred Sykes and S. Skowronski, were duly elected to the offices for which they were nominated. Robert Tally, who was elected to the presidency for 1931-2, is well known to all our members not only because he has served on the Board of Directors since 1928, but through a brief outline of his great achieve¬ments in his chosen profession pub¬lished in our issue of December last. The vice-presidents, Howard N. Eavenson and H. A. Guess, are also well known to our members. Mr. Eavenson has not only been chairman of the Coal Division since its organization, but was also a Director during 1917, 1918 and 1919., Mr. Guess was Director in 1926, was elected a vice-president by the Board last year to fill the vacancy created by the election of Mr. Bassett to the presidency, and is now elected to the usual three-year term.

Jan 1, 1931

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 A. T. Shurick

WHATEVER the outcome of the Industrial Recovery Act, it has currently injected the first hope and optimism into the coal industry for more than a decade. Compared with the recent drab years the results are impressive: Bituminous production for the first ten weeks, 78,000,000 tons, may be compared with 63,000,000 last year; anthracite, 14,600,000 tons and 9,600,000 tons for the same periods, respectively, bringing the heaviest payrolls in ten years with individual checks reminiscent of former boom times. Hurried calls for long deferred new equipment and replacements have stimulated foundry and machine works and the -invigorating effect on the railroads is indicated by the first actual car shortage in a decade. And even in the welter of confusion over code prices, this heavy tonnage has moved at the most profitable figure the coal man has realized for many years, though with the large volume on old contracts, profits were not as large as many think.\

Jan 1, 1934

By T. T. Read

FOR the second time the Mineral Industry Education Division opened the sessions at the Annual Meeting by gathering at the Engineering Woman's Club, Sunday at 3 p. in., and, in spite of the informality of the hour, with a good attendance of representative men in the educational field. The chairman of the Division, Thomas T. Read, after briefly reviewing some of the more significant events of the past year, introduced H. P. Hammond, professor of civil engineering, Brooklyn Polytechnic Institute, a leading figure in the project of the Engineers' Council for Professional Development for accrediting engineering schools. Prof. Hammond made it clear that the project is not to rate engineering schools but to accredit them; not to arrange them in order of excellence, but to segregate them into two groups, those that are entitled to recognition as genuine engineering schools, and those that are not. About thirty schools in the whole country will presumably fall into the latter class; they are typified by an unnamed institution where the teacher of mathematics bears the title of Professor of Civil Engineering and the man who teaches chemistry that of Professor of Chemical Engineering, and having no engineering instruction except some elementary surveying, but still claiming in its catalogue to be an engineering college. While everyone would like to avoid the necessity of accrediting engineering colleges, it cannot be avoided, since the University of the State of New York, and several other agencies, are already doing it. If it cannot be avoided it is best that it should be done by a qualified agency set up by the national engineering societies, so that the results may command respect and general acceptance. It is for this reason, and this alone, that the accrediting committee of the E. C. P. D. has been set up. It is now ready to begin its task, and during-the coming year it will accredit the schools in two of the seven geographical districts into which the country has been divided, beginning with New England and the Mid-Atlantic States.

Jan 1, 1935

By Philip D. Wilson

OF all the metals in the war program the demand for and the production of magnesium have increased percentagewise the most. In the prewar year 1939 the production was 3350 tons. The war program, twice expanded, now provides for nearly one hundred times that amount annually. The goal announced by the War Production Board in February 1942 was 362,500 tons per year. Be- cause of the development during the year of satisfactory types of incendiary bombs other than magnesium this objective has been somewhat reduced but the capacity of the plants already built or under construction will be huge. The Aluminum and Magnesium Division of the W.P.B. has had the responsibility of planning and implementing this expansion and of providing fabricating facilities as well for this greatly increased tonnage of magnesium ingot.

Jan 1, 1943

By R. M. Asimow

Both smith1 and wells2 have shown that the dif-fusivity of carbon in austenite increases rapidly with increasing carbon concentration. Smith has shown, in addition, that part but not all of this increase can be attributed to the concentration dependence of the activity coefficient of carbon in austenite. From the work of Eshelby', it is known that, because of the image displacements, there is a uniform dilatation of the material in a body containing random centers of dilatation. It is thus tempting to explain the enhanced diffusivity as resulting from this apparent negative pressure caused by the interstitial carbon atoms.* That is, the activation free energy for diffusion is not directly a function of concentration if we consider that the alloy is subjected to a concentration-dependent pressure. To proceed with a quantitative solution, it is necessary to determine the activation volume AV for the diffusion process. An exact calculation of AV is quite a difficult problem and does not appear to have been solved as yet. A simpler procedure is to use the semiempirical, macroscopic theory of seyes' which relates the activation free energy AG to AV. Keyes has shown that for many types of diffusion processes the following relationship is valid Where p is the Gruneisen constant and x the compressibility. This relationship is based on the assumption that AG can be identified with strain-energy terms. In general there will also be contributions to AG due to a change in the energy of the valence electrons of the metal; thus the relation must be considered largely empirical. Surprisingly, for self-diffusion where it is well-known that the electronic contribution is quite important,' the Keyes relation works quite well for many systems. For interstitial diffusion where it might be expected that the relationship is on a firmer theoretical basis, the limited experimental data available is not in particularly good agreement as can be seen from Table I. However, it must be remembered that besides the uncertain basis of the Keyes formula there is considerable uncertainty in some of the experimental values of AV. The only real justification for using the Keyes formula in the present analysis is that it gives a result which satisfactorily solves the problem at hand and, further, there are no more reliable procedures for calculating AV available. The coefficient 3 in Eq. [I] is determined such that the room-temperature value for x is to be used. The activation entropy AS is estimated as 8.95 x 10"3 kcal per OK mole using the values in Table I1 and the Zener" relation AS = PAHIT, where p is a dimensionless thermal coefficient of Young's modulus which is to be evaluated at low values of T/T,, aH is the activation enthalpy, and T, is the melting temperature of the alloy. The resulting value of AG at 1000°C is 25.6 kcal per mole. The Gruneisen constant (p = 3cup/XC,), where p is the density, is evaluated from the room-temperature data in Table I1 after calculating C, from the relation. A value of p = 8.32 g per cu cm based on the value of a. in Table I is used. The result is C, = 5.0 x lo6 erg per g, H = 2.32, and AV = 3.41 cu cm per mole at 1000°C and infinite carbon dilution. It is assumed that the activation volume is not a function of carbon concentration. The theory could be refined to consider AV a function of concentration, but due to the uncertainties in the parameters there seems little justification for this. Carbon dissolved in austenite forms a nonideal solid solution, so that in writing an equation for. the diffusivity of carbon it is necessary to take into account the change in activity coefficient with concentration. The resulting equation is16

Jan 1, 1964

By Zay Jeffries

HOSTILITIES in Europe, Asia, and northern Africa were responsible for dislocations in rare-metal supplies during 1940. Although the consumption of some of the rare metals is small the dislocations may be relatively large. In some cases these are advantageous to North America and in others they are disadvantageous. Specific instances will be cited later. Barium T HIN films of barium metal on special steel balls greatly improve the life and reduce the friction of rotating anodes in highly evacuated small X-ray tubes and make possible the operation of these anodes at relatively high temperatures. These remarkable results are described in an article by Atlee, Wilson, and Filmer in the Journal of Applied Physics for September, 1940. Oil could not be used because of the high temperatures on the one hand and its volatility on the other. Fig. 3 shows diagramatically the rotating anode and the method of coating the steel balls with barium. The letters K.I.C. refer to "Kemet Iron Clad." The K.I.C. wire was mounted so that the barium could be evaporated by direct passage of the electric current. At high temperatures the barium dif-

Jan 1, 1941

By Harrison Souder

MAGNETITE mining and milling in the Eastern States showed continuing improvement during the year. Some of the smaller mines remained idle, but the larger operations responded promptly to the improved situation in the iron and steel industry. The output of ore for 1936 was over twice that for 1935. A number of improvements were made in mine plant and equipment, and operating forces were increased and maintained at near normal. The coming year should see additional mines started up and production increased at the larger properties.

Jan 1, 1937

Arthur Jarman, Sydney, New South Wales, Australia (communication to the Secretary*):—All designs for modern metallurgical and chemical laboratories should provide each student's desk with a hood or cupboard for the removal of fumes, but I doubt the advisability of placing air-baths and similar apparatus close to the hot plate. It seems to me that unless the draft be exceptionally strong the fumes from ordinary wet assay work will corrode the iron-work of the fittings, in which case the baths would have to be removed to a general desk in order to lighten the work of the laboratory attendant. Since the laboratory described by Mr. White has been in use for two years, I should like to ask if any inconvenience has resulted from this corrosion. If not, it is certainly an important improvement to have the air-baths and similar apparatus placed on the student's desk. The hoods described by Mr. White are supplied with a good draft by means of a fan, which gives them a great advantage

Jan 1, 1905

By FLOYD T. TAYLOR

IN 1833, less than one hundred years ago, Michael Faraday discovered and stated the laws of electrolysis. His discovery formed the foundation of a new use of metals which has now reached a variety of application not ordinarily appreciated. Furthermore, things can be done with electro-deposited coatings which have thus far defied other methods. Some of the uses of electro-deposited coatings are interesting. The tonnage of metals already finding an outlet through such a channel is considerable. In general electro-deposits have two characteristics: ornament plus utility; utility plus ornament. Both these factors are usually found associated in electro- deposits. Ornament plus utility was probably the first use. For example, the silver-plating of tableware, having its real birth in Birmingham, England, about 1844. However, this same ornament plus utility retarded the development of electro-plating, because in the beginning, electro-plated articles were branded with the odium of imitation and shunned accordingly. The gold brick of the swindler may be an exception to this statement.

Jan 1, 1929

By AIME AIME

THE Petroleum Division will hold two meetings this fall, one on the Coast at Los Angeles, Sept. 29, with the technical sessions in the assembly room of the California Oil and Gas Association and a banquet Friday evening at the Richfield Cafe atop the Richfield building; the other in the Southwest, at Dallas, Texas, Oct. 6 and 7, with the Baker Hotel as headquarters. Dr. Frederick M. Becket, President of the Institute, and A. B. Parsons, Secretary, will attend both meetings. Arrangements for the meetings are not yet complete but the respective local committees, working in close touch with the officials of the Division are rapidly shaping up the programs and other detail.

Jan 1, 1933

By ANTON GRAY

In considering the possibilities and costs of discovering minerals by exploration. mineral occurrences may be classified roughly according to the size of the target they offer to the various methods that have been used to search them out. This classification is advantageous because the methods of search which might be expected to give results in one case may be totally inapplicable in others. Mineral deposits for the most part have been found in groups, or districts, in which the individual deposits occur under the same general geological conditions and usually contain more or less the same metals. There are, also, what are apparently isolated de- posits, although if the truth were fully known many of these probably would not be isolated. These districts, such as the Belgian Congo copper fields, the California Mother Lode, and the Linares lead district of Spain, form the first division of my classification. The second division is formed of the individual deposits of these districts, for example, Kambove mine in the Congo, the Kennedy-Argonaut vein in California, and the Cruz vein at Linares. The third division consists of the separate ore bodies that make up the deposits

Jan 1, 1949

By R. P. Rothwell

THE first difficulty mentioned is that in some instances two or more beds of coal separated by sandstone or slate rocks of considerable thickness in one part of a basin, are found running together in another part. Of course, we may happen to strike first the part of the basin where there is but a single seam, and in this case the bed would appear to divide into two or more branches within a short distance. Such cases are not rare in the anthracite coal-fields. I would suggest as an explanation of this phenomenon the gradual sinking of the peat-marsh-the embryo coal-bed-on one side, and the moving forward of the marsh, so that on one part of the bed the formation of peat would still be progressing, while another part, being under water, would be covered with mud and sand. Thus we have different portions of the same bed of different ages. Now if the sinking of the marsh be stopped for a time, the bed will become thicker in the portions left exposed, and if the sinking now changes in direction, so that the part that had previously gone down com¬mences to rise, we should have the phenomenon of a bed, continuous throughout, with one portion overlying another, and separated from it by rock strata. These are exactly the conditions observed in splitting beds. While one side of the lake is sinking, and the peat-marsh moving on in that direction, the other side may be rising,

Jan 1, 1873

The term metamorphism as commonly used means any change in a rock in either form or composition, from whatever cause. By metasomatism, according to Lindgren, is meant a metamorphism that involves a change in the chemical composition of a rock by the addition or subtraction of substance. Certain types of metamorphism are due to the action of mineralizing solutions, and are closely connected with ore deposition; they form, therefore, valuable guides in the exploration for ore- deposits. Other types of metamorphism are due to regional processes, and are not connected with ore deposition. By dynamo-regional metamorphism is meant a primary alteration of rocks over large areas under conditions of pressure, flowage, and heat. This process produces schists and gneisses from either sediments or igneous rocks. It is thought that there is little migration of minerals or of elements in dynamo-regional metamorphism, and that the changes are due chiefly to recrystallization and rearrangement of original minerals in bands with their major axes oriented normal to the direction of greatest pressure. Under these conditions limestones are commonly altered to marble, and sandstones to quartzite, basic igneous rocks to greenstone or serpentine, while rocks of normal or acid com- position commonly yield the usual types of schist or gneiss. Dynamo-regional metamorphism, extending over large areas, has no connection with mineralizing processes, and is, therefore, no guide to ore deposits; while this process has certain features, such as characteristic mineral associations, in common with contact metamorphism, the results of the two processes may usually be distinguished without difficulty.

Jan 1, 1932