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By M. S. Azun

The authors' paper did not explain the facts and reasons why state companies are established and what their role is in international industrial mineral trading. Also. I do not agree with the conclusion implying that the main goal for state companies is to capitalize natural resources. Almost all state companies are founded by certain laws and their activities are arranged by state regulations. Their only aim is to operate mineral deposits for their people and to protect the rights of the people. Although some ore deposits, such as nonstrategic or small, may be exploited by privately owned companies, the state has the right to control the operation and production. Activities of state companies may or may not be widened because of the character of the deposits and the importance of the mineral market involved. For some countries, although governments may occasionally change hands, the policy of the mineral trading system is not affected by this change. There is no doubt that any government desires to make more earnings to increase GNP, when it is involved in operating and trading mines. It wants to produce and sell the finished products, instead of unprocessed ones, if possible. When it is known that some mineral deposits are relatively rare, such as Turkish boron deposits, the government can nationalize the mines to control production and affect the market. If there is an abundance of a certain mineral in the market, the government can cut production and set a floor price, such as Canadian potash. Also, when production of a specific mineral is unique, such as Turkish chromite, the price of such mineral may be set by correspondent government. One may add that if some governments with their state companies produce a certain mineral in a larger amount, they may decide to establish a cartel to protect their production and price. These are the facts followed by government-owned state companies and partially government-owned companies. The reason being charge of many deposits by the state companies is always the same: "protect" the mineral rights of the people.

Jan 1, 1985

The sedimentery basins of this region developed in the collision zone of the Pacific Ocean plate and the continent. Stresses were transmitted thorough wedge-like lithospheric blocks, such as the Okotsk Sea, East Kamchatka, Aleutian and 2 other smaller blocks. Compression and inversion were more active at the boundaries: P ; P3 ; N1 ; and Z N in places. ? K2 P2 P3 N2 Tension, rifting and the increase in the rate of sedimentation were marked in '-2 , P3, Ni - N2, and also N2 - Q in places. Structural plan changes of the sedimentary basins and possible oil, gas and fluid migration occurred more actively 2 3 1 2 at the boundaries: ; P3 . N? , N1 N1 NZ N2 P2 P3 1 N1 'N 2 N3 Ni 1 1

Jan 1, 1995

By Gennady I. Gulyayev

A mathematical model of plastic deformation occurring in cold plug drawing of mother tubes with initial cross-sectional wall thickness variations (CSWTV) has been developed. The main provision of the model is that eccentricity em is of such value that projection of all forces acting upon the plug in the deformation zone along the axis perpendicular to the drawing axis equals to zero. Calculations have proven that with other conditions being equal increase in the die cone angle and the deformation cycle number reduces CSWTV. Theoretical findings were confirmed by practical results. Keywords: cold, drawing, plug, die cone, plastic deformation.

Jan 1, 2003

CHICAGO SECTION CHAS. H. MACDOWELL, Chairman, LUTHER V. RICE, Vice-Chairman, HENRY W. NICHOLS, Secretary-Treasurer, GEO. P. HULST, ALEX. K. HAMILTON, FREDERICK T. SNYDER, HENRY P. HOWLAND. The Field Meeting of the Chicago Section proved to be the most enjoyable meeting ever held by the Section. It took the form of a visit to the Northern Indiana Industrial District where the day was spent inspecting metallurgical plants in Indiana Harbor and East Chicago and in amusement at the Hammond Country Club. The weather was perfect and about 50 members and ladies attended the meeting. An inspection of the plant of the Inland Steel Co. occupied the morning. The plant was decorated in honor of the occasion and the company provided attractive souvenirs. It was noticed here that many of the ladies displayed an interest in the inspection and an understanding of the processes that would not have shamed professional metallurgists. While the members of the Section seemed to be most interested in the by-product coke ovens and the by-product recovery plant, the ladies enjoyed especially watching the snake-like antics of the red-hot rods in the wire mill. Leaving the steel plant, the Section enjoyed a ride through the district by automobile and arrived at the Hammond Country Club in time for lunch. In the afternoon some of the members inspected the plant of the International Lead Refining Co., at East Chicago, while the rest spent the time at the Country Club in golf, tennis, trap shooting, bridge and other amusements. During the dinner at the Hammond Country Club an informally organized male quartette led the singing in real college boy style. In the evening, E. E. Billow talked on the use of oil burners in metallurgical furnaces, Mr. MacDowell told of the present status of the Potash Industry and the Secretary told of some of the happenings at the Arizona Meeting. HENRY W. NICHOLS, Secretary.

Jan 12, 1916

By R. M. Bustin

"Extensive deposits of tectonically sheared coal of the Mist Mountain Formation occur in the south eastern Canadian Cordillera. The quality of the coal varies markedly; it is commonly partially oxidized and poor washability characteristics.Oxidation of the sheared coal has been promoted by its fine grain-size and by fractures in adjacent rocks which have facilitated penetration of atmospheric oxygen and circulation of oxygenated waters. Oxidation has resulted in a loss of coking power, a decrease in vitrinite reflectance, and an Increase In oxygen and decrease in carbon content.The relatively low clean coal yields of the sheared coal are primarily the result of the greater volume of mineral matter present, which in turn reflects both the greater susceptibility to shearing of coal with abundant rock partings and the shearing and dissemination throughout the coal of formerly discrete rock partings. The high ash content of some sheared coal seams may be artificial, resulting from the difficulty in distinguishing and separating sheared roof rock and floor strata from the coal seam during mining. There is little variation between the quality of the washed sheared and unsheared coal, with the exception of the somewhat higher ash content of the clean sheared coal compared to clean unsheared coal. This poorer separation of the ash from the organic fraction of the sheared coal is considered to be a product of the large amount of fines present as well as the local formation of aggregates of organic material and ash resulting from plastic flowage of the vitrite and clarite during shearing.IntroductionIn the southeastern Canadian Cordillera, coal seams of the Lower Cretaceous Mist Mountain Formation (Gibson, 1979 were in part sheared and comminuted during Late Cretaceous and Tertiary tectonism . Extensive deposits of sheared coal exist, and even in areas of mild deformation the coal may be locally sheared (Bustin, 1979). The quality of the sheared coal varies notably; it is commonly oxidized even far from the present weathering horizon, and locally has a disproportionately large amount of ash and poor washability characteristics even far from the present weathering horizon and locally has a disproportionately large amount of ash and poor washability characteristics."

Jan 1, 1982

By Lauren M. Roberts, Ralph R. Sacrison

The Meikle Mine uses long-hole open stoping and cut-and-fill methods with backfill as the primary ground support technique. The mine operates at 2,858 tonnes per day (3,150 tpd) and has sustained operation in excess of 3,175 tonnes per day (3,500 tpd). Consistent backfill production is critical in achieving these mining rates. The heart of the system is a 7.65 cubic meter (10-cyd) horizontal shaft ribbon mixer located 328 m (1,075 ft) underground. System control is through several PLC's, allowing for a high degree of automation and process flexibility. Aggregate feed is routed 257 m (842 A) through vertical drop pipes in the ventilation shaft, a rockbox, transfer raises, and then into either of two raisebored storage silos. The aggregate is crushed mine waste, nominally 70% 3.8 cm x 1.0 cm (1-1/2"x 3/8") and 30% -1.0 cm (- 3/8"). The binder is routed through a vertical borehole, surge bins, and transfer raises. The binder is a mixture of Type II cement and fly ash. Two primary manufactured fill designs are produced: a high strength mix for stopes which will be undercut; and a low strength mix for stopes with only rib exposure. The high strength target is 5.5 Mpa (800psi) unconfined compressive strength in test cylinders. The low strength target is 2.8 Mpa (400 psi). The systim has allowed consistent achievement of these targets, while experience has allowed reduced costs and increased efficiencies. Fill placement is through 6.1 cubic meter (8 cyd) LHD's dumping into stopes. Specific sills and cut-and-fill drifts are jammed to the back. System enhancements have included colloidal mixers for cemented waste slurry placement and transfer raises for sending manufactured fill to the lower levels of the mine.

Jan 1, 2001

The only definite information available is for the years 1875, 1878, and 1879 and 1880. The total figures in Table 48 are estimated. [ ]

Jan 1, 1942

By Arnlf Muan, Bert Phillips

The quenching technique has been used for- a study of phase velntiorzs within the composition triangle 2CaO.Fe2O3-FeO.Fe2O3 Fe2O3 of the system Ca-Fe-O. Desired total compositions of sanzples were attained by weighing of starting materials in required proportions and keeping them in sealed 80 pct Pt 20 pct Rh tubes during equilibration .runs. The liquidus surface has been delineated. the existence of two ternary compounds has been established, and seven ternary inwariant situations have been determined. ONE unit within the research program on refractory oxides in progress in our laboratories is the study of phase relations in the system Ca-Fe-Si-O. The present paper deals with the ternary system 2CaOFe2O3-FeO.Fe2O3-Fe2O3, which is only a small part of the enormously complex quaternary system. Many of the phases occurring in iron ore sinter products have compositions which can be closely approximated within this ternary system, and a knowledge of stability relations existing among these phases may be expected to be a useful guide for improving sintering operations. Two fundamentally different experimental approach es are commonly used in studies of systems containing iron oxides, both permitting control of the oxidation state of Fe. One method consists in keeping constant the oxygen partial pressure of the gas phase in equilibrium with condensed phases (liquid and crystalline). In the other method, which is the one used in the present investigation, the total composition of condensed phases is kept essentially constant by keeping the samples in a gas-tight container. The details of this experimental procedure will be described in a later section. PREVIOUS WORK Extensive studies of phase relations in the bounding binary system FeOFe2O3-Fe2O3 have been reported by Greig, Posnjak, Merwin, and Sosman,' by Darken and Gurry,2, 3 and recently by Phillips and Muan.4 A diagram summarizing the results of these studies is shown in Fig. 1. Particular attention is

Jan 1, 1961

By H. L. Ehrlich

Processes involving biological solubilization of metal values from ores, or removal of mineral constituents that interfere with metal value recovery from ores by abiological means, published mostly in the last 10 years, are reviewed. Many of them, though promising, have yet to be tested on a pilot scale or applied industrially.

Jan 1, 1987

By D. K. Das, P. A. Beck, S. P. Rideout

IN a previous publication1 1200°C isothermal phase diagram sections were given for the Cr-CO-Ni, Cr-Co-Fe, Cr-Co-Mo, and Cr-Ni-Mo ternary systems, in which the a phase formed narrow, elongated solid solution fields. The present investigation is concerned with the 1200°C isothermal sections of the Co-Ni-Mo, Co-Fe-Mo, and Ni-Fe-Mo ternary systems. A prominent feature of these systems is the presence of narrow, elongated µ phase fields. The crystal structure of the phase designated as µ both here and in the previous publication1 was determined by Arnfelt and Westgren.2 For the (CO, W)µ phase, named by them Co,W, (and also frequently designated as a), these authors found that the crystal system is hexagonal-rhombohedra1 and the space group is D53d — R3,. Westgren and Mag-neli3 later found that isomorphous phases exist in the Fe-W and the Fe-Mo systems (these phases are often referred to as < and E, respectively). Henglein and Kohsok4 stated that the phase described by them as Co7Mo,; (otherwise frequently designated as c) is also isomorphous with the above three. The Co-Fe-Mo system was investigated at 1300°C by Koester and Tonn,5 who found a continuous series of solid solutions between (Co, MO)µ and (Fe, MO)µ Koester6 also indicated similar uninterrupted solid solutions in the Ni-Fe-Mo system. However, since the Ni-Mo binary system does not have a phase isomorphous with F, Koester&apos;s diagram is expected to be erroneous. No data appear to be available in the literature concerning the Co-Ni-Mo system. The face-centered cubic (austenitic) solid solut,ions of iron, nickel, and cobalt, which are quite extensive in all three systems at 1200°C, are here designated as the a phase. The body-centered cubic (ferritic) solid solutions, based on iron, are designated in this report as the ? phase, in conformity with the nomenclature used previously.&apos; Experimental Procedure The alloys were prepared by vacuum induction melting in zirconia and alumina crucibles. The lot analyses for the metals used have been given.&apos; The number of alloys prepared was 46 for the Co-Ni-Mo system, 65 for the Co-Fe-Mo system, and 113 for the Ni-Fe-Mo system. The compositions of these alloys were selected with due regard to maximum usefulness in locating phase boundaries. The alloy specimens were annealed at 1200°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. Alloys consisting almost entirely of the face-centered cubic austenitic a phase, or of the body-centered cubic ferritic c phase were double-forged with intermediate annealing. The double-forged specimens were then final annealed for 90 hr at 1200 °C and quenched in cold water. Alloys containing considerable amounts of any of the other phases could not be forged. Such specimens were annealed for 150 hr at 1200°C and quenched. Microscopic specimens of all alloys were prepared by mechanical polishing, in many cases followed by electrolytic polishing. Description of the polishing and etching procedures used and tabulation of the intended compositions of the alloys prepared are being published in two N.A.C.A. Technical Notes.7,8 , Many of the alloys were analyzed chemically and, in general, the results are in excellent agreement with the intended compositions. X-ray diffraction samples were prepared by filing or crushing homogenized alloy specimens and by reannealing the obtained powders in evacuated and sealed quartz tubes. After annealing for 30 min at 1200°C the tubes were quenched into cold water. X-ray diffraction patterns were made with unfiltered chromium radiation at 30 kv, using an asymmetrical focusing camera of high dispersion. X-ray diffraction and microscopic methods were used jointly to identify the phases present in each specimen. The amounts of the phases in each alloy were estimated microscopically. The phase boundaries were located by the disappearing phase method. The results were used to construct 1200°C isothermal sections for the three ternary phase diagrams. The accuracy of the location of the phase boundaries determined in this manner is estimated to approximately ±1 pct of each component. The portion of the three phase diagrams lying between the µ, P, and 6 phases on the one hand, and the molybdenum corner on the other, has not been investigated. Recently Metcalfe reported0 a high temperature allotropic form of cobalt on the basis of dilatometric results and of cooling curves. In the present work no attempt was made to search for the new phase in the cobalt corner of the Co-Fe-Mo and Co-Ni-Mo systems. No alloy was prepared with more than 80 pct Co; the alloys used were intended to locate the boundary of the a phase saturated with cL. The microstructures of the quenched a alloys near the cobalt COrner gave no suggestion of an in-suppressible transformation On quenching. The location of the boundaries of the a + ? two-phase fields in the Fe-Ni-Mo and Fe-CO-MO systems was determined entirely by the microscopic method. The face-centered cubic a alloys near the ? field transform partially or wholly into the body-centered cubic ? phase on quenching from 1200°C to room temperature. The ? formed in this manner has an

Jan 1, 1953

By Andrés Llatas

El presente trabajo describe el comportamiento anódico de los sulfuros de cobre en las soluciones de ácido sulfúrico y férrico a través de la técnica potenciostática. En este sentido, se realiza una interpretación de los fenómenos psíquicos y cinéticos de la disolución en los sulfuros de cobre, considerando su importancia económica y las características de materiales refractarios que poseen los procesos convencionales de lixiviación.

Aug 26, 1988

By A. J. Barry

[This is the third report related to fundamental retail roof-bolting research in underground mines (1, 2)3/ and describes an investigation of the torque-load relationship for 3/ -inch, expansion-type mine roof bolts. In a previous investigation the relationship between torque and bolt load was established for 1-inch slotted-type bolts (1). The two types of bolts differ in diameter and method of tightening and consequently may exhibit different torque-load behavior. The 1-inch bolt is tightened by turning the nut, the 3/4-inch bolt by rotating the beaded bolt itself. Experience indicates that roof bolts should be tightened to moors satisfactory anchorage sand to minimise nag of tie roof over the mine opening. The generally accepted means for determining the bolt load is to see a torque wrench to measure he torque applied in tightening the bolt and, from a predetermined relationship between torque and molt load, to, determine the corresponding bolt load. Because frictional effects may vary between one type of shell assembly or bolt and others, 7 types of expansion shell units and 3 types of 3/4-inch-diameter, mild steel bolts were tested.]

Jan 1, 1954

By John A. Shuster

Case histories are reported for several soft ground shafts ranging from 6&apos; to 40&apos; in diameter and 50&apos; to 230&apos; in overburden depth for which ground freezing was employed to provide temporary ground support and groundwater control during shaft sinking through the overburden. Cases reported emphasize dealing with difficult site and ground conditions such as working within existing buildings, through very soft, running and bouldery soils, in the presence of substantial lateral groundwater flows, and into salt dome deposits requiring special considerations. Construction procedures, schedule, and relative costs are discussed for each case.

Jan 1, 1985

By Gülay Bulut, Ünzile Yenial

"Water composition has a significant effect on flotation. A better understand the role of water composition in flotation is very important for process quality and performance. Based on source of process water, the concentrations of the dissolved ions, hardness, contaminants and residual composition of reagents can varied in the process water. The various water resources employed during lead and zinc flotation caused activation, depression or selectivity effects on minerals due to the presence of different ions in solution. Metal ions in these water resources were adsorbed on the ore, whilst ions associated with gangue minerals were released into the flotation pulp.This paper includes a research for the effect of different water compositions on lead and zinc sulphide flotation. Experiments were carried out five types of water such as tap water, recycling water, tailing dam water, underground mine water and sea water. The ore sample was obtained from Esan Balikesir-Balya mine. The mineralogical study of ore sample shows that it contains mainly galena, sphalerite, pyrite, hematite, quartz, diopside, epidote, calcite, and chlorite. It is found that recycling water and tailing dam water has a positive effect on recovery of lead and zinc minerals and detrimental effect on content of both minerals. This result may explain with remaining reagents in these waters. Underground mine water and tap water gave nearly the same recoveries of zinc. Sea water affects the recovery lead and zinc negatively."

Jan 1, 2014

By L. Dudley Stamp

In my last report on Petroleum in Burma and India1, details were given of production and development up to 1932. It was pointed nut, that the only statements available for Burma were those published officially by&apos; the Government of India in the Annual Review of the Mineral Production of India (Records of the Geological Survey of India), which are issued about 10 or 11 months after the close of the year. Operations in Burma are almost entirely in the hands of three companies—the Burmah Oil Co., the British Burmah Petroleum Co. (with its subsidiary, the Rangoon Oil Co.) and the Indo-Burma Petroleum Co.—and these companies preserve a policy of secrecy, so that details are not available of new wells, depth, wells abandoned, or of other figures, except in so far as the Government considers it advisable to publish the information in its possession. GeneRal Developments in 1933-1934 As predicted in 1933, there have been no spectacular developments and no new fields have been discovered. Nor are there any new indications of a likelihood of fresh discoveries. The policy of extremely careful exploitation. has been continued and intensified; production is being maintained at an almost steady level and can be so maintained for many years to come—indeed, it is the policy of the leading company to permit refinery and local market requirements to dictate the production required. Contrary to experience in practically every other part of the world, India has shown a slightly decreased demand for petroleum products—especially kerosene, but also for gasoline. The increased use of electricity would explain the lower demand for kerosene, but the falling off in the demand for gasolinc can only be attributed, according to the Chairman of the Burmah Oil Co., to the depression and to the incidence of heavy taxation. In India (including Burma) as a whole, production was 305,018,751 Imperial gallons in 1931 (8,714,822 U. S. barrels); 308,606,031 Imp. gal. in 1932; 306,009,022 in 1933 and is estimated at 308,000,000 in 1934.

Jan 1, 1935

By M. Kawulak

The necessity to protect the environment can limit mining activities and make some areas less attractive for the prospecting and exploration of mineral deposits. In Poland, the main environmental factors that restrain Irumng are: 1. Regional A Protection of the landscape B. Protection of ground water from contamination and depletion 2. Local A Conservation of fertile soils B. Conservation of forest resources C. Preservation of natural, cultural, and historical monuments The regional factors listed above that can limit mining are presented on a map of Poland. These data, combined with maps of known and potential mineral deposits, make it possible to delineate general levels of limitation for various mining-related activities varying from "no existing environmental limitations" to "no allowed industrial activity" As an example, a compilation of such data is presented for lignite exploration and mining in Poland. Lignite deposits occur within Upper Paleocene to Upper Miocene clastic strata at depths ranging from a few to 300 m. The thickness of the lignite is generally a few meters, but can locally reach over 100 m within grabens. As a result, the overburden-to-lignite thickness ratio varies from less than 1 to over 20. Within the same Tertiary strata, and within overlying Quaternary strata, several aquifers exist that produce good quality water that may be contaminated or depleted during lignite mining. The protection of these ground waters is the main factor limiting lignite mining and should be addressed in mining and environmental policy and planning.

Jan 1, 1996

By P. Barnes

It cannot be said that this whole subject is a new one in respect to its presentation to the Institute, but the minute discussion of it has been looked upon as lying more strictly within the field of study of the societies which have to do chiefly with the construction and management of machinery as such. It must be true that the importance of close limits in steam-economy is as fully recognized among the members of this Institute as by any body of men who have to do with steam-machinery. In all directions, nevertheless, among manufacturers as well as among metallurgists, there may still be found those who do not give the same attention to exact methods in fuel-consumption as devoted to steam, as to other technical uses which, to say the least, are not more important. The study of the most efficient methods of use of fuel in operations which are more strictly metallurgical has been long-continued, and in some directions nearly or quite exhaustive. This has led to a rather close bringing-up, in those particulars, all along the line of technical work, of the establishments (and their managers) which had lagged behind. Yet, in the steam-departments of those works, there are too many reasons for believing that the name may still be legion of those whose methods and results are far from the best. If there be room in any given case to suspect any imperfect working or waste of fuel in the steam-supply, the search for the evil, the clear fixing of its cause, and the application of the remedy are, or certainly ought to be, too obvious in their pressure for attention upon a manager to call for even so scanty a mention of them as can be accorded in this paper. It is natural that men should be incredulous as to imperfections which may be noted as existing in their machinery or methods. Still more are they likely to be altogether disinclined to admit that there may be thus an actual and palpable leakage in the compartment of their money-drawer devoted to coalsupplies. But the laws which govern the combustion of fuel, the

Jan 1, 1885

By T. Sterry Hunt

I HAVE in a previous communication called the attention of the Institute to the geognostical relations of the crystalline iron ores belonging to the Eozoic rocks of North America, at which time I noticed (1) those associated with the gneisses of the Laurentian series, (2) those of the crystalline schists of the Huronian, as seen in Northern Michigan and in many localities along the Appalachians ; (3) those of Southeastern Missouri associated with petrosilex porphyries and schistose rocks, and presumed to be nearly of the same age with those of the Huronian schists; and (4) the highly titaniferous ores of the Norian or Labradorian series from Essex County, N. Y., and from various parts of Canada. It may here be remarked that, although the presence of titanium is most marked in the Norian ores, this objectionable element is sometimes found in the schistose ores of the Huronian, and to a lesser extent in certain Laurentian magnetites. The ores of each of these geological divisions have their individual peculiarities, which serve to distinguish them to such a degree that the magnetites and specular ores of the Laurentian are as dissimilar to those of the Huronian as are the crystalline silicated rocks of the two series. As it happens that these mineralogical dissimilarities correspond to differences in composition and in adaptability to different processes of manufacture, which, in the present condition of the iron industry, are objects of special consideration to metallurgists, it will be seen that these geognostical distinctions become of great practical importance. During the past year I was desired by the Geological Commissioners of Pennsylvania to devote a few weeks to certain geological studies in the eastern part of the State, in the course of which I was enabled to make, with regard to its crystalline iron ores, some observations to which I desire to call the attention of the Institute. I may mention, in passing, that the great South Mountain belt, from the Schuylkill to the Delaware, is composed of Laurentian rocks, in which are found the characteristic ores of the series like those of the Highlands of New Jersey and New York, and of the Adiron-

Jan 1, 1876

By T. S. Blair

I feel a certain sense of responsibility in bringing before you the subject of the direct process in iron manufacture. I am aware that, in such a body as I have now the honor of addressing, there are few who are not already so well informed upon its past history that it would be a weariness to them to listen to anything else than an account of practical success. Yet, to claim that success involves so much that, if I do not make good my claim, I deservedly expose myself to severe criticism. The whole literature of the art, so far as it relates to the direct process, is, up to this time, but a history of failure. It is safe to say that more money, time, and talent have been fruitlessly spent in the pursuit of this object than in all the other unsuccessful efforts in the whole line of iron metallurgy. A distinguished authority in patent law has remarked that " the invention records of the United States and of foreign countries are filled with the waifs and abandoned relics of these abortive struggles." Dr. Percy, whose great work may be taken as an epitome of all that was worth mention, whether useful or curious, in pig-iron metallurgy, up to the date of its publication (1864), after giving elaborate accounts of various attempts at the direct process, condenses his own opinion of all that had been then effected, into a brief but summary comment upon a pamphlet of one of the sanguine inventors who had said: "It is evident that the present mode of working iron

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts&apos;1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969