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By William Campbell

(Cleveland Meeting, October, 1912.) THE structure of iron and steel, though the object of so much study and research for the past 25 years, is by no means thoroughly understood. In the first place, we have three or more distinct iron-carbon thermal diagrams, each with its own supporters, and each representing a theory of the structure and constitution of cast-iron. In the second place, by reason of the fact that austenite, the solid solution of carbon in iron, decomposes in the solid state into ferrite, or pure iron, and cementite (Fe3C), and that quenching from above this transition-range, no matter how rapid, cannot entirely prevent the change and thus preserve the austenite by itself at ordinary temperatures, it happens that under the microscope we find, in addition to the ferrite, Fe3C, and austenite, which the thermal diagram of steel requires, it series of transition-products with distinctive structures, to which have ,been given the names martensite, troostite, sorbite, etc. Now these transition-products, in addition to the solid solution, austenite, have been the source of much controversy, at times very bitter. One side would insist that, say, troostite was an entity, which the other side would deny, pointing out that it must be a transition-mixture, with a particular structure. That austenite was a solid solution of carbon in iron has been denied by one school ; we have been told that Fe24C dissolved both Fe3C and Fe, and thus gave rise to a whole series of quenching-products-all this in spite of the fact that no matter how the thermal diagrams differ in regard to cast-iron, they all agree in regard to the solid solution, austenite, for Fe24C finds no place on the diagram. Thus it happens that while the authorities fight both in regard to the iron-carbon diagram and the structures met with in hard- * Associate Professor of Metallurgy, Columbia University in the City of New York.

Dec 1, 1912

By Joseph A. Holmes

I. INTRODUCTORY. THE plans for the investigation of fuels and structural materials now being conducted by the Technologic Branch of the United States Geological Survey were, before being decided upon by the Director of the Survey, submitted for consideration to the National Advisory Board, upon which there are nine representatives from the membership of the American Institute of Mining Engineers, viz.: Messrs. John Hays Hammond, Robert W. Hunt, B. F. Bush, and E. V. d'Invilliers (representing the Institute); Messrs. Julian Kennedy and C. S. Robinson (representing the Iron and Steel Institute); Dr. Charles B. Dudley (representing the American Society for Testing Materials); Mr. F. H. Newell (representing the U. S. Reclamation Service); and Dr. Richard Moldenke (representing the American Foundrymen's Association). It seems fitting, therefore, that a report of these investigations of the past three years should be submitted to the Institute for publication in its Transactions. The above, together with other representatives of the national engineering societies and allied organizations, were invited by President Roosevelt to serve, along with the Chiefs of the several Government Bureaus who have charge of public works and large. fuel purchases, on the National Advisory Board to give advice concerning these investigations. The appointment of this National Board grew out of a wish on the part of the President, the Secretary of the Interior, and the Director of the Geological Survey not only that the appropriations for these investigations be expended in a manner most beneficial to the several branches of the government

Jan 7, 1908

By Wolfgang Hermann

The ancit-process of the Eschweiler Bergwerks-Verein, an affiliate Company of ARBED S.A., Luxembourg, was developed in its principles by the Dutch State Mines, Limburg, in the mid-50's with the aim of producing a smokeless domestic fuel on the basis of low volatile hard coal. In 1967, the EBV erected a 10 t/h large- size pilot plant along these principles in the Aachen mining district and further developed the acquired know-how. In hardly 10 years more than 650 000 t of ancit briquettes with unit weights between 17 and 100 grams were produced and in the meantime stream rates of over 85 % of the yearly utilization hours have been reached. In more than 10 blast furnace trial runs involving substitution rates up to 100 p. c. ancit have proved the suitability of ancit as a metallurgical fuel both for a burden with a high and a poor iron content. Construction work for a minor process-step to enable processing of coal with a higher content of volatile matters is finished and first results are expected by summer this year. A pilot plant with a 30 t/h capacity working on a low-volatile coal basis is being planned. Engineering and construction are supervised by MecanARBED. Luxembourg, as responsible contractors.

Jan 1, 1977

By Sooi P. Chong

Expansion of concentrator capacity at Iron Ore Company of Canada's Carol Lake plant resulted in a dramatic increase in the production of fines. With iron recovery from the fines running only 18%, Carol Lake engineers initiated an extensive test program which resulted in the installation in July 1977, of a full-scale plant utilizing Reichert cone concentrators. Results to date have indicated a 100% increase in iron recovery from the concentrator's fines product. Carol Lake is located near the western boundary of Labrador, Newfoundland, some 960 km (600 mi) northeast of Montreal. Concentrator operations began in 1962 with a design capacity of 7 million t/y (7.7 million stpy). The bulk of the concentrate was pelletized at a 6 million t/y (6.6 million stpy) pelletizing plant completed in 1963. The remaining concentrate was sold in the international market. The concentrator was first expanded in 1966 to 10 million t/y (11 million stpy) capacity. In 1967, the pellet plant was expanded to match the increase in concentrate production. Sales increases led to a further expansion in 1973. By 1977, more than 40 million tons (44 million st) of crude ore were processed to recover in excess of 17.42 million tons (19 million st) of concentrate and 10.4 million tons (11.5 million st) of pellets.

Jan 12, 1978

By R. G. Davies

THE effect of ordered structures upon steady state creep has not been extensively studied although it has been demonstrated that the brass,' ie,' and Fe3Al3 superlattices increase the creep resistance. Suzuki and Yamamoto observed an acceleration in the creep rate of Ni3Fe below the critical temperature for order, (T, - 505"), for both the ordered and disordered states, and that the activation energy for creep was independent of the applied stress. They concluded that a dislocation climb creep mechanism was operative down to 300°C which is - 1/3 TM where TM is the absolute melting temperature. This is quite remarkable in that it is usually observed that climb controlled creep in both pure metals and alloys ceases below - 1/2 TM (590" for ie). With this anomaly in mind it was decided to reinvestigate creep in a 75 at. pct Ni-25 at. pct Fe alloy. The creep apparatus and operating conditions have already been decribed. Since Ni-Fe alloys order very slowly, it is possible to have a disordered alloy at a temperature below T,. A long anneal at a temperature just below T, produces considerable long-range order;5 the ordering treatment in the present investigation was 150 hr at 485°C which gives an antiphase domain size of-SOW

Jan 1, 1963

The Raymond Memorial Volume, which the Members of the In-stitute have been so anxiously awaiting since the beloved man's death, is nearly ready for publication. It will contain about 45,000 words and some illustrations and a frontispiece portrait. This book promises to fill every expectation of the contributors to the volume and the host of admirers of the genius who so long guided the destiny of the Institute. It will contain one of Doctor Raymond's best stories, entitled "James and Jim;" his famous article on "Job on Mining;" and one of his poems entitled "The Grand Canyon." A biography of Doctor Raymond has been written by his daughter, who is the wife of a member of the Institute. The memorial addresses delivered by Dr. Henry F. Drinker and T. A. Rickard at the annual meeting in New York in 1919 will be included. There will also be very interesting reminiscences by H. M. Howe, A. S. Dwight, C. W. Goodale, R. W. Hunt, Lyman Abbott, J. F. hemp, T. A. Rickard. The volume has been edited by T. A. Rickard, which promises all that can be wished for the volume from a literary standpoint. The edition will he limited so that it is very desirable that orders for this volume be sent in to the Institute as promptly as possible. The price will be $5.00.

Jan 12, 1919

By R. V. Lundquist

R. T. Hukki (Finland Institute of Technology, Helsinki, Finland)—Two schools of thought are developing concerning the order of the rate of flotation. The paper by Morris is intended to show experimental evidence in favor of the first order rate. Arbiter, on the other hand, has presented an earlier paper" to demonstrate the validity of the second order rate equation. Unfortunately his method of plotting is open to criticism, as pointed out by Morris." A more sensitive method of plotting has been described by the writer,= whereby the data presented by Arbiter demonstrate the superiority of the second order plot. The general rate equation may be written in the following forms for the integrated first and second order equations: (A) t =------In—-------- (first order) [4] 1 1 (B) — = — kc, + KC°²— (second order) [5] t R As a first approximation the value of C, may be taken as a unity, 100 pct or 1. Whether or not this is the case in all tests performed by Morris is impossible to judge, owing to the fact that the flotation times are extremely short, e.g. 150 sec in tests A. It would, indeed, be very interesting to know what the total recovery R would be after 1 hr of flotation, for example, instead of after 150 sec. Certainly there are circumstances when C, approaches unity within a very small

Jan 1, 1954

(The following list contains the names of those members of the Institute of whose connection with military service we have only recently become acquainted; it also includes the names of a few who have recently been promoted or transferred, indicated by a *. A complete list was published in the Year Book, issued as a supplement of the Bulletin for March, 1918.) ANDERSON, AMIL A., Co. A, 309th Regiment Engineers, 84th Div., American E. F., Care Postmaster, New York. ARMSTRONG, HAROLD K., Pilot, Naval Aviation, U. S. Naval Air Station, Miami, Fla. BASSETT, ARTHUR F., Co. 6, -E. 0. T. S., Camp Humphreys, Va. BEDDALL, THOMAS H., Adjutant, 1st Battalion, 1st Gas Regiment, American E. F. BERNARD, CLINTON P., Candidate, 12th Observation Battery, F. A. C. 0. T. S., Camp Taylor, Ky. BROOKE, LIONEL, 50th Co., 13th Battalion, 5th Replacement Engineers, Camp Gordon, Ga. BROWNING, EDWARD, Corp., 1st Regiment Engineers, Co. D, American E. F. BUGBEE, EDWARD E., S. A. T. C. Headquarters, Raleigh N. C. BUTTERFIELD, G. BRUCE, CO. C, 605th Engineers, American E. F. CADOT, J. J., 1st Lieut., U. S. Air Service, American E. F., Care Post- master, New York. CARLOCK, J. B., Major, 2d Battalion, 1st Gas Regiment, American E. F., France.

Jan 12, 1918

By John C. Ludlum

A most stimulating event in the development of world mineral production and technology, the Eighth Commonwealth Mining and Metallurgical Congress was convened at Melbourne Town Hall on March 1 by Sir Maurice Mawby, President of the Congress. Continuing successively at Melbourne, Canberra, Sydney, and Surfers Paradise in Australia and then at Wellington, New Zealand, the four plenary sessions, 50 technical sessions, and both local and extended mine and plant tours during the seven weeks of the Congress, provided a superb medium for assessing the present and looking into the future. There were more than 2300 participants from 32 countries in the various functions of the Congress, including 500 delegates and wives from countries other than Australia and New Zealand, and from 18 countries not members of the British Commonwealth of Nations. Registrants from South Africa numbered close to 200 and there were about 100 from Canada, 70 from the United Kingdom, 60 from the United States, and 20 from Zambia. Although most of the overseas delegates held administrative positions with companies, government agencies, and colleges or universities, professions identifiable from registrations included 100 engineers, 60 geologists and 30 metallurgists.

Jan 8, 1965

By John W. Langley

In the summer of 1888 it was the fortune of the writer to present the subject of the desirability of establishing a set of samples of steel, which should be analyzed with extreme care, in order that they might become standards to which scientific and commercial analyses of iron and steel could be subsequently referred; also, that greater uniformity in the results of analyses might be brought about, since these standards would bear towards analytical methods somewhat the position which the original units of weight and length, the gramme and meter, or the pound and yard, preserved in Paris, London, and Washington, do to the mechanical arts. The plan met with hearty co-operation, with the result that com mittees were appointed in Sweden, Germany, France, England, and America, to receive the material and to see that the necessary au alyses were executed. In England, the British Association for the Advancement of Science appointed a committee, which subsequently published a plan

Jan 1, 1891

Herewith are transmitted the joint report of the Treasurer and Finance Committee for 1934 and the reports for the same year of the Chairmen of the following Committees: Admissions, Membership, Papers and Publications, Library, and MINING AND METALLURGY. TO these reports you are referred for details of the year's activities. Finances.-Income for 1934 from all sources totalled $134,967 com- pared with $121,689 in 1933. The increase is accounted for principally by four items: $6000 increase in initiation fees and dues of new members; $1800 in current dues; $4000 in "back" dues; and $2800 in the sale of publications, including TRANSACTIONS volumes and technical papers in the form of "separates." In passing, it may be remarked that income from back dues during 1935 will be less than in 1934, for the obvious reason that the total amount of dues in arrears has shrunk and consequently there is less to draw from. Income from

Jan 1, 1934

By J. F. Abel, F. T. Lee

Subsidence is controlled by a complex com¬bination of mining and geologic factors. For example, a compilation of worldwide data shows that, as the percentage of shale in the overlying rock mass decreases and the amount of sandstone increases, the angle of draw (and the area affected by subsidence) decreases. Limestone in the over¬burden appears to cause a more than twofold decrease in the angle of draw compared to a like amount of sandstone. Increased amounts of sandstone were accompanied by a greater surface subsidence relative to the mining height. The total thickness of overburden did not appear to influence the subsidence magnitude above super-critical panels. The greater the thickness extracted, the smaller percentage of that thickness shows up at the surface as subsidence. The greater the percent of the seam extracted, the greater the subsidence reaching the surface. The maximum subsidence above room-and-pillar panels de¬pends on the pillar height and minimum width as well as the other factors listed.

Jan 1, 1984

NEW MEMBERS The following list comprises the names of those persons who became members during the period Mar. 10 to Apr. 10, 1914. Members ADAMS, DANIEL T., Mining 1416 Westminster Bldg., Chicago, Ill. BLICKENSDERFER, FRANK CLEVELAND, Sampler Morenci, Ariz. CAVERS, THOMAS WILLARD, Met Copperhill, Tenn. CLAPP, CHARLES H., Geol Univ. of Arizona, Tucson, Ariz. CLARK, PATRICK T., Pres Bullwhacker Mine, Spokane, Wash. COMSTOCK, HARRY, Mining Mineville, Essex Co., New York. COOKE, JOSEPH H., Gen. Mgr Mono Dev. Co., Gisborn, Tooele Co., Utah. COOPER, DEXTER P., Civ. and Hyd. Engr 101 Park Ave., New York, N. Y. DEGOLYER, E. L., Geol Apartado 269, Tampico, Mexico. DESHAYES, ERNEST F., Mine Foreman Baldy, N. M. DOUGLASS, WILLIAM CRAWFORD, Min. Engr 107 Leonard Hotel, Butte, Mont.

Jan 5, 1914

By R. S. Archibald

THE Blueberry mine is about 10 miles west of Ishpeming, Marquette County, Michigan. The property consists of about 2000 acres in sets. 3, 4 and 5, T. 47, N.R. 28W. and sets. 32, 33 and 34, T. 48, N.R. 28W., and, excepting one intervening 80-acre tract, contains the iron formation for a length of about 2 1/4 miles. The property is traversed by State Highway M-28 and is served by three railways, the Chicago & Northwestern, the Duluth, South Shore & Atlantic, and the Lake Superior & Ishpeming. The Northwestern transports the ore to a dock at Escanaba; the other railways, to Mar¬quette. Ore for Chicago goes via Escanaba and that for Lower Lake ports, as Detroit, Cleveland, and Buffalo, via Marquette.

Jan 1, 1935

The North American Coal Corp. Increasing demand for coal, stimulated by the national energy shortage, and complicating and often conflicting, demands by government and ecology groups for better land reclamation methods continued to propel advances in surface mining technology during 1974. To meet current demands for coal (estimated at more than 700 million t for 1975 and 1.5 billion t in 19851, equipment manufacturers and coal operators concentrated on increasing the productivity of all surface mining equipment. The trend towards larger equipment, particularly in overburden removal, loading, and haulage machinery, prevailed during the year, notwithstanding the perennial debate over the economics and practicality of using large, inflexible equipment. Increasingly, the industry called on computers to monitor productivity and help design more efficient production systems

Jan 2, 1975

By W. J. Parton

THE efficient recovery and preparation of small sizes of anthracite called No. 4 Buckwheat (3/3 2 by 1/3 2 in.) and No. 5 Buckwheat (1/3 2 in. by 0), present a difficult problem to the anthracite operators. In many instances preparation of these sizes, particularly No. 5 anthracite, is extremely inefficient. In many of the older preparation plants, inadequate facilities, and often none at all, were provided as an integral part of the plant for cleaning this fine anthracite. Consequently, much of the material smaller than s, 32 in. was discarded. As the demand for these sizes increased, facilities for preparing the fine sizes were often crowded into existing structures with consequent sacrifices of capacities and efficiency. In addition to this condition, the methods of preparing the finest sizes are being developed in an attempt to improve their efficiencies. Because the demand for small sizes of anthracite still is increasing, many operators would benefit by investigating and improving the cleaning equipment employed on these sizes.

Jan 1, 1949

By William E. Ford, Edward Salisbury Dana

The Nitrates being largely soluble in water play but an unimportant r81e i~ Mineralogy. SODA NITER. Rhombohedral. Axis c = 0.8276; rr" 1071 A 7101 = 73' 30'. Homeo- morphous with calcite. Usually massive form, as an incrustation or in beds. Cleavage: r (1011) perfect. Fracture conchoidal, seldom observable. Rather sectile. H. = 1.5-2. G. = 2'262.29. Luster vitreous. Color white; also reddish brown, gray and lemon-yellow. Transparent. Taste cooling. Optically -. w = 1'5874, e = 1'3361. Camp. - Sodium nitrate, NaN03 = Nitrogen pentoxide 63'5, soda 36'5 = 100.

Jan 1, 1922

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation's resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,' however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor' and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750' or 650°C. Since a trans-

Jan 1, 1954

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970