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By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring's predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,' who applied Eyring'sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann's constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers' data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By J. C. Fisher

Martensite transformations in steels and other alloys are characterized in part by the absence of composition changes during the growth of a new phase. Transformation occurs rapidly, and there is insufficient time for long range diffusion or partition of alloying elements to take place; martensite reactions in alloys thus are similar to phase transformations in single component systems. A fundamental understanding of martensite transformations in steels is impossible without knowledge of the free energy change upon transforming austenite (face centered cubic iron containing alloying elements) to ferrite (body centered cubic iron containing alloying elements) of the same chemical composition. The present paper assembles the best information available concerning the influence of temperature and composition on this free energy change. Most of the material has been taken from the work of Johansson,' Mehl and Wells,2 Zener3,4 and Smith;5 and indirectly, through these authors, from the work of Austin.6 In agreement with the generally accepted viewpoint, martensite is assumed to be an ordered solution of carbon in ferrite of the same composition as the parent austenite; only at high temperatures and low carbon concentrations is the carbon in ferrite distributed at random. The properties of the disordered solution are estimated by extrapolating the known properties of iron-carbon solid solutions into the range of supersaturation, and the free energy change associated with ordering is estimated from the theory developed by Zener. By incorporating Smith's recent thermodynamic measurements and Zener's theory of ordering, the present analysis modifies previous estimates of the free energy change associ- ated with martensite transformations. Consider a two component system consisting of a solvent A and a solute B. Let Na and Nb represent mol fractions of A and B respectively, let aa = raNa and ab = YbNb represent activities, and let superscripts 1 and 2 refer to phases 1 and 2. The partial molal free energies of A and B in phases 1 and 2 can be summarized as follows: free energy standard state Fa' - Fao1 = RT In an1 pure A' Fa2 - Fa2 = RT In aa2 pure A2 Fb1 - Fbo = RT In ab1 pure B Fs2 - FB2 = RT In aB2 pure B. The free energy of a gram atom of phase 1 is* AF1 = Na'Fa1 + Nb'Fb1 and that of phase 2 is AF2 = NA2FA2 + NB2Fb2. A martensite transformation from phase 1 to phase 2 requires Na1 = Na2 = Na and NB1 = NB2 = Nb, and the free energy change per gram atom accompanying transformation is AFi-2 = NA(Fa2 - Fa1) + Nb(Fb2 - Fb1) = NA[RT In (aA2/aA1) + AFa1?2] + Nb RT In (aB2/aB1) = Na[RT In (ra2/ra1) + AFa1?2] + Nb RT In (TaVTB1). [1] where yn2, yn1, yB2, yB1 are activity coefficients, and where Ma'+* is the free energy change upon transforming a gram atom of pure A from phase 1 to phase 2 at the temperature in question. For martensite transformations in plain carbon steels, A = iron (Fe), B = carbon (C), 1 = austenite (7). 2 = ferrite (a), and Eq 1 is AFr ?a= NFe[RT In (rf.a/rfer) + AFF.r?a] + TVc RT In (eca/rc1)- L2] Nothing is known concerning the values of yFea and yca for carbon concen- , trations in excess of 0.025 pct. However, the approximation rf.7 = 7f." = 1 cannot be appreciably in error for small carbon concentrations, and Eq 2 reduces to Afr-a = NfeFfer?a1 + NC RT In (rca/rcr)- [3] Johanssonl and Zenera have calculated MFfr?a from the specific heat measurements compiled by Austin.6* Their calculated values agree closely, and are summarized in Table 1. The activity coefficients relative to graphite for carbon dissolved in iron vary with temperature according to the relationships d In rcr/d(1/T) = AHcr-R dlnyca/d(l/T) = AHCa/R where AHc? and AHca are the heats of solution of graphite in y and a iron. Assuming the values of AH to be independent of carbon concentration and temperature, In rCr = AHcr/RT + I1 In rca = AHCa/RT + 12

Jan 1, 1950

By ERNEST A. HERSAY

ACCURATE ore-sizing with screens is drawing attention to certain details that now, more than ever before, require attention. There are many tests that must be preceded by careful sizing. The assayer often could profit by a more careful selection of screens. In milling, more attention is given the slimes produced. Cement-manufacturers are pulverizing and screening finer than they formerly did, and others are reducing materials to fine sizes at high cost, with screens used to govern the fine¬ness of the pulverized product. Fine screens are expensive, easily injured by mis-use, are carried in stock sparingly by most dealers, and are handled often by those who know little about them except their designated number. More attention, on the whole, needs be given the actual size of the mesh-openings, and less emphasis placed upon any custom or conventionality in numbering. An effort to classify wire screens, in this respect, leads at once into computations, where one is confronted with details of sizes and standards, of different wires, different gauges, and different customs. There is always uncertainty about the exact working-size of a screen until one gives the matter special attention, and devotes more time to it than its simplicity seems to demand. To know only the number is not sufficient for all uses. Often, in sets, superfluous sizes are used; and sizes are omitted that are of critical importance. In wire screens, the use of different standard sizes of wire makes important differences in dimensions that must be taken into account. The dealer usually grades screens by the number of openings per linear dimensions, regardless of the size of the openings or of the wire. Certain 100-mesh screens in use are found, by measurement, to he actually coarser than others of 90-mesh, a result which is due, of course, to the use of larger

May 1, 1906

United Engineering Trustees, Inc. W. D. B. MOTTER, JR., '40 A. L. QUENEAU, '41 ALBERT ROBERTS, '39 The Engineering Foundation GEORGE D. BARRON, '40 F. F. COLCORD. '42 A. L. QUENEAU, '41

Jan 1, 1939

Jan 1, 1937

Mining headlines in 1952 dealt mainly with expansion as the industry aimed for an ever increasing production to meet the nation's needs. Huge sums were expended for equipment, research, and development. Headlines told part of the story. Negotiations between San Manuel Copper Co. and the RFC finally resolved in a $94 million loan for the development of low grade Arizona ores. Magma Copper, parent firm was to supply an additional 8 million. Kennecott Copper Co., deepening its Deep Ruth Shaft of its Ruth, Neyy mine, announced that the shaft would be in full production in 1953.

Jan 2, 1953

By E. P. Pfleider

IT is generally believed that the amount of diamond drilling will increase appreciably in the next decade, as the search for minerals throughout the world becomes more difficult and intense. An attendant problem may be one of short diamond supply, resulting in higher bit and drilling cost. With this background, the U. S. Bureau of Mines1 and the School of Mines at the University of Minnesota2 have established comprehensive research programs in diamond drilling. One of the several aims is the design of a more efficient bit, which would lower diamond consumption and increase rate of advance, both essential in reducing drilling costs.

Jan 2, 1953

Jan 1, 1925

By John J. Cioston

THE steadily rising flood of gold production from all parts of the world has created an avalanche of rumors regarding the stability of the present price of this metal. Markets have been unsettled from Johannesburg to London from New York and Toronto to Melbourne, despite repeated denials from, American and British authorities of any immediate intention to alter the price. Various economists and financial writers have blossomed forth with predictions that the price would be set at the old level of $20.67 per oz.; some have even been so brash as to state That a price of $15 would be necessary to bring production within control. These effusions, based entirely upon monetary theories and with no regard to production costs, serve to confuse rather than clarify the situation.

Jan 1, 1937

ELECTROREFINING Canadian 1,023,691 -Removal of bismuth from slime filtrate in the Betts process refining of lead. The filtrate is subjected to electrolysis in a cell having an anode of crude lead and a cathode of refined lead under operating conditions to preferentially deposit bismuth on the cathode. The substantially bismuth-free filtrate is recycled for use in the process as the electrolyte for producing high-purity lead. S. Hirakawa and R. Oniwa, assigned to Mitsui Mining & Smelting Co., Ltd. Jan. 3, 1978. 8 pp. (204-73). Filed: 2-18-74 (192,810). Same: U.S. 4,026,776, dated May 31, 1977.

Jan 1, 1979

By E. J. Haug, M. M. Fine

FOR several years work has been carried on by the U.S. Bureau of Mines at Rolla, Mo., to develop improved methods of concentrating the oxidized ores of lead and zinc. Various samples have been investigated, and results on some have been published 1,2 lished.l, 2 Details of the progress to date are given in a mineral dressing study now being conducted for an extensive oxidized lead-bearing tract in southeast Missouri, property of St. Joseph Lead Co. These oxidized ores present problems typical of many encountered in modern mineral dressing research in that recovery of very fine particles is of

Jan 1, 1956

United Engineering Trustees, Inc. ARTHUR S. DWIGHT GEORGE D BARRON J V. N DORR Engineering Societies Library Board ROBERT PEELE PHILIP W. HENRY GEORGE C STONE JOSEPH E. POGUE The Engineering Foundation H C BELLINGER GALEN H CLEVENGER J V N DORR

Jan 1, 1923

By Thomas E. Ban, Charles D. Thompson, Charles A. Czako

Continuous sintering-a metallurgical process for more than 50 years-has broadened from its origin in nonferrous metallurgy to present-day applications in ferrous, chemical, and nonmetallic fields. During the past year, self-fluxing sinter production has been a subject of active interest to iron metallurgists in North America. Accomplishments however, have come predominantly from Europe and proper interpretation of these reports requires an understanding of European raw materials and European economics. The technology, of course, can be applied universally.

Jan 10, 1959

By A. W. Fahrenwald

Cell depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence—i.e., the depth in the pulp at which the impeller is required to produce aeration. The Flotation Machine a Compressor A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure† (14.7 Ib. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 Ib. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 Ib. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 ÷ 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the her, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. The Flotation Machine as a Pump Since, in impeller machines that rely upon their own operation to produce aeration, pulp Passes through the im-

Jan 1, 1947

By A. W. Fahrenwald

Cell depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence—i.e., the depth in the pulp at which the impeller is required to produce aeration. The Flotation Machine a Compressor A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure† (14.7 Ib. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 Ib. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 Ib. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 ÷ 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the her, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. The Flotation Machine as a Pump Since, in impeller machines that rely upon their own operation to produce aeration, pulp Passes through the im-

Jan 1, 1947

By A. W. Fahrenwald

CELL depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence-i.e., the depth in the pulp at which the impeller is required to produce aeration. THE FLOTATION MACHINE A COMPRESSOR A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure[t] (14.7 lb. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 lb. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 lb. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 [-] 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 [=] 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the finer, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. THE FLOTATION MACHINE AS A PUMP Since, in impeller machines that rely upon their own operation to produce aeration, pulp passes through the im-

Jan 1, 1946

By Paul Weir

BLEACHING clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller's earths fall within the general group of bleaching clays and gradually the commercial term "fuller's earth" has been applied to natural clays originating, for the most part, in the south-eastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States.1 Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). TABLE 1.-Physical and Chemical Composition of Different Types of Clays Composition, Per Cent Constituents and Properties Bentonite Fuller's Mud Clay (Wyoming) Earth (P Peak)' (Alluvial) Silica (SiO2) 60.0 69.6 61.67 Alumina (Al203) 19.0 14.3 20.34 Ferric oxide (Fe203) 2.8 3.90 7.70 Titanium oxide (Ti02) 0.13 0.70 1.01 Lime (CaO) 0.5 0.80 0.00 Magnesia (MgO) 2.0 1.00 0.24 Soda (Na2O) 2.4 0.40 0.31 Ignition loss 4.7 6.77 8.51 Moisture content 8.0 10.0 20.0 Isoelectric point, pH 9.2 9.2 6.5 Average swelling volume 15.0 0.0 0.0 Weight per cubic foot, lb 55.0 40.0 65.0 Material passing 200-mesh sieve, per cent 90.0 85.0 50.0

Jan 1, 1939

By Edward Keller

In a paper, " A Study of the Elimination of Impurities from Copper-Mattes, etc.," presented to the Institute at the Atlantic City meeting, February, 1898, I gave certain figures which I called the relative slaggability in refining copper. In that paper* will be found the following pertaining to this subject: Relative Slaggability in Refining Converter-Copper. Cu. Pb. Bi. Sb. As. Se, Te. 1 129.5 1.13 7.30 5.22 0.81 and Relative Slaggability in Refining Electrolytic Copper. Cu. Pb. Sb. As. 1 41 9.97 7.13 Since there is a, possibility of misinterpretation of the above values, the following supplementary information may seem justified in explanation. As the contents of impurities in the unrefined or crude copper were unknown, the contents of the refined copper were substituted therefor, merely in order to obtain the two series of figures for comparison. These figures are higher than they would be had I been able to take the correct ones for the unrefined copper. The high figure, 129.5, for lead, in the case of converter-copper, means simply that more lead was slagged from the crude copper than remained in the refined copper; or, in definite values, that to 1 per cent. of copper slagged, the ratio of the lead gone into the slag and the lead remaining in the refined copper is 129.5 : 100. It is possible to approximate the true slaggability much more closely by adding the quantities of impurities in the refined copper to those in the slag, thus obtaining values for the crude copper in which the amounts volatilized are ignored (the latter

Jan 1, 1901

By P. R. Sperry, P. A. Beck, J. Towers

Dahl and Pawlek1 found that electrolytic copper develops extremely coarse grains at 1000°C after about 90 pct reduction by rolling. This coarsening occurs only under conditions of penultimate grain size, deformation, and alloying which lead to the "cube" recrystallization texture.l,2,3,5 The peculiar angular shapes and straight grain boundaries of the coarse grains were noted by several investigator.1,4,5 On the other hand, coarsening in Fe-containing aluminum or in AI-Mn alloys8 does not depend on a "cube" (or any well developed) recrystallization texture. It is true that increasing deformation by rolling, and, therefore, an increasingly well developed re-crystallization texture, are associated with decreasing incubation periods of coarsening.6-7-8 Nevertheless, coarsening readily develops in aluminum even after only 30 pct reduction by rolling, where the recrystallization texture is very weak.6,8 Also, coarsening was observed by Jeffries9 many years ago in sintered thoriated tungsten, which presumably has no preferred orientation. In all these cases coarsening is associated with grain growth inhibition by a dispersed second phase.8,9 The annealing temperature has to be suficiently high to overcome the inhibition at a few locations. But if it is too high, growth starts at many points, and the resulting grain size becomes much smaller.9 Normally, the coarse grains are more or less equiaxed, and the boundaries have a typical ragged appearance.6.8 Cook and Macquarie4 demonstrated that, in addition to the texture-dependent coarsening previously found at 1000°C,l electrolytic tough pitch copper may also coarsen at 800°C after 50 pct reduction by cross rolling. The coarse grains formed under such conditions have rounded shapes and ragged boundaries, like those in aluminum. When the annealing temperature is higher, the tendency for their formation decreases. All these observations suggest that the coarsening at 800°C is associated with inhibition by a second phase. Actually, coarsening at 800°C after 50 pct reduction by cross rolling was observed only in tough pitch copper,4 which contains Cu2O particles. On the other hand, the texture-dependent 1000°C coarsening occurs in both tough pitch and oxygen-free copper;4 it does not appear to depend on the presence of a dispersed second phase. However, the interpretation of the 800°C coarsening in Cu after 50 pct rolling as an inhibition-dependent process, similar to the coarsening in A1-Mn alloys, is somewhat weakened by the fact that this coarsening was reported4 to occur only after cross rolling, and not after straight rolling. It was, therefore, decided to re-examine this question. A 1 in. diam electrolytic tough pitch copper rod, No. 2 hard drawn, was annealed for 20 min at 700°C, rolled to 0.5 in., annealed 10 min at 700°C, and straight rolled to 0.064 in. It was then given a penultimate anneal of 20 min at 500°C and it was cut into four sections, which were given final reductions by straight rolling as follows: A 30 pct reduction of area B 50 pct reduction of area C 70 pct reduction of area D 90 pct reduction of area Specimens cut from the four sections were finally annealed at 800°C in an oxidizing atmosphere. Strip A remained fine grained up to 10 hr, but the specimen annealed 12 hr consisted of only 2 large grains. Strip B had a few scattered large (1/2 to 3/4 mm) grains after 1 min, although the balance of the specimen consisted of fine grains of about 0.02 mm. After 5 min there were several 10 to 15 mm grains present, and after 1 hr strip B was completely coarsened. The coarse grains had the same characteristics (see Fig 1) as those obtained by Cook and Macquarie at 800°C after cross rolling. Strip C had several grains of 0.05 to 1 mm after 1 min, but it was still largely fine grained after 12 hr. After 48 hr it consisted entirely of grains of about 0.5 to 4 mm, with an extraordinarily large number of twin bands. Strip D remained com- pletely fine grained after 4 hr at 800°C. These results indicate that, in the deformation range of 30 to 70 pct reduction, the incubation period for coarsening as well as the rate of growth and the final size of the coarse grains decreases with increasing deformation. Similar

Jan 1, 1950

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain' and magnesia.' Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann'" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965