Oxidation of Metals. Chemical Engineering Fundamentals Review

Ind. Eng. Chem. , 1961, 53 (4), pp 319–324. DOI: 10.1021/ie50616a038. Publication Date: April 1961. ACS Legacy Archive. Note: In lieu of an abstract...
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Chemical Engineering Fundamentals Review

Oxidation of Metals by W. W. Smeltzer and J. M. Perrow, Department

McMaster University, Hamilton, Ontario, Canada

of Metallurgy and Metallurgical Engineering,

Ever-increasing fundamental research reflects technological pressure for more corrosion resistant materials

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JL here are incisive challenges for researchers in this field of study at commencement of the new decade. Oxida-

tion theory still remains in a state of flux because of inconclusive experimental observation. The theoretical bridge has not been constructed for the gap between oxide nucleation and layer formation; also, the roles of ion and electron transfer and line and point defect interactions remain undefined for oxidation, mechanism. Research with the most precise techniques is required to classify phenomena for theoretical interpretation. High resolution electron and field emission microscopy is a fruitful approach. The consensus of views suggests that emphasis will be placed in the future on studies of oxide film structures, composition, nucleation, and diffusion parameters. Data accumulated during the past year have demonstrated that dislocations may play an important role in formation of oxide nuclei. Although the relative magnitudes of their effects are unknown, both boundary and lattice diffusion must be considered in the growth of oxide films. Determinations of diffusion constants for oxides, which are essential for interpretation of parabolic scaling, were extended. Several notable contributions to the subject of alloy oxidation showed the importance of oxide spinel formation and stability to development of oxidation resistant materials. So voluminous is the literature that the reviewer is limited to discussion of representative reports from a continually expanding literature. As in previous years, the review covers the literature to Nov. 30, 1960.

Reviews Excellent reference texts and monographs are now available. Evans (4A) has published a comprehensive text of metallic corrosion and oxidation. This work is especially noteworthy, as it presents the pioneering approach of the research group from Cambridge University. Metallic corrosion inhibitors were discussed in a monograph by Putilova and others (14A). The proceedings of the international conference on structure properties of

thin films (13A) contain diverse studies chemisorption, oxide nucleation,. and kinetics of film growth. Investigations dealing with lattice defects in oxides and diffusion mechanisms are contained in proceedings of the kinetics of high temperature processes conference { ). Many presently known oxidation characteristics of metals and alloys for nuclear technology were summarized in a monograph (15A). Also, valuable oxidation studies and reviews were presented at the third metallurgical symposium on corrosion {17A). Several years’ work in surface oxidation at high temperatures and low oxygen pressures was reviewed by Belin (1A) and Bénard {2A). A new edition of the monograph on surface finishing of aluminum was published (19A), and the oxidation of copper (16A) and germanium (7A) was reviewed. The chemical physics and growth of ferrites was discussed by Gray (6A) and Harrison {9A). Fairman (5A) reviewed the accelerated corrosion of metals by vanadium pentoxide. The oxidation and corrosion of zirconium alloys was the topic of several reviews (3A, 10A, 12A, 20A). The technique of electron microscopy was aptly demonstrated in investigations by Gulbransen and Copan {8A) and Trozzo (78Á) on the oxidation of iron and tin, respectively. on

Theory of Oxidation Many of the complexities of oxidation

phenomena are associated with multistage processes, for as oxidation proceeds the structure of the superficial oxide film changes by heterogeneous reactions and

solid state transformations. Using refined techniques under rigorously controlled experimental conditions, investigators are gaining an insight into these

interlocking processes. The chemisorption of oxygen

on

a

thin oxide film on a metal has been compared to that on bulk oxide by Grimley {10B). Chemisorption is larger on the composite system, and, apparently, sufficient ions are present to give the electrical potential across a homogeneous film required by the Cabrera-Mott theory of film growth. Investigations were carried out on the initial oxidation stages of several metals.

The oxidation of evaporated magnesium films at low pressures and temperatures was studied by Sack {15B) and Cohen (75). In the initial period of oxidation, the sticking probability increased with the uptake of oxygen, suggesting a nucleation effect. Although the latter stages of oxidation could be represented by a logarithmic law, substantiation was not obtained for the Cabrera-Mott theory of film growth. Copper of known impurity and dislocation contents was oxidized, in a study by Young {18B), to determine the correspondence, if any, between dislocations and oxide nuclei. For crystals doped with tellurium or tin, nuclei were formed at There was no correladislocations. tion between nuclei and dislocations for high purity copper and copper doped with silicon. Bfnard and others (25, 3B) favor the viewpoint that the number of nuclei on a surface of given crystallographic orientation is dependent upon surface diffusion parameters. The physical properties of oxide layers on metals continued to be actively investigated. The effect of volume ratio, surface configuration, and plasticity on the adherence of oxide films was considered by Tylecote {16B). In the absence of plasticity, adherence at high temperature may be due to a balance between inward and outward diffusion of oxygen and metal. Spalling of adherent films can result from differential cracking on cooling. The negligible difference of the relative expansion coefficients of nickel and nickel oxide may explain the good adherence of films on nickel. Borie (55) employed a diffraction technique to measure the strain present in the thin oxide film on copper. The porosity of oxide during linear oxidation was the subject of several investigations. Aylmore and others (75) showed that the scale was porous for a number of metals by measurements of specific surface and density. The nonprotective oxide film on tantalum was examined by Cathcart and others (65) with metallographic and electron microscopic techniques. It was shown that the oxide film became nonprotective through the formation of microscopic blisterlike cracks in the oxide. AlVOL. 53, NO. 4

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relief probably plays a the mechanisms leading to porosity of oxide, experimental justification has not been advanced to this time for specific mechanisms. The Wagner diffusion formalism for parabolic oxidation can be expressed as a proportionality between a reaction and an affinity. As shown by rate Moore (12B), this is the relation postustress

though

in

role

lated by irreversible thermodynamics. This relationship was applied to several diffusion experiments. Jepson (11B) expressed the parabolic rate constant in terms of the defect concentration at one interface by introducing the free energy change for the oxidation reaction. A technique based upon controlled interruption of parabolic scaling was advanced by Rosenburg (73B) for the determination of the defect concentration and diffusion coefficient. Using neutron diffraction, Roth (7415) obtained information on the lattice defect of wustite. structure The most notable contributions to theoretical knowledge were obtained in The scaling the field of alloy oxidation. of alloys was compared to that of pure metals by Wagner (7 7B). The oxide layer and the adjoining alloy become enriched with respect to some of the alloying elements, depending on the form of the phase diagrams, on the affinities of the alloying elements for oxygen, and on the mobilities of the reactants in The the metallic and oxide phases role of the spinel oxides in the oxidation of iron and its alloys was discussed by Birchenall (4B) and Condit and others (8B). Alloying elements decrease the oxidation rate by lowering the composition range of wustite or by eliminating it as a stable phase. Additional protection may be obtained if the alloy'ing elements decrease the range of defect concentration in the spinel phase or the ion mobilities. If the decrease in the cation mobilities becomes sufficiently large, the growth rate of the spinel phases may be controlled by' anion migration. The influence of alloying elements in low concentrations on the oxidation of iron was shown by Engell (9B) to depend on their affinities for oxygen and on the reactions between their oxides and wustite.

Diffusion

constants

of oxides remain

required parameter for the elucidation of parabolic scaling of metals and alloys. The reader is referred to the monograph on the kinetics of processes at high temperatures (77A) for the advances in this field. The diffusion of oxygen in alumina and germanium oxide was studied by Oishi and Kingery (.37C) and Canina and Denoncin (73C), respectively. most

320

pressures. The literature

on

Metal Oxidation Current work is concentrated on measof diffusion and interfacial controlled reaction kinetics, structures, lattice defect types, and transport phenomena. References discussed in the text and contained in Table II include those reports which emphasize the fundamental approach. The effect of surface properties and oxide structures on the kinetics of oxidation was electrochemically investigated. Several comprehensive studies appeared the anodic oxidation of niobium. on Adams and Kao (ID) established that the measured temperature dependence of the Tafel slope agreed with that predicted by' the Cabrera-Mott theory'. A zero field interfacial barrier of 1.19 e.v. and barrier half-width of 2.40 A. were obtained. On the basis of the electrical, optical, and structural properties of these films, Young {91D) suggested a correlation between dielectric constant and ionic conductivity. This investigation and that by Bakish (71D) illustrated that the formation and crystallization phenomena of the anodic films on niobium and tantalum exhibit common characteristics. The mechanism of the anodic oxidation of aluminum was studied by Somogyi {83D) and Skoulikidis and others (79D) with respect to film growth under conditions of anodic dissolution. Lake and Casey' (57D) studied the electrical properties of the anodic film on cadmium, and Zwerdling and Sheff {93D) illustrated that a thin uniform anodic film may be formed on both n- and /)-t\'pe germanium. Empirical conclusions w'ere formulated for the formation of oxide whiskers and oriented crystallites on metals during oxidation and corrosion. The growth of copper oxide whiskers from copper at temperatures 450° to 500° C. was observed by Ftohling and others (48D). The initial growth was high, a whisker reached half its final length in 5 to 17 minutes, and after 1 hour the growth W'as very slow'. Albert and Jaenicke (2D) showed that the whisker length was limited by7 an inhibition effect.

urements

the thermodynamic

and structural properties of oxides continued to expand, the results being incorporated into current investigations of metal oxidation. Klemm and Scharf (25C) investigated the evaporation pressures of several alkali metal oxides. The substitution of metallic ions in ferrites was investigated by' Pickart (35C) and Lensen (27C). As illustrated by the research of Tuxworth and Evans continues to be (43C), information accumulated on the habit planes of oxide precipitates. Other studies of oxides are outlined in Table I.

Table

I.

Oxides Subj ect

Metal Oxides a

The self diffusion constant of zinc oxide w'as determined by Roberts and Wheeler (37C), and investigations were carried out on the diffusion of iron and chromium in several oxides by Ignatov and others (19C) and Kingery and others (24C). Moreover, the work of Izvekov (22C) demonstrated that the diffusion constants of iron in magnetite were progressively larger for lattice, boundary, and surface diffusion. Such determinations will aid in the interpretation of oxide film growth kinetics. Chemisorption studies demonstrated that the adsorption centers for oxy'gen ions on oxide surfaces are often associated with the oxide lattice defect structure. For example, Matsuura and others (29C) have shown that oxygen adsorption on zinc oxide and nickel oxide may be explained by interaction of oxygen with defects. Because of their connection with problems of extractive metallurgy, the oxidation and reduction kinetics of iron oxides have become progressively more important. The oxidation kinetics of magnetite were investigated by Paidassi and Lopez (32C) and Feitknecht and Lehmann (77C), while the reduction kinetics of iron oxides were determined by McKewan (28C) and Quets and others (36C). Because reduction involves precipitation of iron, these kinetics remain too complex for interpretation. Phillips and Mu an (34C) determined the phase relations of magnetite and hematite at high oxy'gen

Reference

ZnO Oxides of Pb, Ni, Fe, Ti SnO, CuO, CusO

Oxygen chemisorption Crystal structures

UC) (30. 70. 200, 260, 390) (210, 400, 410

U02, Ag.O, Ag2Os, ZnO Ti02

Decomposition

(20, 180, 38C, 440 (230) (60, 140 (300) (IOC, 160, 330) (80, UC, 42C, 460) (90)

Fe2Os, FesOj

Electrical conductivity and lattice defect structure Diffusion of iron Phase relationships

FesOi-CraOs-SiOj

Fe-Mg-O, Mn-Cr-O, Mn-Fe-O, V-O, U02, WOi, Zn-Fe-O Cr2Oa

Reduction kinetics Sublimation

UOs, BeO, MoOs, A1203, WOs

Thermodynamic properties

CuO

INDUSTRIAL AND ENGINEERING CHEMISTRY

(45C) (1C, 50,

120,130,150)

an

Apparently the development of the oxide film has little effect on whisker length. The corrosion products of oxide whisTable Metal A1

II.

Metal Oxidation ano-

(133D,

High temperature

cor-

(5 2D)

dic film

Be B C

Co

References 85D)

Subject Double sealing of

rosion products Oxide on sintered Be Oxidation in CO2 High temperature oxidation Oxidation by CO2 Oxidation 400°-1400°

(76D) (39D, 78D) (SSD)

(5D, 15D) (22 D)

C.

Cu

Ge

Au Fe

Mg Metals

Oxidation initiation al low temps. Surface activity of O in liquid Cu Oxidation in CO2 Limiting oxide thickness 20°-100° C. in Oxide formations H2O Oxidation for long ex-

(SOD)

(31D)

(SID) (67 D)

(26D, 53D)

(3D)

posures

of oxide Formation film Structure of rust Effect of oxygen solubility in metal on oxide formation Inhibition of oxidation

by fluorides Oxidation of powders Rate equation for forof volatile mation oxides Rate of gaseous diffusion Combustion

(21D, 24D) (90D) (27 D)

(25D) (58D) (SOD)

(35D) (49D, 55D, ,70 D)

Mo Ni Nb Pt Si

Ag Ta Sn Ti

Heat of oxygen adsorption Oxidation 450°-550° C. Oxygen chemisorption phase Metal-oxygen diagram Oxygen chemisorption

(32D, 8SD) (29D) (8SD)

(69D) (69D)

Reaction vapor

(12D)

168°-212° C. with

water

W

Oxygen chemisorption Reaction with water

U

Oxidation by CO2 Decoration oxide growth Oxidation l50°-500° C. X-Ray determination of oxide film V-O phase diagram High temperature oxidation Anodic oxidation Effect of fission fragments on oxidation Breakaway oxidation High temperature oxidation Anodic oxidation

Zn Zr

(1SD)

PtOz oxide film Solid state reaction of O in Si Anodic oxide film Ta-0 phase diagram Dielectric losses of anodic films Logarithmic oxidation

Sorption of oxygen Phase T12O

V Y

(18D)

(87D) (88D) (93D)

(56D)

(20D) (82 D, 88 D) (47 D) (46 D)

vapor

(4D) (48 D)

(10D) (S6D) (30D) (19D) (84D) (89D) (57D) (74D, 75D, 82D) (73D, 92D)

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Chemical Engineering Fundamentals Review

kers and protruding crystallites on iron were shown by Gulbransen and Copan (43D) to be several hundredfold larger in water vapor than in dry oxygen. The orientation of the oxide crystallites on and y-iron was investigated by aHaase (44D). The orientation relationship between oxide and -iron was explained by the spatial needs of oxygen ions deposited on the iron surface during the initial stage of oxidation. The interfacial controlled oxidation kinetics of iron were the subject of several investigations. Petit and others (65D) and Smeltzer (80D, 81D) have shown that the magnitudes of the linear kinetics in carbon dioxide atmospheres were directly proportional to the partial These pressures of the gaseous reactant. data confirmed the supposition that the rate-determining step involved surface processes for the dissociation of carbon dioxide into absorbed oxygen ions and incorporation of these ions into the wustite lattice. It was demonstrated by Fuller (34D) that the oxidation kinetics of iron with water vapor at elevated temperatures were governed by linear kinetics before the onset of parabolic scaling. Rahmel and Engell (68D) observed no pressure effect on the parabolic scaling of iron in oxygen between 100 and 600 mm. Sufficient information is becoming available for the interpretation of oxygen penetration into polycrystalline titanium, zirconium, and hafnium during scaling reactions. The diffusivities of oxygen in a- and /3-titanium were presented by Roe and others {7ID), and the diffusion of oxygen in hafnium was measured by Pemsler (64D). The adsorption of oxygen and oxide formation on alumina films were investigated by Eley and Wilkinson (28D). The first two monolayers of oxygen uptake were too rapid for measurement, and film growth involved electron tunnelling and cation migration. Aylmore and others (8D) investigated the high temperature oxidation of aluminum in dry oxygen. Because of crystallization of amorphous oxide, the oxidation rate decreased to a very low value. It was demonstrated by Bernard and Randall (13D) that the film formed on aluminum by the action of water at temperatures to 100° C. consisted of a hydrated oxide of high water content. As shown by Blackburn and Gulbransen (14D), the reaction of aluminum with water vapor at high temperatures promoted blister formation by hydrogen. The reaction of antimony with oxygen between 265° and 385° C. was investigated by Rosenberg and others (72D). The initial parabolic rates degenerated to linear rates controlled by the diffusion of gaseous antimony trioxide from the surface. The initial

layer of trioxide

supported

a

further

growth of pentoxide.

The oxidation of beryllium over the temperature range 500° to 1300° C. was investigated by Aylmore and others (9D) and Bradshaw (17D). Parabolic and linear oxidation corresponded to regions of protective and nonprotective oxidation. Discontinuities in rate curves were ascribed to crack-heal growth. The oxidation of calcium was investigated by Gregg and Jepson (40D). Below 475° C., the oxide film exhibited protective properties. A breakaway reaction occurred at 550° C. and above, with formation of a yellow oxide. Utilization of the semiconducting properties of germanium is dependent upon its oxidation characteristics. Ligenza (54D) demonstrated that the time laws during initial stages of oxidation change with temperature and the extent of oxidation. Results on the high temperature oxidation characterisintertics of single crystal faces were preted by Gouskov (38D) in terms of oxide volatilities. Niobium was shown, by Aylmore and others (7D) and Argent and Phelps (6D), to oxidize in a complex manner between 350° and 1050° G. The oxide film was protective at 350° C., but at higher temperatures a linear law was obeyed with an anomalous temperature This characteristic and coefficient. anomalies in oxidation rates were explained by departures from oxide stoichiometry and by sintering effects. As shown by Cathcart and Smith (23D), potassium and rubidium also form protective films at very low temperatures which break away at temperatures lower than for sodium. An extensive investigation of the oxidation of tungsten over the temperature range 500° to 1030° C. by Gulbransen and Andrew (41D) demonstrated many of the oxidation characteristics of the refractory metals. The rate data fitted to the parabolic law showed a number of deviations and transitions caused by preferential oxidation and breakdown of the scale. The rate of oxidation was limited by oxide volatility and oxygen diffusion to the surface. Marker measurements were employed by Schnizlein and others (77D) to identify the diffusing species in uranium oxidation, and Gulbransen and Andrew (42D) have proposed the application of hydrogen permeation for studying protective oxide films on zirconium.

Alloy Oxidation Much research on alloy oxidation dealt with the properties required for formation of protective oxide layers, with film breakdown, and with empirical correlation of oxidation characteristics with compositions and structures of the VOL. 53, NO. 4

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oxide layer and metal substrate. The kinetics of alloy oxidation remained under active investigation, and electron microscopy and radioisotopes were more widely used for elucidation of structural and diffusion parameters. Investigators dealt with factors of internal oxidation. Gatti and Fullman (20E) examined the recrystallization kinetics and tensile properties of internally oxidized aluminum-silver alloys. Under the experimental conditions chosen, a very fine dispersion of alumina with particle size of 50 to 100 A. radius was produced. This dispersion increased markedly the yield strength of the alloy. Also, Wood (66E) studied the mechanical properties of internally oxidized copper-aluminum alloys. Some factors affecting the intergranular brittleness of internally oxidized alloys were examined by Seebohn and Martin (48E). Selective corrosion of aluminum-iron-nickel alloys between solid solution and eutectic was shown by Lelong and others (30E) to cause total destruction. The mechanism of protective scale formation on copper-base alloys was investigated by Blade and Preece (3E) and Sartell and others (46E). The formation of a continuous oxide film at the scale/metal interface of the alloying element occurred at a critical concentration of the latter. In the case of copper-nickel-magnesium alloys, the formation of a solid solution with magnesia markedly reduced the oxidation rates.

Table III. Alloy Al-Cu Cu-Al Cu alloys Cu-Ni Cu-Zn Fe-Al Fe-Cu-Al Fe-Si-Al Fe-S Liquid alloys

Mg-Be

Ni Ni-Al-Cr Ni-Cr Ni-Cr-Al Ni-Mn

Refractory alloys SIC

Ag-Cr-Ti Steel

Th-Zr TIB, TIC Ti-Fe Ti-Ni U-Mo Zr alloys Zr-Nb

Zr-Nb-Sn Zr-Sn

322

Investigators have continued work on the oxidation of binary iron alloys under selected conditions in attempts to correlate empirically their behavior with properties of the surface layers. Brauns and others (9E) studied the effect of alloying elements on shifting the nonvariant eutectic point betw'een iron, wustite, and magnetite, and Seybolt (50E') equilibrated the scale with the iron-chromium metal substrate to obtain isothermal phase diagrams. As

illustrated by the high temperature investigations of Foley and Guare (17E) and Seybolt (51E), iron-nickel alloys oxidize for short exposures by a parabolic relation, whereas iron-silicon alloys oxidize in a complicated manner ow'ing to order-disorder phenomena. Although high quality research w'as completed on the ternary iron alloys and steels, little inroad has been made in the understanding of their corrosion resistance. In steels alloyed with chromium or aluminum, Bénard and others (2E) have showrn that a rapid and transitory acceleration of oxidation occurs after exposure to air. Radovich (42E) examined the effect of silicon on the high temperature oxidation of stainwas inless steels. As silicon content creased, oxidation resistance increased rapidly. An enrichment of chromium at the metal/oxide interface and in the oxide film retarded the outward diffusion of iron to form oxide. Sugiyama and others (59E-61E) and Pfeiffer (40E) have

Alloy Oxidalion Reference

Subject Reaction with steam Oxidation kinetics Internal oxidation and electrical Oxidation characteristics Corrosion products

resistance

Scale structures Rust formation Scale structure Scale structure Oxide scale structure Oxidation characteristics Oxidation resistance of binary alloys Oxidation resistance Oxidation of electrodeposits Internal oxidation Oxidation kinetics Oxidation resistance Gas diffusion in silica layer Internal oxidation Scaling of cast iron Effect of oxygen on passivity Corrosion products Diffusion of Cr Breakdown of protective film Oxidation in CO2 Oxidation resistance Oxidation resistance Oxidation characteristics Stabilization by oxygen Oxide scale properties Reaction with steam

Oxidation kinetics Corrosion film Oxidation kinetics

INDUSTRIAL AND ENGINEERING CHEMISTRY

(65 E) (.18E)

(13E) (7E. 8E) (26E) (S6E) (3 IE) (58E)

(IE)

(52E, 06E) (S3E)

(24E, 63E) (62E) USE)

U7E) (22E) (5SE) (64E) (55E) UE, 10E, 19E, 2SE) (21E) (57 E) (45E) (54E) (5E) (27E) (34E, 38E) (58E) (37E) (29E) (HE, 12E, 25E, 39E, 42E) (68E, 69E)

U4E)

(28E, 32E, 35E)

applied the techniques of electron mi-

and croscopy to interpret the structures compositions of oxide films. The high temperature oxidation behavior of nickel-copper alloys was compared to the parabolic law by Yamashina and others (67E). The composition of the scales were deterand structure mined. Semmel (49E) has show'n that the addition of tungsten to niobium increased its oxidation resistance. Several empirical investigations were carried out on the effect of alloying additions on the oxidation characterisSamo and others tics of zirconium. (44E) demonstrated that the addition of tellurium prolonged the time for breakaway oxidation. The oxidation of 20 binary zirconium alloys at 700° C. w'as examined by Porte and others (41E) Diffraction studies indicated that the breakaway coincided with a polymorphic transformation in the zirconia film. The relation of electron configuration to passivity of transition metal alloys w'as investigated by Bond and Uhlig (6E) and Feller and Uhlig (16E). The effect of electron configuration maybe explained by an electron interaction betw-een chromium and iron w-hich is distinct from the interaction between and nickel. Draley and chromium others (15E) investigated the effect of gamma quenching and aging on the corrosion resistance of uranium alloys. Other reports are listed in Table III.

Lirerature Cited Reviews (1A) Belin, P., Corrosion et anti-corrosion 8, 96, 140 (I960). (2A) Bénard, J., Ind. chim. beige 24, 1328 (1959). (3A) Bost, W. E., U. S. Atomic Energy Comm. TID-3548, March 1960. (4A) Evans, U. R., “The Corrosion and Oxidation of Metals,” St. Martin’s Press, New York, 1960. (5A) Fairman, L., Chem. & Ind. (London) 46, 1436 (1959). (6A) Grav, T. J.. U. S. Govt. Research Refits. 32, 26 (1959). (7A) Green, M., Progress in Semi-Conductors 4, 35 (1960). (8A Gulbransen, E. A., Copan, T. P., Am. Soc. Testing Materials, Spec. Tech. Publ. No. 256, 44 (1960). (9A) Harrison, F. W., Research (London) 12, 395 (1959). (10A) Hoch, M., Wright Air Development Command WADC TR59-539 (1959) (11 A) Kingery, W. D., ed., “Kinet. HighTemp. Processes,” Conf., Dedham, Mass., 1958, Wiley, New York, 1959. (12A) Kofstad, P., Svensk. Kem. Tidskrijt 72, 69 (1960). (13A) Neugebauer, C. A., Newkirk, J. B., Vermilyea, D. A., eds., “Structure Properties Thin Films,” Proc. Intern. Conf., Bolton Landing, N. Y., 1959, Wiley, New York, 1959. (14A) Putilova, I. N., Balezin, S. A., Corrosion Barannik, U. P., “Metallic Inhibitors,” Pergamon Press, New- York, .

1960.

(15A) “Reactive-Metals,” Proc. Third Annual Conf., Buffalo, N. Y., 1958, Vol. II, Interscience, New York, 195

an

(16A) Ronnquist, A., Fischmeister, H.,

J. Inst. Metals 89, 65 (1960). (17A) “Third Metallurgical Symposium on Corrosion,” Centre d’Etudes Nucleaires de Saslay, Gif-sur-Yvette, France, and North Publishing Co., Amsterdam, 1960. (18A) Trozzo, P. S., Am. Soc. Testing Materials, Spec. Tech. Publ. No. 262, 57 (1959). (19A) Wernick, S., Pinner, R., “Surface Treatment of Al and its Alloys,” 2nd ed., Robert Draper Ltd., Teddington, England, 1959. (20A) Zima, G. E., U. S. Atomic Energy Comm. HW-60908, 1959.

Theory (IB) Aylmore, D. W., Gregg,

S. J., Jepson, W. B., J. Electrochem. Soc. 106, 1010 (1959). (2B) Bénard, J., Acta Met. 8, 272 (1960). (3B) Bénard, J., Gronlund, F., others, Z. Elektrochem. 63, 799 (1959). (4B) Birchen all, C. E., Ibid., 63, 790 (1959). (5B) Borie, B., Acta Cryst. 13, 542 (1960). (6B) Cathcart, J. V., Bakish, R., Norton, D. R., J. Electrochem. Soc. 107, 668 (1960). (7B) Cohen, M. S., Acta Met. 8, 356 (I960). (8B) Condit, R, H., Brabera, M. J., Birchenall, C. E., Trans. Am. Inst. Mining, Met., Petrol. Engrs. 218, 768 (1960). (9B) Engell, H. J., Z. Elektrochem. 63, 835 (1959). (IOB) Grimley, T. B., Discussions Faraday Soc. 28, 223 (1959). (1 IB) Jepson, W. B., J. Electrochem. Soc. 107, 53 (1960). (12B) Moore, W. J., Z. Elektrochem. 63, 794 (1959) (13B) Rosenburg, A. J., J. Electrochem. Soc. 107, 795 (I960). (14B) Roth, W. L., Acta Cryst. 13, 140 (1960) (15B) Sack, ., Z. Elektrochem. 63, 806 (1959) (16B) Tylecote, R. F., J. Iron Steel Inst. {London) 195, 135, 380 (1960). (17B) Wagner, C., Z. Elektrochem. 63, 772 (1959) (18B) Young, F. W., Jr., Acta Met. 8, 117 (1960) Metal Oxides (IC) Ackermann, R. J., Thorn, R. J., others, J. Phys. Chem. 64, 350 (1960). (2C) Anderson, J. S., Sawyer, J. O., others, Nature 185, 915 (1960). (3C) Anderson, J. S., Sterns, M., J. Inorg. & Nuclear Chem. 11, 272 (1959). (4C) Barry, T. I., Stone, F. S., Proc. Roy. Soc. {London) 255A, 124 (1960). (5C) Belykh, L. P., Nesmeyanov, A. N., Doklady Akad. Nauk S.S.S.R. 128, 979 (1959). (6C) Blackman, M., Kaye, G., Proc. Roy. Soc. {London) 75, 364 (1960). (7C) Bogatskii, D. P., Mineeva, I. A., Zhur. Obshchei Khim. 29, 1382 (1959). (8C) Bogdanova, N. I., Ariya, S. M., Ibid., 30, 3 (1960). (9C) Bond, W. D., Clark, W. E., U. S. Atomic Energy Comm. ORWL-2815, .

.

.

.

1960.

(IOC) Broz, J., Krupicka, S., Zaveta, K., Czechoslov. J. Phys. 9, 481 (1959). (11C) Bórdese, A., Gazz. chim. ital. 89, 718 (1959). (12C) Burns, R. O., DeMaria, G., others, J. Chem. Phys. 32, 1363 (1960). (13C) Canina, V. G., Denoncin, J., Compt. rend. 250, 1815 (1960). (14C) Carter, R. E., J. Am. Ceram. Soc. 43, 448 (1960). (15C) Dowart, J., DeMaria, G., others, J. Chem. Phys. 32, 1366, 1373 (1960). (16C) Edwards, P. L., Phys. Rev. 116, 294 (1959). '

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(17C) Feitknecht, W., Lehmann, H. W., Helv. Chim. Acta 42, 2035 (1959). (18C) Herley, P. J., Prout, E. G., J. Am. Chem. Soc. 82, 1540

(I960).

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