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The Mechanism of Scale Formation On Iron at High Temperature « By B. W. DUNNINGTON,"» F, H. BECK) and M. G. FONTANA“ Introduction ODERN APPLICATIONS in jet engines and gas turbines require metals that will success- fully resist extreme temperature conditions. Scaling in the oxidizing atmospheres that are used in these and other high temperature applications is a problem of prime importance. In order to design alloys with satisfactory oxidation resistance the metallurgist needs, among other things, a knowledge of the rates and mechanisms of oxidation of the pure metals. Many accurate rate measurements are available for a variety of useful metals. Information on mecha- nisms of oxidation is still in an embryonic stage Investigations conducted in an attempt to explain mechanisms are frequently studies of weight change with time.» Recently several investigators have studied oxide growth by microscopic methods.* One of the main purposes of this investigation was a comparison of the two above procedures, Weight measurements result in an averaging over’ the entire surface. Microscopic examination may be made at a particular’ point so that, if one section is reacting differently from another, this may be noted and measured, In addition to comparing rates derived by the two different methods, microscopic examination has re- vealed a series of new oxide structures and modes of occurrence. Literature Survey There is general agreement that the formation of an oxide layer is a diffusion process. The theoretical treatment of Wagner® permits evaluation of the rate constant of oxidation from certain erystal properties. Usually these values are not known so that it is still necessary to actually run oxidation tests and measure the rates. However, several systems have been in- vestigated® sufficiently to demonstrate that Wag- ners treatment is correct. The oxides are composed of ionic erystals in -which the components (anions, cations and electrons) diffuse as charged particles. Diffusion across the oxide layer forming on a pure metal requires a concentration gradient. This means that the oxide must vary from the stoichiometric composition, even though no variation is detectable by existing analytical means. Wustite (FeO) is a metal deficient lattice and may exist with several 4 Submitted for publication July 12, 1961 {G) Research Associate, ‘The Ohio Stato University Research Founda Hon, The ‘Ohio Blate University, Columbus, Onto, (2) Asslotant Research Profesor, Kngineoring, Experiment. Station, he Ohio Hate University. (2) Professor and Chairman, Department of Motallursy, ‘The Onio State “University Abstract A new mechanism of high temperature oxidation of iron, is proposed. Diffusion of lattice vacancies in the iron is shown to influence the type of oxide that forms. Tt was found that with thin specimens an ad- herent film grew on one side and a loose filin on the gther. The adherent film followed the parabolic law. ‘The loose film grew in a pseudo-linear manner. The formation of these two types of films is shown to be necessary from consideration of diffusion of iron through the metal and oxide lattices. Applying the same principles to large specimens it is shown that a different kind of oxide layer forms which was observed by Pfeil, Photographs of magnetite slowly cooled from a high temperature indicate that a plate-like precipitate of Fe,Os forms on the [111] planes of the magnetite. A brief study was made of blistering, It is demon- strated that superficial blisters form on heating in air and photographs show the later positions of the blisters as the oxide layers grow thicker percent of the iron sites vacant.™ Magnetite (FesO.) is also a metal deficient structure but has a smaller range of variation than wustite. Neither of these two oxides exist with greater than the stoichiometric amount of iron. Hematite (Fe,O,) is an oxygen de- ficient structure but no range in composition is de- tectable.* The diffusion process may be assumed to be due to the movement of vacant lattice sites, or in some cases, not considered here, interstitial movement of ions. If only vacant cation sites exist then only cations will be expected to diffuse. On this basis, FeO and Fe,O, should diffuse only iron and Fe,O, should diffuse only oxygen. Birchenall? has recently meas- ured the diffusion coefficients of the components of these compounds. His work supports the considera~ tions above. Various investigators have .reported on the ap- pearance of the oxide layers. Pfeil? demonstrated that the surface of metal retreats during oxidation. The area between the original and final positions of the iron is occupied by a loose aggloineration of oxide (herein referred to as the “Pfeil layer”). This work was on specimens 34-inch in diameter. Others*®# have studied polished cross-sections in which three continuous coherent layers appeared with the FeO directly in contact with the iron. Most of that work was done on fairly thin sheets or thin wires. The importance of the difference in occurrence of the oxides on large and small specimens has not previ ously been mentioned, Apparatus All of the oxidation tests described below. were run in the vertical tube furnace illustrated in Figure January, 1952 1. This equipment with certain improvements is essentially that previously described? Gases passed into the furnace were dried as indicated. Any residual oxygen in the argon was removed by passing over hot magnesium turnings. The valves between the drying train and furnace permitted routing the gas through the furnace tube in either direction. Tem- perature was controlled to within +10 degrees F (5 degrees C). Continuous weighings were made in certain tests by use of the analytical balance set directly above the furnace tube. There is a moveable Pyrex extension ‘on the upper end of the furnace tube which may be raised far enough to insert the sample. The specimen is hung on a hook at the end of a platinum wire. The Pyrex tube and furnace tube is connected by a ground bevel joint. After assembly it was sealed by wrap- ping with electrical Scotch tape. Hardness measure- ments were made on a Bergsman microhardness tester. Experimental Procedure ‘The majority of these experiments were conducted on Armco iron sheets provided by Westinghouse Electric Corp. through Dr. J. K. Stanley. This mate- rial was received rolled to size and was stress re- lieved by holding for one hour at 1400 degrees F (760 degrees C). Impurities present in the material are: Total Carbon 0.028 We. % Manganese 0.019 Phosphorus 0,007 Sulphur ost si 0.006 0.007 Specimens 2 em square were cut from a sheet 0.16 em thick for the microscopic work. Specimens used in the continuous weighing experiments were 3.80 x 10.25 cm cut from the same 0.16 cm sheet. The wire specimens were 2 cm lengths of 0.8 mm iron wire. Composition of this wire was approximately the same as that of the Armco iron sheets. All specimens were polished by hand with 280-grit silicon carbide paper, followed by $00 grit. The surface was then cleaned with 20 percent HCI, washed in acetone and dried before oxidation. Manipulation of the furnace was arranged so that the specimen was not in contact with oxygen until it reached test temperature. After having been sealed in the furnace the specimen was held in the:cold zone while the’entire system was flushed with tank argon from which oxygen and water vapor had been re- moved by suitable purifying trains. When the system was completely flushed the specimen was lowered into the constant temperature zone. Once the speci- men was up to temperature, dried oxygen was sent through the furnace tube and the test started. At the end of each test the specimen was quickly raised into the cold zone, where it cooled to below 300 de- grees F in less than one minute, In the case of continuous weighing tests, the plat- inum wire passed to the balance through a 1/16-inch hole in a thin Teflon disk on the top end of the Pyrex extension. Arrangements were made to move the disk without disturbing the seal, so that the wire could always be centered and binding prevented. MECHANISM OF SCALE FORMATION AT HIGH TEMPERATURE 3 frogenane [POE ri F = Er as r= = Figure 1—Experimental oxidation apparatus with controlled atmosphere. omy Contamination due to diffusion of air in through this orifice was successfully prevented, by running at least four liters of gas per minute vertically through the 2-inch diameter furnace tube. Metallographic mounting and polishing of the oxi- dized specimens was the most difficult procedure to establish. Successful mounts were made both in low temperature casting resins such as used by Stanley,! and in Woods metal. Contamination of polishing wheels discourages the use of the latter. ‘The polishing method finally settled upon con- sisted of three steps: 1) Rough polishing-dry grind- ing on a 280-grit belt grinder down to the desired cross-section followed by wet hand grinding on 280 silicon carbide, Extreme care is necessary in this step. 2) Intermediate Polishing—wet polishing on a rapidly rotating wax wheel using first a soap solu- tion of 3F silicon carbide and then of alpha alumina. 3) Final Polishing—not critical, may be either on wax or cloth and with a variety of polishing agents. AlsOs, Fe.O3, and MgO were all excellent, Use of a deep piled cloth tends to round the edges of small voids. Etching was accomplished with 20 percent HCl. This solution attacks the oxide in the decreasing order FeO-Fe,O,-Fe:03, Results and Discussion Measurement of Oxide Thicknesses The thickness of FeO and Fe,O, were measured from a series of tests at 2000 degrees F (1090 de- grees C). FeO, thicknesses cannot accurately be de- termined because the layer is rounded off during polishing. Careful study with the microscope reveals that the thickness of Fe.O, increases with time, but it was impossible to record it photographically be- cause of insufficient depth of focus. A method of coating the oxide with some hard material must be developed before precise measurements on the outer layer will be feasible. A plot of thickness vs. time is given for FeO and 4 CORKOSION—-NATIONAL ASSOCIATION OF CORROSION ENGINEERS Vols le eo os 4 ra _ e |f— E £ ol 8 ow 08! ee + — Figure 4—Oxide scale on Armco irom after five minutes at 2000 degrees | {90 eares Conon side of same’ specimen ox in Figure 3 Ysa separoted oxide. X260, Etchant 20 percent HCL 1 2 3 + Time in hours 1¢ 2Thickness measurements of adherent oxide films on Armco iron ot 2000 degrees F (1090 degrees C) in pure oxygen, Measurements from photomicrographs. Figure 3Oxide scale on Armco iron after five minutes in pure oxygen. ‘an adherent oxide, X260. Etchant 20 percent HCI. Fe,O, in Figure 2, The measurements were taken directly from photomicrographs. The thicknesses plotted above are in each case from measttrements taken on an adherent scale. It is important to note that in every case only about one half of the surface was covered with an adherent oxide. The oxide on the remaining surface had sep- arated from the metal, and occurred in a great variety of relative thicknesses. No constant relationship among the oxide layers occurred on the separated oxide. Figures 3 to 6 show examples of such be- havior. In Figures 3 and 5 the Fe,O, layer is not resolved, but there is a thin one present. The precipi- tation in the FeO phase is Fe,O, formed by cooling below about 1060 degrees F (570 degrees C). It will be discussed in detail later. The iron undergoes more contraction on cooling than the oxide, so only rarely is any part of the oxide ‘on flat specimens still ad- herent after cooling. That part which was adherent at temperature may be identified by the smaller amounts of FesQ, that precipitate and the concen- tration gradient of the precipitate. Figure 5 illustrates well the adherent type while Figure 6 shows the indications of separation of metal and oxide. Figures 8 through 12 further illustrate different structures all occurring on the same specimen, Figure 7 is a key to Figures 8 through 12. A more quantitative means of determining separation is by measuring FeO/FesOx thickness ratios over the entire surface. It will be found that this ratio varies up to a maximum. The maximum represents the lowest state of oxidation of the film and, therefore, the portion which was in contact with the metal. Figure 12 shows a transition between adherent and separated oxide. Almost with- out exception, the oxide on one complete side of a specimen was adherent, while the opposite side was separated. Cooling cracks may be observed, but it is easy to distinguish a cooling crack and a separation at temperature. The latter is always accompanied by transformation to a higher oxide. It becomes increasingly apparent that studies of adherent oxide represent only a portion of the total oxidation process. Complementary experiments on iron wires show similar results, An adherent oxide forms on one side with a thinner more highly oxi- dized layer on the opposite side as shown by Figure 13. Figure 14 is a schematic diagram of the oxidation process on.a small iron wire. It is apparent that for thin sheets and wires there is a controlling influence of one side of the piece upon the opposite side. It appears reasonably certain that for the adherent oxide the Fe/FeO interface remains practically fixed in space. If the FeO reaction occurs solely by dif-