METAL 2003 20. - 22. 5. 2003 Hradec nad Moravicí __________________________________________________________________________________________ _ THE OXIDATION’S KINETICS OF SOME HIGH ALLOYED STEELS Maciej Hajduga, Dariusz Jędrzejczyk University of Bielsko-Biała, Material’s Engineering Department, Willowa 2, 43-309 Bielsko-Biała, Poland, E-mail:[email protected] Abstract The results of surface oxidation and decarburization of (Fe,C,Mn,Si,Cr,Ni) steels are reported. The oxidation anneals were carried out at temperatures T= 980, 1020, 1060, 1100 °C. The aim of presented experiment was to compare typical alloyed steel behavior in the same high temperature corrosion conditions. The estimated oxidation kinetics in connection with later microstructure investigations and measurements of decarburized thickness layer will allow for complex evaluation of examined steels. It follows from the experiment that according to expectations steel H18N9S that belongs to the heat-resisting group characterizes with greatest resistance against influence of high temperature. On special attention deserve fact that the measurement indicate decreasing of the sample weight. This process is systematical and with increasing of oxidation time and temperature the weight of oxidized samples decrease. Among the rest of materials the high resistance against the high temperature shows steel: NC10 and SW18. Steel SK5 is situated in the middle of the range of weight increase, whereas steel: 11G2 and ŁH15 show weight increases nearing to the greatest. 1. INTRODUCTION The high temperature atmospheric corrosion is the most frequent example of chemical corrosion and brings serious loses in chemical industry, power engineering, air and road transport. The corrosion wear has essential influence on the lifetime both steel constructions and machine elements. Atmospheric corrosion cause also the considerable loses during metals production treatment. According to the statistical data about 1/3 of metallic materials is withdrawn from uses in consequence of damages caused corrosion [1, 2]. Naturally part of these materials is used again among other things as the charge materials in metallurgical process, however about 10% of material is irrevocably lost. During the production of hot working elements about 7% of treated material creates the scale layer and makes in this way receiving of high quality product more difficult. Total elimination of losses caused by corrosion is not possible. However advisable is aspiration for it’s limitation both by suitable protection and by exact recognition of rights ruling corrosion. The most of papers and monographs published till now refers to the oxidation process of the samples corresponding to semi-infinitive plane. Results of these investigations find practical application in relation to some constructional elements and mainly to thin steel sheet. Considering the practical application of cylindrical shape products (rods, wires), authors from many years lead research regarding the oxidation of the cylindrical shaped samples with diameter 3-50 mm [3-5]. It was stated among others thing that the oxidation process of the sample with small diameter differs essentially from the oxidation of the flat samples, and it’s kinetics could be described by exponential equation, whereas the kinetics of flat samples is usually described by parabolic equation. One of the methods of enlarging the steel resistance against corrosion is the proper chemical composition choice of alloys working in corrosion circumstances. Most often introduced alloyed elements are chromium and nickel. 1 METAL 2003 20. - 22. 5. 2003 Hradec nad Moravicí __________________________________________________________________________________________ _ The aim of presented experiment was to compare typical alloyed steel behavior in the same high temperature corrosion conditions. The estimated oxidation kinetics in connection with later microstructure investigations and measurements of decarburized thickness layer will allow on complex evaluation of examined steels. 2. THE OWN INVESTIGATIONS The experiment was realized using cylindrical shape samples turned from typical alloyed steel presented in table 1. The example of speciment appearance after oxidation is presented at Fig. 1. a) b) Figure 1. An example of specimens appearance after oxidation – steel SW7Mo; a – T = 9800C, t = 1000 min, b – T = 10200C, t = 1000 min. Table 1. Chemical composition of materials used in the experiment, %. Steel design. Chemical composition, % ŁH15 C 0,79 Mn 0,2÷0,4 11G2 0,93 11,5 H18N9S 0,07 SW18 0,80 55 0,55 NC10 1,60 max. 2,0 max. 0,4 0,50÷ 0,80 ab. 0,4 SW7Mo 0,79 ab. 0,30 ab. 0,25 SK5 1,06 max. 0,40 Si 0,15÷ 0,35 0,4÷0,7 0,8÷1,5 max. 0,5 0,17÷ 0,37 ab. 0,4 max. 0,40 P max. 0,027 max. 0,10 max. 0,035 max. 0,03 max. 0,040 max. 0,03 max. 0,030 max. 0,03 S max. 0,02 max. 0,030 max. 0,03 max. 0,03 max. 0,040 max. 0,03 max. 0,030 max. 0,03 Cr 1,40 17,0÷ 20,0 4,0 max. 0,25 13,0 ab. 4,00 3,80÷ 4,80 Ni max. 0,3 - Cu max. 0,25 - 11,4 - ab. 18%W; 1,25%V max. 0,30 - max. 0,30 - ab.6,5%W; ok. 2,00%V; 5,5% Mo 16,6÷19,5%W; max.0,40%Ni; 1,2÷1,7%V; 4,9%Co Sample with diameter φ=30 mm and length l =20 mm after polishing were oxidized in silite chamber furnace PKS 600/25. The experiment was conducted in four different 2 METAL 2003 20. - 22. 5. 2003 Hradec nad Moravicí __________________________________________________________________________________________ _ temperature levels – 980, 1020, 1060 and 1100 0C. Samples were taken from the furnace one by one after: 250, 400, 700 and 1000 min. After cooling samples were exactly measured and weighted, then the scale layer was removed and the metallographic specimens were prepared perpendicularly to the cylinder axis to enable structure observation and micro-hardness measurement. For these research the optical microscope NEOPHOT-2 and durometer DURIMET-20K were used. 3. RESULTS’ ANALYSIS Because investigations relating to the micro-hardness measurements and structure analysis are in the course of executing, the presented analysis will refers only to the oxidation kinetics of tested materials. Data regarding internal materials’ structure, micro-hardness measurements and estimated diffusion coefficients will be published gradually depending on the progress of research work. a) Weight increase,g increase,g Weight H18N9S SW7Mo b) 200 20 0 15 -0,2 400 600 800 1000 1100 1060 1020 980 10 -0,4 5 -0,6 0 -0,8 200 400 600 min 800 Time, Time min 1000 Figure 2. The kinetics of oxidation of steel H18N9S and SW7Mo At the Fig. 2 the results of the weight change for two extreme materials: steel H18N9S, in chance of which in every oxidation temperature the weight decreasing was stated and steel SW7Mo, which shows the greatest weight increase. Only in chance of steel H18N9S the weight decrease was stated, the rest of materials showed systematical weight increase. The maximal relative weight increase of steel SW7Mo was about 14% (T = 1020 0C, t = 1000 min.), considering the initial sample weight about 114g. The final confrontation of obtained weight measurements is presented at Fig. 3. Not typical – maximal weight increase of steel SW7Mo was measured at temperature 1020 C (see Fig.1). Such material behaviour could be explained by scale layer structure covering sample oxidized at this temperature level. The observed scale was cracked and distorted. There was no similar scale layer both in higher and lower temperature of oxidation. It follows from presented results that according to expectations steel H18N9S that belongs to heat-resisting group characterizes with greatest resistance against influence of high temperature. On special attention deserve fact that the measurement indicate decreasing of the 0 3 METAL 2003 20. - 22. 5. 2003 Hradec nad Moravicí __________________________________________________________________________________________ _ sample weight. This process is systematical and with increasing of oxidation time and temperature the weight of oxidized samples decrease. Although differences between the initial and final weight are not large and reach about 0.7g, which mean decreasing about 0.7%, the stated trend shows rather, that this dependence it is not result of measuring error. Among the rest of materials the high resistance against the high temperature corrosion shows steel: NC10 and SW18. Steel SK5 is situated in the middle of the weight increase range, whereas steel: 11G2 and ŁH15 show weight increases nearing to the greatest. a) b) 980 oC ŁH15 11G2 H18N9S SW18 7 5 3 55 NC10 SW7Mo 1 SK5 15 Weight increase, g Weight increase,g 9 500 800 13 11 9 7 5 3 1 -1 200 1020 oC 17 -1 200 1100 500 800 1100 Time, min Time, min c) d) o 1060 oC 9 9 Weight increase,g Weight increase,g 7 5 3 1 7 5 3 1 -1 200 1100 C 500 800 -1 1100 200 Time, min 500 Time, min 800 1100 Figure 3. The kinetics of oxidation the investigated alloyed steel at different temperature level: a- 980 0C, b – 1020 0C, c – 1060 0C, d – 1100 0C. 4. CONCLUSIONS 1. 2. Among the investigated steels the greatest resistance against influence of the high temperature expressed by weight increase reveals steel H18N9S (in the range of temperature 980-1100 0C, within time 250-1000min). Unexpectedly, the relatively large weight increase (about 14% of initial value) was measured for steel SW7Mo in oxidation temperature 1020 0C. Both in lower and higher temperature of oxidation such surrosion was not stated. 4 METAL 2003 20. - 22. 5. 2003 Hradec nad Moravicí __________________________________________________________________________________________ _ 3. The complex resistance estimation of examined materials against the high temperature corrosion demands further investigation - measurements of: scale layer thickness, decarburized layer thickness, micro-hardness of subsurface layer and X-ray microanalyze. BIBLIOGRAPHY 1. KUčERA J., HAJDUGA M.: High-temperature and long-time oxidation of iron and steels; Edt. PŁ Filia w Bielsku-Białej, 1998, p.88. 2. KLESNIL M., LUKAS P.: Fatigue of Metallic Materials, ACADEMIA Praha, 1992 3. HAJDUGA M., JĘDRZEJCZYK D., JURASZ Z.: Influence of Fe-samples diameter on the process of oxidation at high temperature. METAL’99. 8th International Metallurgical Symposium 11-13.05.1999. Ostrava Czech Republic. Proceedings V.4., pp. 33-38. 4. HAJDUGA M., JĘDRZEJCZYK D., JURASZ Z.: High temperature time dependence of Fe-C samples oxidation. EDEM’99. International Conference on Environmental Degradation of Engineering Materials. 19-23.09.1999. Gdańsk-Jurata. Poland. Proceedings pp.119-127. 5. HAJDUGA M., JĘDRZEJCZYK D.: The influence of high-temperature oxidation on decarburization, hardness and on fatigue limit in Fe-C-Cr-Mn-Si steels. KSCS 2000. 3rd Kurt Schwabe Corrosion Symposium. August 30 – September 2, 2000. Zakopane. 5
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