ECCC Creep Conference, 1214 September 2005, London.

etd@etd1.co.uk

Influence of Normalizing Heat Treatment on Precipitation Behavior in Modified 9Cr-1Mo Steel

Masataka Yoshino1), Yoshinao Mishima1), Yoshiaki Toda2), Hideaki Kushima2), Kota Sawada2) and Kazuhiro Kimura2) 1) Tokyo Institute of Technology, Japan. 2) National Institute for Materials Science, Japan.
Abstract Precipitation behavior during normalizing heat treatment has been investigated on modified 9Cr-1Mo steel. Heterogeneously distributed spherical MX particles and platelet M3C were observed in the as normalized condition. Number of the precipitates decreased with increasing normalizing temperature and no precipitates was observed after normalizing at 1250oC. The size of MX increased with increase in normalizing temperature up to 1200oC. For MX, not only size, but also composition of metallic elements was influenced by normalizing temperature. Since equilibrium composition of MX depends on temperature, MX particle with non-equilibrium composition dissolves and precipitation of it takes place with its equilibrium composition at the normalizing temperature. A phase field diagram of NbX-VX quasi binary system in modified 9Cr-1Mo steel was experimentally determined. It has been supposed that precipitation of M3C takes place during cooling from normalizing temperature in the surrounding area of MX particles where the concentration of niobium and vanadium in matrix is poor. Keywords: ferritic creep resistant steel; modified 9Cr-1Mo steel; MX; M3C; phase equilibrium; precipitation behavior; two-phase separation; normalizing 1. Introduction High Cr ferritic creep resistant steels such as a modified 9Cr-1Mo steel (ASME P91/T91) have been widely used as materials for high temperature structural components such as header and main steam pipe in power generation plant. High strength ferritic creep resistant steels are usually subjected to normalizing and tempering heat treatment prior to service and, therefore, microstructure of those is a tempered martensite. Creep strength of these steels are improved by its martensitic lath structure, precipitation strengthening effects of M23C6 carbide and MX carbonitride (M=Nb, V, Cr and X=C, N) and solid solution strengthening effects of Mo and W atoms in the matrix [1]. Especially, precipitation strengthening effect of MX is important because its coarsening rate is small and fine particle size is maintained for long-term [2-4]. Many researches have been conducted on features and role of MX [2, 5-10]. A possibility of further improvement in creep strength by controlling MX has been also investigated [11]. Recently, Inoue et al. reported that two-phase separation behavior of primary MX into Nb-rich MX

153

M.Yoshino, Y.Mishima, Y.Toda, H.Kushima, K.Sawada and K.Kimura

and V-rich MX was caused by the miscibility gap between primary MX and another two phases at the temperature [9]. Such two-phase separation behavior has been clearly demonstrated by experimental results during tempering heat treatment at 765oC in a 9Cr-1Mo-V-Nb steel by Suzuki et al. [10]. Since MX particles are major strengthener, precipitation behavior in cooperate with two-phase separation of those during normalizing and tempering heat treatment strongly influences on creep strength. However, it has not yet been clearly understood, and presence of M3C in the as normalized condition in 9-12Cr ferritic creep resistant steels [12-17] has not yet been authorized. Aim of the present study is to understand phase equilibrium between austenite and MX at the elevated temperature in modified 9Cr-1Mo steel and influence of normalizing temperature on the precipitates in the as normalized condition has been investigated. 2. Experimental procedure The steel used in this study was a modified 9Cr-1Mo steel, chemical composition was shown in Table 1. An ingot of the steel with weight of 10kg was prepared by high frequency vacuum induction furnace. The ingot was heated to 1150oC for 1.5h and hot rolled in a range of temperatures from 1150oC to 900oC into bar with a diameter of 16mm. Normalizing heat treatment conditions are shown in Table 2. Normalizing heat treatments were performed for 600 sec in a range of temperatures from 1050oC to 1250oC and for 3600 sec at 1100 and 1200oC, followed by air cooling. Table 1. Chemical composition of the steel used in this study. Fe Bal. Cr 8.93 C 0.090 Mo 0.98 Si 0.26 V 0.22 Mn 0.41 Nb 0.067 P 0.001 sol. Al 0.002 S <0.001 N 0.051 (wt%) Ni <0.01

Table 2. Heat treatment condition of the steel studied. Temperature / oC 1050 1100 1150 1200 1250 Time / s 600 600 3600 600 600 3600 600 Air cooling Cooling

Distribution of precipitates was observed on carbon extracted replica under Field Emission

154

Normalizing Heat Treatment & Precipitation in Modified 9Cr-1Mo Steel

Transmission Electron Microscope (FE-TEM). Each precipitates were analyzed by Energy Dispersion X-ray Spectroscopy attached to FE-TEM (TEM-EDS). Mechanically polished specimen surface was etched in a saturated solution of picric acid in ethyl alcohol with 1% hydrochloric acid (Villelas reagent). The carbon was deposited on the etched surface, and the carbon film was detached from the specimen surface in a Villelas reagent. The carbon extracted replica was cleaned in ethyl alcohol and collected on copper grids for TEM examination. Precipitates were identified by means of X-ray diffraction analysis on an electrolytically extracted residue. 3. Results and discussion 3.1. Macrostructure Figure 1 shows optical micrograph of the steels in the as normalized condition at (a) 1050oC, (b) 1100oC, (c) 1150oC, (d) 1200oC and (e) 1250oC. Microstructure in the as normalized condition was martensite and no delta ferrite was observed for the range of normalizing temperatures from 1050 to 1250oC. The material was austenite single phase at the normalizing temperatures investigated.

Fig. 1. Optical micrograph of the steels normalized for 10min. at (a) 1050oC, (b) 1100oC, (c) 1150oC, (d) 1200oC and (e) 1250oC. Figure 2 shows Vickers hardness and prior
Grain size number
12 10 8 300 6 200 4 2 0 // as received 1000 1050 100 : Grain size number : Hardness 1100 1150 1200 1250 0 1300 // Load : 98N, 30s 500 400

austenite grain size number in the as normalized condition. Prior austenite grain size number was measured according to JIS G 0552 [18]. Prior austenite grain size of the steel increased with increase in normalizing temperature, but hardness of about HV400 was almost the same independent of normalizing temperature.

Normalizing temperature /

Fig. 2. Normalizing temperature dependence of a grain size number and hardness of the steel. 3.2. Precipitates in the as received condition Figure 3 shows a TEM micrograph of the carbon extracted replica prepared from the steel in the as received condition. Fig. 3(b) is a higher magnification image of the area indicated by square in Fig.

155

Hardness / HV

M.Yoshino, Y.Mishima, Y.Toda, H.Kushima, K.Sawada and K.Kimura

3(a). Precipitates distributed within grain were observed. There were two types precipitate which is spherical shape with a diameter of about 20~30 nm and coarse platelet one with a length of about 100 nm. According to TEM-EDS and XRD analysis, spherical precipitate and platelet one was identified as Nb-rich MX and M3C, respectively. A detail of phase identification and the morphology of precipitates were described in a previous work [19].

Fig. 3. TEM micrographs of carbon extracted replica prepared from the steel in the as received condition: (b) is an enlarged image of the area indicated by square in (a). 3.3. Precipitates in the as normalized condition Figure 4 shows the TEM micrographs of carbon extracted replica prepared from the steels normalized for 600 sec in a range of temperatures from 1050 to 1250oC. In the steel normalized at 1050oC (Fig. 4(a)), a lot of precipitates were observed within prior austenite grain. Many precipitates were also observed in the steels normalized at 1100oC (Fig. 4(b)) , 1150oC (Fig. 4(c)) and 1200oC (Fig. 4(d)), however, number of those decreased with increasing normalizing temperature and distribution of those was heterogeneous, in comparison with that in the steel normalized at 1050oC (Fig. 4(a)). In the steel normalized at 1250oC (Fig. 4(e)), no precipitate was observed. Consequently, it has been supposed that amount of undissolved precipitate decreased with increasing normalizing temperature and it does not exist at 1250oC. Moreover, any precipitation did not take place during cooling from normalizing temperature of 1250oC. Precipitates observed in the steels normalized in a range of temperatures from 1050 to 1200oC were also identified by X-ray diffraction and TEM-EDS analysis to be MX and M3C similar to those in the as received condition. It has been also observed that M3C cementite tends to precipitates around MX.

Fig. 4. TEM micrographs of carbon extracted replica prepared from the steel normalized for 600 sec at (a) 1050oC, (b) 1100oC, (c) 1150oC, (d) 1200oC and (e) 1250oC. 156

Normalizing Heat Treatment & Precipitation in Modified 9Cr-1Mo Steel

350

Particle diameter / nm

300 250 200 150 100 50

// : MX : M3 C

Figure 5 shows temperature dependence of average size of MX and M3C particles. Average size of M3C was in a range of 50 to 60 nm independent of normalizing temperature. On the other hand, that of MX increased with increasing normalizing temperature from 35 nm after normalizing at 1050oC to 315 nm after normalizing at 1200oC. It should be noted that average size of MX particles after normalizing was larger than that of 24 nm observed before normalizing heat treatment, and no MX particle was observed after normalizing at 1250oC. Above observation

0 // 1000 as received

1050

1100

1150

1200

1250

Normalizing temperature /

Fig. 5. Changes in particle diameter of MX and M3C with increase in normalizing

indicates that no precipitation of MX takes place during cooling from the normalizing temperature of 1250oC, therefore, observed MX particles after normalizing heat treatment are undissolved particles. Increase in average size of MX particles with increasing normalizing temperature could be caused by following two mechanisms, (1) finer MX particles tends to dissolve at the lower normalizing temperature and coarser one remains after normalizing heat treatment at higher temperature and/or (2) coarsening of MX particles takes place at the normalizing temperature. On the other hand, precipitation of M3C should take place during cooling from the normalizing temperature, since solubility of M3C in austenite phase at the normalizing temperature is high enough to dissolve it [20]. As a result of that, average size of M3C was almost the same independent of normalizing temperature. However, M3C was not observed at 1250oC. Thus, it is considered that precipitation of M3C was closely related to presence of MX particle. 3.4. Influence of normalizing temperatures on MX According to TEM-EDS analysis, major composition of MX was niobium, vanadium and chromium, and sum of concentrations of those three elements was higher than 93 mass% of metallic elements, moreover, sum of niobium and vanadium was about 90 mass%. In this section, influence of normalizing temperature on MX particle is investigated from a viewpoint of composition of MX, with a special attention to niobium. A sum of niobium, vanadium and chromium concentrations of MX particles was standardized to be 100 mass% and plotted in a Cr-Nb-V ternary triangle as shown in Figure 6. In the as received condition (Fig.6(a)), distribution of composition in a range of niobium from 50 to 90 mass% was observed along a line between 100 mass% Nb and 80 mass% V - 20 mass% Cr. This result was similar to that reported by Suzuki et al. [10] on a 9Cr-1Mo-V-Nb steel in the as normalized condition, although low niobium particles less than 50 mass% were not observed in this study. On the other hand, composition of MX particle was clearly divided into two groups by its niobium concentration after normalizing at 1050oC (Fig.6(b)). In addition to high niobium particles, those with low niobium concentrations of 20 to 30 mass% were observed. Those compositions distributed along 157

M.Yoshino, Y.Mishima, Y.Toda, H.Kushima, K.Sawada and K.Kimura

the same line as that observed in the as received condition. The number of particles with niobium concentration of 50 to 80 mass% observed in the as received condition decreased after normalizing at 1050oC. After normalizing at 1100oC (Fig.6(c)), distribution of compositions along the same line as those observed in the as received condition and after normalizing at 1050oC (Figs.6(a),(b)) was observed. However, many precipitates with niobium concentration of 40 to 70 mass% were observed instead of those with low niobium observed after normalizing at 1050oC. After normalizing at 1150 and 1200oC (Figs.6(d),(e)), small number of MX particles with high niobium concentration of 85 to 95 mass% were observed.

Fig. 6. Nb-V-Cr balances of MX in the steels in the as received condition (a) and normalized for 600 sec at (b) 1050oC, (c) 1100oC, (d) 1150oC and (e) 1200oC.
(a) Nb content / mass%
100 as received 80 60 40 20 0

(b) Nb content / mass%

100 1050/10min 80 60 40 20 0

(c) Nb content / mass%

100 1100/10min 80 60 40 20 0

Particle diameter / nm
1150/10min

10

100

1000

Particle diameter / nm
1200/10min

10

100

1000

Particle diameter / nm

10

100

1000

(d) Nb content / mass%

100 80 60 40 20 0

(e) Nb content / mass%

1 10 100 1000

100 80 60 40 20 0

Particle diameter / nm

Particle diameter / nm

10

100

1000

Fig. 7. Relationship between particle diameter and Nb concentration of MX in the as received steel (a) and steels normalized for 600 sec at (b) 1050oC, (c) 1100oC, (d) 1150oC and (e) 1200oC.

158

Normalizing Heat Treatment & Precipitation in Modified 9Cr-1Mo Steel

Relationship between diameter and niobium concentration of MX is shown in Figure 7. In the as received condition (Fig.7(a)), diameter and niobium concentration of MX was widely distributed in a range of 10 to 100 nm and 50 to 85 mass% of Nb, respectively. After normalizing at 1050oC (Fig.7(b)), low niobium MX with 20 to 30 mass% of Nb which did not detected in the as received condition was observed. Number of high niobium MX with 80 to 90 mass% of Nb increased and those with 50 to 80 mass% of niobium decreased. After normalizing at 1100oC (Fig.7(c)), diameter of MX distributed from 30 to 300 nm and was larger than that in the as received condition. Concentration of MX was roughly divided into two groups by niobium concentration of 75 mass% and low Nb MX indicated larger diameter than that of high Nb one. MX particles with niobium concentration of 40 to 70 mass% were not detected after normalizing heat treatment, except for normalizing temperature of 1100oC. After normalizing at 1150 and 1200oC (Figs.7(d),(e)), all MX particles contained high niobium of 80 to 90 mass% and those were larger than 100 nm. From the above results, it has been found that change in chemical composition of MX takes place during normalizing heat treatment and normalizing temperature influences on chemical composition of MX. Since low niobium MX observed after normalizing at 1050oC does not exist in the as received condition and MX particles are considered as undissolved precipitate that exist at the normalizing temperature as mentioned above, not only dissolving of MX, but also precipitation of it should take place during normalizing. Mean diameter of high niobium MX particle normalizing temperature and shown in Figure 8. Average diameter of MX particles increased with increasing normalizing temperature, as mentioned in Fig.5. Low niobium MX particle was larger than high niobium MX for the same normalizing temperature. Amount decreased of undissolved MX precipitates normalizing with increasing
Particle diameter / nm
350 300 250 200 150 100 50 0 // as 1000 received 1050 // : High Nb MX : Low Nb MX

and low niobium one was plotted against a

1100

1150

1200

1250

Normalizing temperature /

Fig. 8. Changes in diameter of high Nb and low Nb MX particles with increase in normalizing temperature.

temperature (Fig.4), however, low niobium MX particle which did not exist in the as received

condition was observed after normalizing at 1050 and 1100oC. It has been supposed that, consequently, not only dissolving of MX particle, but also precipitation of it with a chemical composition depends on normalizing temperature should take place during normalizing heat treatment. Inoue et al. has investigated phase equilibrium between austenite and (Nb,V)(C,N) complex carbonitride in Fe-Nb-V-C-N alloys, and binodal curve and phase separation behavior in quasi binary system of NbC-VC have been reported [9]. Suzuki et al. [10] investigated on precipitation behavior of MX during normalizing and tempering heat treatment in 9Cr-1Mo-V-Nb steel and observed a distribution of chemical composition of MX carbonitride along the line between 100 mass% Nb and 85 mass% V 15 mass% Cr in a Cr-Nb-V ternary triangle, similar to the results in the present study (Fig.6). It has 159

M.Yoshino, Y.Mishima, Y.Toda, H.Kushima, K.Sawada and K.Kimura

been reported by Suzuki et al. [10] that chemical composition of MX varies along the tie line between Nb-rich MX and V-rich MX and phase separation of undissolved primary MX into Nb-rich MX and V-rich MX takes place during tempering. Temperature dependence of chemical composition of MX observed in the present study should be influenced by phase equilibrium between austenite and MX. Phase field diagram of NbX-VX quasi binary system obtained from the experimental result is shown in Figure 9. Solid circle indicates average niobium concentration in MX precipitates and error bar means range of the experimental data. Additionally, the data examined by Suzuki [21] which was measured on 9Cr-1Mo-V-Nb steel in the as
1100 1200
1216

1300

Austenite Austenite + MX Temperature / oC

tempered condition after normalizing for 600 sec at 1050oC, was also indicated indicated determined by by square dashed by symbol. line was Solubility limit temperature of MX Thermo-calc

1000

Austenite + NbX + VX

900 Ac3: 835oC 800 Ac1: 815oC

calculation for NbX that was 1216oC and experimental results on NbX and VX reported by Iseda et al. [20]. Ac1 and Ac3 temperatures determined by dilatometer were also indicated. Peak temperature of binodal curve between 1100 and 1150oC is significantly

700

Ferrite + NbX + VX
: Suzuki [20]

600 100

NbX

Nb content / mass%

VX

Fig. 9. Phase field diagram of NbX-VX quasi binary

lower than the result reported by Inoue et al. [9] in which that is about 1530oC. The difference in peak temperature of binodal curve should be derived from difference in niobium, vanadium, carbon and nitrogen concentrations. Concentrations of 0.61 - 2.08 mass% Nb, 0.45 - 2.29 mass% V, 0.18 - 0.42 mass% C and 0.057 - 0.119 mass% N for the steels used in the study of Inoue et al. [9] are significantly higher than those of the steel used in the present study. During normalizing heat treatment, dissolving of MX with non-equilibrium composition and precipitation of it with equilibrium composition takes place corresponding to binodal curve. It has been considered that temperature dependence of equilibrium composition of low niobium MX is larger than that of high niobium MX, since solubility limit temperature of VX is about 100oC lower than that of NbX. Moreover, larger size of low niobium MX than that of high niobium MX (Fig.8) should be also caused by lower solubility limit temperature of VX, because higher concentration of vanadium in solid solution of austenite matrix may result in higher coarsening rate of low Nb MX. 3.5. Re-precipitation of MX Amount of undissolved MX decreased with increasing normalizing temperature, however, not only dissolving, but also precipitation of it took place, corresponding to equilibrium composition along a 160

Normalizing Heat Treatment & Precipitation in Modified 9Cr-1Mo Steel

binodal curve. It should require enough time for normalizing in order to attain phase equilibrium at the temperature. In order to investigate an influence of normalizing time on phase equilibrium, the steel was normalized for 3600 sec that is six times longer than a condition for the steels discussed in the above. Figure 10 shows TEM micrographs of carbon extracted replica prepared from the steel normalized for 3600 sec at 1100 and 1200oC. Although heterogeneously distributed precipitates were observed in both conditions similar to those normalized for 600 sec (Fig.4), amount of particles after normalized for 3600 sec was smaller than that after normalized for 600 sec, especially in the steel normalized at 1200oC. Precipitation of M3C takes place during cooling from the normalizing temperature in cooperation with a presence of MX, since M3C tends to precipitate around MX particles and no M3C precipitation takes place during cooling from the normalizing temperature of 1250 C where no undissolved MX particle exist. normalized at 1250oC where no undissolved MX particle exist, it is considered that precipitation of MX particle during normalizing heat treatment should influence on precipitation of M3C during cooling from the normalizing temperature. Area fraction where the M 3C precipitated was of area measured from TEM micrographs (Figs.4 and 10) by image analysis and shown in Figure 11. Area
Area Fraction
o

Fig. 10. TEM micrographs of carbon extracted replica prepared from the steel normalized for 3600 sec at (a) 1100oC and (b) 1200oC.
1.0 0.8 0.6 0.4 0.2 0.0 0 1050 : 10min. : 60min.

Since no M3C was observed in the steel

1100

1150

1200

1250

1300

Normalizing temperature /

Fig. 11. Normalizing temperature dependence fraction where the M 3C was

fraction where M3C was precipitated gradually decreased with increase in normalizing temperature and time. Therefore, it has been supposed that decrease in amount of M3C precipitate with increase in normalizing time should be influenced by time dependent phenomenon such as diffusion related to precipitation of MX particle. Schematic illustrations on changes in MX particle during normalizing heat treatment are shown in Figure 12. Only dissolving phenomenon of MX particle corresponding to solubility limit of it is described in Fig.12(a) and multiple behavior of dissolving of MX particle with non-equilibrium composition and precipitation of it with equilibrium composition is demonstrated in Fig.12(b). Vertical axis indicates concentration of niobium and/or vanadium. If only dissolving of MX particles takes place during normalizing (Fig.12(a)), diffusion of niobium and vanadium atoms in austenite matrix occurs from dissolved MX. In this case, coarser MX particles tend to remain after normalizing, since 161

M.Yoshino, Y.Mishima, Y.Toda, H.Kushima, K.Sawada and K.Kimura

finer particles are easy to dissolve. However, experimental results on the change in composition of MX particles that strongly depends on normalizing temperature and coarsening of undissolved MX particles with increasing normalizing temperature can not be explained by such simple dissolving model. On the other hand, both dissolving and precipitation of MX particles should take place during normalizing heat treatment (Fig.7(b)). Since equilibrium composition of MX strongly depend on temperature, especially at the temperatures higher than 1000oC (Fig.9), particles with non equilibrium composition dissolve and MX precipitates with its equilibrium composition during normalizing. By considering these precipitation behavior, temperature dependence of composition of MX and coarsening of it with increase in normalizing temperature can be understood. In contrast to simple dissolving model, concentration of niobium and vanadium in solid solution in the surrounding area of precipitated MX particle should be lower than the other region far from the particle, until the equilibrium is attained. With increase in normalizing time, niobium and vanadium poor area is reduced with progress in diffusion in austenite matrix. Although a lot of M3C particles have been observed in the as normalized condition, M3C is easily replaced by more stable carbide and/or carbonitride such as M23C6 and MX [22]. Affinity of niobium and vanadium with carbon and nitrogen is much stronger than that between iron and carbon. It has been considered that precipitation of M3C takes place in a surrounding area of MX particles precipitated during normalizing heat treatment, since concentration of niobium and vanadium in solid solution should be poor. Consequently, amount of M3C particles decreased with increase in normalizing time since niobium and vanadium poor region was reduced by diffusion and no precipitation of M3C was observed after normalizing at 1250oC where precipitation of MX did not take place.
(a) Nb, V
MX
M 3C

(b) Nb, V

MX

Distance

Distance

Fig. 12. Schematic illustrations of (a) dissolution model and (b) dissolution and precipitation model of MX particles at the normalizing temperature. 4. Conclusions The precipitation behavior of MX carbonitride during normalizing heat treatment has been investigated in a modified 9Cr-1Mo steel. The following results were obtained. (1) In the as received condition and after normalizing heat treatment, heterogeneously distributed fine spherical MX and coarse platelet M3C cementite were observed, except for the steel normalized at 1250oC. MX and M3C were clearly distinguished by those chemical compositions. Amount of

162

Normalizing Heat Treatment & Precipitation in Modified 9Cr-1Mo Steel

precipitates decreased with increase in normalizing temperature. (2) Although a size of M3C was almost the constant independent of normalizing temperature, average diameter of MX particle increased with increase in normalizing temperature from 35 nm after normalizing at 1050oC to 315 nm after normalizing at 1200oC. (3) Chemical composition of metallic elements in MX consisted mainly niobium, vanadium and chromium, and sum of those three elements was higher than 93 mass% of the metallic elements. Chemical composition of metallic elements in MX was influenced by normalizing temperature. Phase field diagram of NbX-VX quasi binary system with binodal curve based on experimental results was proposed. (4) Not only dissolving of MX with non-equilibrium composition, but also precipitation of it with equilibrium composition takes place corresponding to binodal curve during normalizing heat treatment. (5) It has been considered that precipitation of M3C occurs in a surrounding area of MX precipitated during normalizing heat treatment, since concentration of niobium and vanadium in solid solution is lower than the other region. References 1. Maruyama K, Sawada K and Koike J. Strengthening mechanisms of creep resistant tempered martensitic steel. ISIJ Int. 2001;41(6):641-653. 2. Suzuki K, Kumai S, Kushima H, Kimura K, Abe F. Heterogeneous recovery and precipitation of Z phase during long term creep deformation of modified 9Cr-1Mo steel. Tetsu-to-Hagan 2000;86(8):550-557. 3. Httestrand M, Andrn H-O. Evaluation of particle size distribution of precipitates in a 9% chromium steel using energy filtered transmission electron microscopy. Micron 2001;32(8):789-797. 4. Gustafson , Httestrand M. Coarsening of precipitates in an advanced creep resistant 9% chromium steel quantitative microscopy and simulations. Mater. Sci. Eng. 2002;A333(1-2):279-286. 5. Yamada K, Igarashi M, Muneki S, Abe F. Creep properties affected by morphology of MX in high-Cr ferritic steels. ISIJ Int. 2001;41(Supplement):S116-S120. 6. Tokuno K, Hamada K, Uemori R, Takeda T, Itoh K. A complex carbonitride of niobium and vanadium in 9% Cr ferritic steels. Scripta Metall. Mater. 1991;25(4):871-876. 7. Sawada K, Kubo K, Abe F. Contribution of coarsening of MX carbonitrides to creep strength degradation in high chromium ferritic steel. Mater. Sci. Technol. 2003;19(6):732-738. 8. Sawada K, Hara T, Kubo K, Abe F. Characterization of MX distribution in P92 steel by EF-TEM. Proc. First International Conference on Advanced Structural Steels, May 2002, 179-180. 9. Inoue K, Ishikawa N, Ohnuma I, Ohtani H, Ishida K. Calculation of Phase Equilibria between Austenite and (Nb, Ti, V)(C, N) in Microalloyed Steels. ISIJ Int. 2001;41(2):175-182. 10. Suzuki K, Kumai S, Toda Y, Kushima H, Kimura K. Two-phase separation of primary MX 163

M.Yoshino, Y.Mishima, Y.Toda, H.Kushima, K.Sawada and K.Kimura

carbonitride

during

tempering

in

creep

resistant

9Cr1MoVNb

steel.

ISIJ

Int.

2003;43(7):1089-1094. 11. Taneike M, Abe F, Sawada K. Creep-strengthening of steel at high temperatures using nano-sized carbonitride dispersions. Nature 2003;424(7):294-296. 12. Jones WB, Hills CR, Polonis DH. Microstructural evolution of modified 9Cr-1Mo steel. Metall. Trans. A 1991;22A(5):1049-1058. 13. Thomson RC, Bhadeshia HKDH. Carbide precipitation in 12Cr1MoV power plant steel. Metall. Trans. 1992;23A(4):1171-1179. 14. Saroja S, Vijayalakshmi M, Raghunathan VS. Influence of cooling rates on the transformation behaviour of 9Cr-1Mo-0.07C steel. J. Mater. Sci. 1992;27(9):2389-2396. 15. Kim HD, Kim IS. Effect of austenitizing temperature on microstructure and mechanical properties of 12% Cr steel. ISIJ Int. 1994;34(2):198-204. 16. Janovec J, Svobada M, Blach J. Evolution of secondary phases during quenching and tempering 12% Cr steel. Mater. Sci. Eng. 1998;A249(1-2):184-189. 17. Kobayashi S, Toshimori K, Nakai K, Ohmori Y, Asahi H, Muraki T. Effects of boron addition on tempering processes in an Fe-9Cr-0.1C alloy martensite. ISIJ Int. 2002;42(Supplement):S72-S76. 18. Japan Industrial Standards: G 0552 (1998). 19. Yoshino M, Mishima Y, Toda Y, Kushima H, Sawada K, Kimura K. Phase equilibrium between austenite and MX carbonitride in a 9Cr-1Mo-V-Nb steel. ISIJ Int. 2005;45(1):107-115. 20. Iseda A, Sawaragi Y, Yoshikawa K. Effects of nitrogen content and tempering treatment on creep rupture properties of 9Cr-1Mo-V-Nb steel with simulated HAZ heating. Tetsu-to-Hagan 1991;77(4):582-589. 21. Suzuki K. Unpublished work. 22. Bhadeshia HKDH. Design of ferritic creep-resistant steels. ISIJ Int.2001;41(6):626-640.

164