431

DEVELOPMENT OF 2Cr-Mo-W-Ti-V-B FERRITIC STEEL FOR ULTRA SUPER CRITICAL BOILERS (NKK TEMPALOY F-2W)
Akira Tohyama , Yusuke Minami Materials and Processing Research Center, NKKCORPORATION, Kawasaki, JAPAN

Abstract This paper deals with newly developed 2Cr-Mo-W-Ti-V-B ferritic heat resistant steel rube (TEMPALOY F-2W) which is used for water wall tubes and the economizer tubes of USC boilers, and for superheater tubes and reheater tubes of SC boilers. This steel is made by adding Mo and Was solution strengthening elements, and V and Ti as precipitation strengthening elements to a base of 2% Cr steel in order to improve its high temperature strength, and one whose matrix is a bainite single phase. The developed steel has superior creep rupture strength, its ordinary temperature and high temperature strengths are almost 1.5 times those of 2.25Cr-1Mo, and its allowable stress is equal to that of 9% Cr high strength material, SA213-T91 (9Cr-l Mo-Nb-V). Cost advantages can also be expected by reducing the wall thickness of tubing in boiler design due to its high strength. This newly developed steel is a material usable as for water wall tubes up to the 575t range in future high temperature, high pressure plants. Keywords : ferritic steel, bainite phase, solution strengthening, precipitation strengthening

Introduction

Recent boilers for the thennal power generation are designed for higher temperature and pressure than in the past. Especially enonnous efforts were made to establish the technology for the new nitra super critical power plant all over the world. In order to construct these high efficiency plants, it is essential to obtain materials with improved high temperature strength, superior resistance to oxidation, and resistance to high temperature corrosion. It is also important that these new material s are easy to weld or process, that they can be used for a long time at high temperatures without their material properties deteriorating, and that their costs are low enough for plant economy. As the temperature rises, the final superheater tubes must be made of material with superior high temperature strength. As the pressure increases, not only the [mal superheater tubes, but all steel tubes inc1uding the economizer tubes and water wall tubes must provide improved high temperature strength. While it is possible to increase their strength by making their walls thicker, this causes many design problems such as an increase in the overall plant weight. High strength materials which can be used to design plants with present rube dimensions are required from the low temperature range up to high temperatures. TEMPALOY F-2W(2Cr-Mo-W-Ti-V-B) steel was considered as a prospective material. In order to improve the creep rupture strength of 2.25Cr-1Mo steel; the new 2Cr steel has been developed. This report describes the development of this new 2Cr-Mo-W-Ti-V-B steel with high temperature characteristics.

432

2 Experimental Procedures and Results

2.1 Materials Chemical compositionof steel samples are given in Table 1.All of the steelswere prepared from ingots cast in 50kg electric fumace and hot rolled to plates with a thickness of 14mm after heating to 1200"C. inal heat treatments are the nonnalizing (1O50"Cx30min, cooling) and the F air tempering (780"Cx1hr, ir cooling).The normalizing temperatureis high for low alloy steel. The a purpose of this is to make solutionenough because of the large amount of additions of V and Ti which are carbide forming elements. V and Ti are precipitated as fine carbides during tempering. Steel samples WA WD were investigated for the effect of W content, steel samples VA VD for the effect of V content, steel samples TA TD for the effect of Ti content, steel samples NA-ND for the effect of Nb content, and steel samples BA-BD for the effect of B content.

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Steel WA WB WC WD VA VB VC VD TA TB TC ID NA NB NC ND BA BB BC BD

C 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.11 0.10 0.11

Si 0.50 0.49 0.50 0.50 0.48 0.47 0.48 0.48 0.48 0.48 0.49 0.49 0.48 0.48 0.48 0.48 0.57 0.61 0.61 0.59
"

Mn 0.50 0.50 0.50 0.50 0.51 0.50 0.50 0.50 0.51 0.51 0.50 0.50 0.51 0.50 0.50 0.50 0.54 0.57 0.57 0.55

Cr 2.02 2.00 2.01 1.99 2.07 2.04 2.02 2.02 2.01 2.01 2.01 2.00 2.02 2.00 2.01 1.99 1.92 1.90 1.91 1.90

Mo 0.51 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.58 0.62 0.61 0.60

W <0.01 0.19 0.39 0.59 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.32 0.33 0.33 0.34 0.34 0.34 0.34

V 0.34 0.34 0.34 0.34 <0.01 0.14 0.30 0.51 0.34 0.34 0.34 0.34 0.33 0.33 0.33 0.33 0.35 0.37 0.37 0.36

TI 0.14 0.14 0.14 0.13 0.12 0.12 0.12 0.12 <0.01 0.05 0.10 0.15 0.12 0.11 0.11 0.10 0.12 0.12 0.12 0.12

Nb

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0.0033
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2.2 Microstructure Typical microstructuresof steel samples are shown in Photograph 1. A basie structure of these steels is a bainite single phase, and the grain size of these steels is ASTMNo.8.5-9.5 and a fine comparatively grain in the majority of materials. The crystal grain grows as Ti decreases, it is ASTM NoA in the Ti-free material.Moreover, a fine grain of ASTM No.8.5-9.5 and the coarse grain of ASTM No.3 level mightexist togetherby the Nb addition.

434

2.3 TensileTestResults The results of tensile test at room temperature and 550"C are shown in Figure 1. These data indicate that both W and V has the effect to improve tensile strength by the addition of 0.2% or more. Moreover, there is a slight increase in tensile strength for Ti contents up to 0.15% but with a tendency to decrease with further increasing Ti content. B is also effective in tensile strength improvement, and the addition of 0.002% is effective . On the other hand, Nb decreases tensile strengthby rising of the content.
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435

2.4 Charpy Impact TestResults The results of charpy impact test at Ot are shown in Figure 2. The specimen used is ns NoA type (lOxlOx55 mm), and the V notch depth of the direction ofthiclcness of the plate is 2mm. W, V, and Ti indicate in any case an excellent value hardly exerting the effect on the absorbed energy in the range of the component examined at this time. On the other hand, Nb and B decrease the absorbed energy respectively by the addition of 0.1% or more and the addition of 0.004% or more. ,-... 400 >-;)
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436

2.5 Creep Rupture TestResulte The results of creep rupture test at 650'C-147MPaand 600'C-196MPaare shown in Figure 3. The addition of TI, W of 0.2% or more, V of 0.05% or more and B of 0.004% are effective to the improvement of the creep rupture strength . The addition of Nb of 0.1% or less is effective to the improvement of the creep rupture strength, but the creep rupture time is shortened and the creep rupture strength is decreasedby increasingthe Nb contentbeyond 0.1%.
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437

3 Manufacture of Steel Boiler Tubes and High Temperature Characteristics

3.1 Manujactureoj Steel BaUerTubes Using a five ton vacuum melting fumace, one heat of this new developed steel was melted. The steel ingot obtained from the five ton fumace was forged and machined into round billets, hot roIledto manufacturethe boiler tubes with an OD of 108 mm and wall thickness of 13 mm. The tubes were heat treated by normalizing at the temperature of 1O50'Cand tempering at the temperatureof 780'C. The chemicalcomposition of the tube materialis given in Table 2. W and Mo are contained respectively by about 0.3 and 0.6% as solid solution strengthening and a precipitation strengthening element based on Cr of 2%, and V and Ti are added as carbide forming elements 0.37 and 0.14%. For the investigation of properties, tests were carried out on samples taken from rube materials. Tensile tests were carried out at room temperature and elevatedtemperaturesup to 650'C.Creep rupture tests were carriedout at 500,550,600and 650'C.
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.
Cr 1.91 Mo 0.60 W 0.33 V 0.37 Ti 0.14 B 0.0046

C 0.10

Si 0.60

Mn 0.51

3.2 Microstructure and High Temperature Characteristics Microstructure of rube material is shown in Photograph 2. This photograph shows the structure of the rolling direction etched with nital. The structure is a bainite single phase, and the grain size is comparatively fine with ASTM No.8.5-9.5.
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The results of flattering and flaring tests did not exhibit any surface defects, indicating that the Workability of this developed steel is acceptable. The results of tensile tests are shown in Figure 4. The tensile strength at room temperature is 7ooMPa, and strength decreases along with the rise of the test temperature. Even at 6oo'C, the tensile strength of this developed steel is 4ooMPa or more, and this strength is higher than that of SA213-T91(9Cr-1Mo-Nb-V). The results of Charpy impact tests are shown in Figure 5. Charpy impact property of this steel is not so good. Charpy absorbed energy of this steel is less than 50J at O'C.

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The creep rupture test results are shown in Figure 6. The results of tests conducted on creep rupture strength arranged as Larson-Miller parameters (constant C= 25) are given in Figure 7. The creep rupture strength of this steel is high from 500'C to 600'C, and it decreases rapidly for a long time at 650'C.

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439

Allowablestresses of this steel provisionally calculated are shown in Figure 8 as compared with SA213-T22(2.25Cr-lMo) and SA213-T91(9Cr-lMo-Nb-V). The allowable stress of this developedsteel is higher than that of T91 at temperatures up to 5751: and is significantlyhigher than that of T22. 200

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Discussion

The effect of the small amount of the alloying elements on the creep rupture strength of the low Cr ferritic heat resistant steel was investigated. Using the creep ruptured specimen of the rube material (550'C-245MPa-12338hr ruptured specimen), the precipitates were extracted and the residue was analyzed. Identification results by X-ray diffraction of extracted residue are shown in Figure 9. ~C, M23C6and V4C3are clearly identified and the precipitation of (Ti,V)C is also noted. The state of precipitates was observed by using TEM(Transmission Electron Microscopy). The TEM observation results are shown in Photographs 3 and 4. The grain boundary is mainly composed of ~C and M23C6precipitation. On the other hand, precipitation of [me V4C3 and (Ti,V)C are present in the grains. Based on the state of precipitation and the effect of the alloy elements on the creep rupture strength which was mentioned above, it is considered that fine precipitation of these carbides (V4C3and (Ti,V)C) in the newly developed steel contribute to high

creep rupture strength.

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ConcIusion

The following conc1usionsare reached on assessing the newly developed low Cr ferritic heat resisting steel tubes used for USC and SC boilers to raise heat efficiencythrough improvedsteam conditions. (1) The effects of various alloying elements on the creep rupture strength of 2Cr-Mo-W-Ti-V-B steel were examined. As a result. O.lC-2Cr-O.6Mo-O.3W-O.3V-O.lTi-O.0040B was steel developed. The creep rupture strength of this steel is significantly higher than that of conventional 2.25Cr-lMo steeL (2) The excellent creep rupture strength of this newly developed steel was provided by the ~ precipitation of fine V4C3 (Ti.V)C which are present in the grains. and This newly developed steel is considered to be a steel that is economicallyadvantageous.because the Cr content is at the same level as for conventional2.25Cr-lMo steel,but its allowablestresses are equal to those of9Cr-lMo-Nb-V steeL