The 69th WFC Paper amy November 2010 Advanced manufacturing technologies of large martensitic stainless steel castings with ultra low carbon and high cleanliness *Lou Yanchun and Zhang Zhongqi (Shenyang Research Instat of Foundry, Shenyang 110022, China) Abstract: The key manufacturing technologies associated with composition, microstructure, mechanical properties, casting quality and key process control for large martensitic stainless stee! castings are involved in this paper. The achievements fuly satisfied the technical requirements ofthe large 700 MW stainiess steel hydraulic turbine runner for the Three Gorges Hydropower Station, and become the major technical support for the design and manufacture ofthe largest 700 MW hydraulic turbine generator uni inthe world developed through our own effort. ‘The characteristics of a new high yield to tensile strength (Ryaa/R) ratio and high obdurabilty martensitic stainless steel with ultra low carbon and high cleanliness are also described. Over the next ten years, the large martensitic stainless ste! castings and advanced manufacturing technologies wil see @ huge demand in clean energy industry such 8s nuclear power, hydraulic power at home and abroad. Therefor, the new high yield o tensile strength (Ro R,) ratio and high obdurabilty martensitic stainless steel materials, the fast and flexible manufacturing technologies of large size castings, and new environment friendly sustainable process wil face new challenges and opportunities. Key words: large martensitic stainless stoe! castings; ultra low carbon and high cleanliness; turbine runner and blade CLC number: TG 142.71 Document code: A ‘Abticle ID: 1672-6421(2010)04-383-09 [i 2220s the tow carton martensisstainers tel (ZGO6Cr13Ni4Mo) and associated manufacturing process were developed in China; using large are furnace melting and traditional casting process, the world’s largest martensitic stainless steel turbine blades were sucessfully cast and applied in the world’s largest axial-flow hydraulic turbine generator unit (capacity of 125170 MW, installed in the Gezhou Dam Hydropower Station on the Yangri River). The net weight of a single stainless steel turbine blade is 25~40 the outline size is 8 mx -4.m x LS my the section size varies between 40-500 mm, see Fig. 1. Since 1981, the 21 hydraulic turbine generator units with capacity of 125-170 MW in the Gezhou Dam Hydropower Station on the Yangtze River, have been successfully operated for nearly 30 years; this marked that the Chinese manufacturing technologies of hydraulic turbine generator units have entered “Lou Yanchun ‘Male, bom in 1963, Ph.D. Professor and President of Shenyang Research Insitute of Foundry. He graduated ‘fam Shenyang University of Technology in 1986 and obtainod his Ph.D from China Academy of Machinery Science and Technology in 2008. His research interests mainly focused onthe special metals anc their forming process technologies. E-malt [email protected] Received: 2010-05-06; Accepted: 2010-07-20 the era of stainless ste! from 1980s, In April 1992, China launched the Yangtze River Three Gorges Project; the development of large martensitic stainless steel with ultra low carbon and high cleanliness and the large 700 MW turbine runner started at the same time. At the beginning of this century, the new ultra low carbon martensitic stainless steel (ZGO3Cr13Ni4Mo) and associated manufacturing technologies were successfully developed in China. At the same time, the design and manufacturing technologies of the runner forthe large 700 MW mixed-flow turbine generator unit reached the top rank inthe world, Fig. 1: The world’s largest martensitic stainless steel turbine blade 383,sums CHINA FOUNDRY 384 ‘The 700 MW unit ofthe Three Gorges Hydropower Station is the world's largest mixed-flow hydraulic turbine generator unit, The operating water head is 61-113 m, The stainless steel runner of the hydraulic turbine has the Largest outer diameter of 10.6 m, weight of 500 t, and consists of a crown, faring and 13-15 blades fabricated by casting and welding, see Figs, 2 and 3, Advanced integrated technologies have been used for the ZG03Cr13Ni4Mo large martensitic stainless steel castings with ultra ow carbon and high cleanliness, including: VOD, AOD refining process; advanced computer solidification simulation and casting technology; combination of welding and ‘machining process of large steel turbine runners; microstructure and mechanical properties control, phase transformation and heat treatment process control of large martensitic stainless steel; thermal stress and transforming stress control; deformation and cold cracking control and s0 on Fig, 2: Stainless steel turbine blades for the Three Gorges Power Station Fig. 3: Stainless sto Gorges Power Station turbine runner for the Three Clean energy is an important and preferential development field in China, By 2020, in China the new installation of capacity of hydropower will excced 120 GW, among which there are alpout 150 large mixed-flow turbine units of stand-alone capacity 700 MW similar to the unit of the Three Gorges Hydropower Station, hout 150 pumped storage power units with stand-alone capacity 300-400 MW, and about 150 large through-flow type turbine generator units with stand-alone capacity 30=60 MW; the Vol.7 No.4 development work on the large stainless see! turbine runner for the level of 1,000 MW capacity unit will also be carried out, In the near future, the preferentially developed 150 large units alone reed more than 2,000 large stainless stel blades. Accordingly, the large martensite stainless steel castings with ulira low carbon and high cleanliness have @ huge market demand Because large ultra low carbon martensitic stainless steel ‘castings and associated manufacturing processes have many advantages, they are widely used in the clean energy industry Advantages: (1) High strength and toughness: Rye,>600 MPa, R,> 800 MPa, A>18%, Z>50%, Ayy>100 J (2) Good low temperature impact property, fracture toughness and FATT (Fracture Appearance Transition ‘Temperature, -173 t0 -196). (3) Good welding, casting and machining properties. (4) Good underwater fatigue resistance, good cavitation ccorrosion/erosion and wear resistance, (5) High hardenability and good mechanical properties of heavy seetion castings. (6) The defects of martensitic stainless stel castings can he ‘easily and accurately tested and evaluated by non-destructive testing methods, and the defects can be easly repaired. ‘The key problem for us to deal with in manufacturing ‘process is that the ZGO3Cr13Ni4Mo (Nid steel for short) has some fatal disadvantages. Disadvantages: (1) Mechanical properties are very sensitive tothe variation in microstructure and chemical composition, (@) Mechanical properties are very sensitive to heat treatment process control () Phase transformation process is more complicated; stress and cold cracking are dificult to contro. (4) Long manufacturing cycle and delivery leading time. In this paper, the Nid steel and the associated key manufacturing technologies used for the stainless stee] turbine runner of 700 MW nil in the Three Gorges Hydropower Station are described. 2 Key manufacturing process of large martensitic stainless steel castings with ultra low carbon and high cleanliness (Ni4 steel) 2.1 Chemical composition and cleanliness control of molten steel The chemical composition and cleanliness control of the molten steel of martensitic stainless steel with ultra low carbon snd high cleanliness are listed in Table 1" ‘Compared with the current standards of ASTM, ISO and GB (Chinese National Standard), the Three Gorges Hydropower Station Specification has the highest requirement for chemical composition (by weight): C=0.03% (or C<0.04%), S<0.008%, P=<0.028%. Control of Ni and Cr equivalent: NigfCrg= 039-045November 2010 The 69th WFC Paper amy ‘Table 1: Chemical composition and cleaniness of Nid steel (wt.%) Elements (=) SK=)_-M=) PLS) =) cr AP 008 080 1000085025 115-135 eB? 004 080 © 1.80 oga a S15 cP 004 060 © 1.00 «onze one) 120-138 DY 008 080 © 1.80005 ons S130 e° 008 100 «4.004 Note: Ni +0.5Ma + 30(C4N)” Cr4Mo + L5Si+55Al Among them, Cr = 12.0%~ 13.5% is a key and proper content range. Study showed that with variation of Cr between 146-13.5%, the mechanical properties ofthe steel maintain in the same level, But only for Cr>10%, the reverse transformed austenite accurs in microstructure. It is obvious that with variations of Cr content, the corrosion fatigue resistance, low temperature impact property, fracture appearance transition temperature and welding property of the stainless steel are significantly different **. Inthe technical specification of the Three Gorges Hydropower Station turbine runners, the cleanliness and residual element content of molten steel are specified: [0|=80 ppm, [N] 160 ppm, [H]=<3 ppm, and the up-imit of [Al] and [V] is specified. ‘Among them, the key manufacturing technologies for large martensitic stainless steel turbine runner with casting and ‘welding process are: the control of C < 0.03%, [H] <3 ppm and the residual [AI] and [V] 2.2 Control of microstructure and mechanical properties Test on four groups of Ni steels named as SF-1, SF-2, SE-3 and SF-4, respectively were caried out under different heat- treatment process including normalization (N) and tempering (1), SP-1: N(,000°C) + T(600-650°C), SF-2: N(1,000°C) + 1(500-550°C), SE-3: N¢1,000"C 850°C), SF-4: N(1,000°). Residual lomonts (=) N Mo Nv @ WE 25-60 04-10 pos 00 010 050 25-60 04-10 pos 050 010 050 3845 04-06 006 002 050 080 25-60 1.00 2545 04-10 02 00 010 060 ~ Chinese Naoral Standard 6869672008; ~ Theo Gorges Spocfcaton:(@ ~ ISOT1972 @- ASTM 352 386 487 743, (1) The microstructure of Nif steel are low carbon lath, martensite matrix + 10%-15% reverse transformed austenite + d-forrte (<3%%), see Figs. 4 and 5. It is seen that a slight change in double tempering process and microstructure causes yield strength to increase by 90 MPa (an increase of 14%) While keeping other properties the same level ‘The microstructure of low carbon lath martensite is dislocation martensite, and the mechanism of phase transformation is shear process without diffusion; during the phase transformation process surface relief and volume expansion (face-centred cube-rbody-centred cube) occur leading to phase transformation stress in large martensitic stainless steel castings. If dusing cooling, large castings experience the double stresses ~ the phase transformation stress due to microstructural transformation and thermal stress due to the variation of temperature in different sections, this will be the main reason causing cold cracking defects in large martensitic stainless steel castings. ‘The reverse transformed austenite (Fig. 6) has extremely high thermal stability and mechanical instability, which will result in significant influence on mechanical properties, low temperature impact and welding property Reverse transformed austenite has mechanical instability and strong ability of deformation strengthening, A simple stress has no effect on reverse transformed austenite, Under the action of strain, strain-induced martenisite phase transformation takes place. The phase transformation mechanism is; stacking fault ~ face centred cubie ~ close-packed cubie ~ body-centred Fig, 4: Microstructures of Nid steel (SF-1) (R,q;: 635 MPa, Ry: 810 MPa, A: 24%, Z: 72%, A,>150 J) 385somes CHINA FOUNDRY 386 (2) Dar ois (©) Bright ls Fig. 6: Reverse transformed austenite . 2 0-608 01257 0.2107 0.3969 0.575 0-685 Fig, 7: Relationship between reverse transformed austenite and true strain cubic structure. During the deformation process under stress, the reverse transformed austenite changes to martensite which increasing the strength and hardness, see Fig.7"! The amount, morphology and distribution of &-ferite have direct influences on mechanical properties, resistance to cold bending, fracture appearance transition temperature and the 6-o teansformation during welding process of Nid steel. ‘Therefore, i is very important to contol of ratio of Ni and Cr equivalent to 0,390.45 in chemical composition and 6-ferrte -<3% in microstructure. (2) The mechanical properties of various standards and specif tions in the world are presented in Table 2. Table 2: Mechanical properties of Nié steel No. Rigs Ry AZ Ay HEW Standort Mpa (=) MPa (=) % (=) %() J) 550 750 15 «9550 <5 (NAGE 2 50 750 «15 «35 SD 220-200 ASTM 2 50 750 18 45 220-200 180 450 72018 «580 20-200 GB. 5 5807802055100 220-280 Three Gorges, After normalization and tempering, the mechanical properties of Nid steel used for the Three Gorges stainless steel turbine runner ae listed in Table 3 It is scen that the Three Gorges Standard has mechanical property requirements even higher than other standards. The high strength, high ductility and toughness and high impact property of martensite stainless stecl with ultra low earbon and high cleanness are due tothe high stength and ductility of ultra low carbon lath martensite, the deformation strengthening and ‘extremely high thermal stability of reverse transformed austenite. ‘The mechanical properties of full lath martensite steel under normalized condition are: Ryss 940 MPa, R, 1,000 MPa, A 16%, 267%, Mey 121-130 J, BBW 307-315, Research work on stability under different cooling rates of normalization showed that the Nid steel has extremely high hardenability and good mechanical properties of heavy section ‘castings, as shown in Table 4November 2010 Natriais Ry (MPa) sr SF Table 4: Mechanical properties of normalized Nis steel No, Cooling Ry(MPa) 1 8 1000 2 1900 2 F000 4 fF 43900 14900 Sra f 4090 Note a1 810 20s, 810 a8 818 220 220 RystMPa) Ae) 0 6 ors 18 50 6 92 8 os 138 a0 14 ir cooling, F-fumace cooing Table 3: Mechar Ras (MPa) 620 es eas 650 720 18 730 120 Ae) 25 45 240 45. 240 2s 20 20 20%) 6 60 n n 560 ors The Nid steel has very good resistance to cold bending, see Fig. 8. Ifthe chemical composition and microstructure of Nis steel fall outside the control limits and higher &-Ferrite (23%) appears in the microstructure, the resistance to cold bending decreases dramatically, see Figs. 9 and 10. (3) Low temperature impact toughness, dynamic impact toughness and underwater fatigue property FATT =-173 to -196'C Fig. 8: Cold bending tested Nié steel samples without crack Fig, 9: The microstructure of Nid steel with 8% Servite ZH) es ns 730 0 728 700 700 690 2150 2150 2150 2150 5 >180 a 8 properties of the Nid steels. fod) >150 >150 >150 >150 45 ae 148 143 Aid) HEN oat oo 1778s m 310 att oat to 136 128 331335 196 45 a5 at The 69th WFC Paper amy 20 253 255 2st 285 263 202 263 under air and furnace cooling RR on ove rr rr one 088 089 089 CChomical composition ‘and cleaninas (.) 0.020 (or 00015, Mo: 048 c:0.0a (0; 0.0077 Mo: 099 Note 0.006 N:o0058 VF 0.083, P0021 Inroor AOD A:0017 Fig.10: The cold bending tested sample of Ni steel with 8% Servite with erack At loading rate of 35 m/s, critical dynamic fracture toughness of the Ni steel K,= 240-270 MPa, the fracture is fully tough fracture, see Fig. 11. The resistance to crack propagation and P-S-N fatigue test results of the Nid steel are shown in Figs. 12, 13 and 14 8 g ‘See tent fair, K(MPam') Time Fig.11: Relationship between stress intensity factor (K) ‘and time (9) 387somes CHINA FOUNDRY 19 Sie -sowemen | ‘Senet iSimnd a sk open) Fig. 12: Crack propagation rate in the air qe i Ses a ‘es «spine 3 Seen 2K Wea Fig, 13: The crack propagation rate inthe simulated ‘Yangtze River water + so Spo 0 10 1 Fig. 14: P-S-N curve for a average stress of 400 MPa (400 MPa ress for is the actual measured maximum residual the large cast and welded turbine runner) ‘Table 5; Threshold and the results of Paris, equation fting Experimental Threshold envionment AK (MPa?) Ineo 453 tntane2.7326%10"(0K7™ Inthe simulate 10 ane Yangze River water “°° etaaciceeaale ate 340-360 MPa (in the air) (CF) = 260-280 MP (in the simulated Yangtze River watet) Results of Table 5 showed that the Ni¢ steel has good sue resistance which is reduced by 25%—-27% underwater fal compared with the fatigae in ar. 388 Vol.7 No.4 2.3 Phase transformation and heat treatment process control of large Ni4 steel castings Study on the relationship between high temperature mechanical properties and structure transformation during heating and cooling of castings can supply theoretical bases for manufacturing process design of large castings. The high temperature properties of castings during heating and cooling after solidification are shown in Figs, 1S and 16" “The results showed thatthe instantaneous change in property and Volume during martensite phase tansformation i the technological reference for solidification and heat treatment process control, The typical heat treatment cycle is shown in Fig. 17 10 —] Th, Be =f : =f e 10% g dé =2 14 |: od Fig. 15: The varlation of mechanical properties of NI4 Stee! with temperature during heating — ° Te, =k . <3 8 Bel tee 8 z de 468 e 2 ee aE xe Fig, 16: After solidification, the variation of mechanical properties of Nié steel with temperature during coolingNovember 2010 Softening annealing at 600-650 °C is a unique annealing, process for large martensitic stainless steel castings, and can entirely replace the high temperature diffusion annealing: then normalization between 1,000-1,0S0'C+ first tempering: at last, normalization and cooling to the temperature range between M,-M,and double tempering, The purposes of double tempering are (1) Contcol HB<2S5 or increase the ratio of yield strength to tensile strength (Ryo JR) (2) Increase the reverse transformed austenite content, {improve mechanical and processing properties. (3) Control phase transformation stress and prevent cold cracking (4) Make the manufacturing fast and flexible thus shortening. ‘manufacturing cycle, 2.4 New high yield to tensile strength ratio and high obdurability martensitic stainless steel (Type SF-2) With AOD and VOD refining processes, and through contol of the composition equivalent, cleanliness and the residual clement content, and the control of phase transformation stress, the ultra low carbon martensitic stainless steel with high yield to tensile strength ratio and high strength has been successfully ‘manufactured by using of lower temperature (480-520 ‘C) heat tteatment, In addition to high strength and high hardness, the new steel also has high ductility, high toughness, good welding property and high resistance to cavitation erosion/abrasion, The microstructure of lth martensite single phase is shown in Figs. The main technical characteristics of the Nid stel (SF-2): (1) Carbon: C=0.03% (or C=0.045); Control the element equivalent and residual clement Al, V and Cy (@) High cleanliness: [0}<60 ppm, [N}<150 ppm, [1}<3 ppm, $<0.005%, (3) Lath martensite single phase structure with 8-ferrte <39% ‘which has good mechanical properties The mechanical properties of high strength martensitic stainless stel specified by GB and ISO standards are listed in Table 6. (4) The mechanical properties for new high strength high yield-tensile ratio Nid steel are listed in Table 7. It can be ‘seen that Ry 21,000 MPa, Ry:>850 MPa, A= 15%, Z250% gy 100 J, HBW2=300 (5) The resistance to cavitation and abrasion is improved 2-3 times, see Fig 19” (6) Good resistance to cold bending: samples were bent to ‘90° without cracking, see Fig.20. (1) Good fatigue resistance property with P. The 69th WFC Paper amy Fig.18: Lath martensite single phase microstructure In Nid stool (SF-2) ‘Table 6: Mechanical properties of high strength martensitic stainless steel (min.) No. Re(MPa) Ra (MPa) ACK) 21%) Aes (d) HBW Standards 1 0 © 90012535 04-260 aKEET 2 m0 ©9002 = 5a HSONTOTE showed in Fig. 2. (8) The steel has been successfully used in the blade of Kaplan turbine and wicked-gate at home and abroad and inthe runner blade of small to medium mixed flow turbine unit in ‘China; and has been also used in heavy section castings such tas the large mechanical arms, large jack catch and so on. 2.5 Casting and combination welding technologies of the 700 MW hydraulic turbine generator unit stainless turbine runner for the Three Gorges hydropower station The computer simulations of casting filling and solidification ‘Table 7: Mechanical properties of Nié steel with high strength and high yleld-tensile ratio Material Ra (MPa) Ras(MPa) AC) 1.100 05 180 sro 10 05 185 1.100 ‘905 75 1.100 20 170 20%) Aa) HBS Rly eo 1 ar wae e500 14 196 a3 0125 9 5 es 16 1M a7 389somes CHINA FOUNDRY 390 25 15? ee Sa oN ete ae wet — a” gop ol tt oC a 56 a +09 Fig. 19: Relationship between time and mass loss rate of SF-2 and Ni Fig, 20; Cold bending testing (SF-2) ‘ress esis (MPa) Fig, 21: P-S-N curve with average stress of 400 MPa process, temperature field, stress field, deformation and porosity defect prediction for the erown, ring and blade castings of the Three Gorges Hydropower Station are illustrated in Figs 22-23", ‘The Nid steel castings with ultea low carbon and high cleanliness have high leunlines, (0)*<80 ppm and (§)*=50 ppm, and have very good fluidity and filing ability, thus benefiting the surface and intemal quality of castings, ‘The Nid steel castings with ultea low carbon and high cleanliness contain (C]=0.03% and [H]<3 ppm, and have very good welding property, which is an important technological promise for the quality of Three Gorges turbine runners fabricated by large martensitic stainless steel castings Vol.7 No.4 . j a Fig, 22: Temperature field of the Three Gorges’ turbine blade casting 1. 23: Deformation field of the Three Gorges’ blade (crown, ring and blade) and combination welding. 2.6 Short leading time — Fast and flexible manufacturing technology Improving quality, reducing manufacturing eycle, decreasing ‘consumption and using environmentally friendly technologies will strengthen our nation’s global competitiveness and sustainable development. Thus we should make improvement in the following aspects ao mould (2) Cooling process within the mould and knock out process; {) Heat treatment process of castings; (4) Welding and finishing process; (5) The cleanliness and inclusion defects of molten steel, (@) Advanced casting technology: (7) Co-current engineering and simultaneous design, jmulation of cooling curve of large castings within the 3 Conclusions (1) The composition, mechanical properties, casting {quality and associated manufacturing technologies of the large martensitic stainless steel castings with ultra lowNovember 2010 carbon and high cleanliness fully satisfy the technical requirement of the stainless steel turbine runner for large hydropower generator unit, and offer the technical support for achieving world advanced level in design and ‘manufacturing of large hydraulic turbine generator unit with capacity above 700 MW. (2) The preferential development in elean energy such as hydropower, nuclear power and so on, creates a huge market demand for ultra low earbon martensitic stainless steel in the next ten years, Therefore, high yield to tensile strength ratio and high obdurability martensitic stainless steel with ultra low carbon and high cleaalness, the application of fast and flexible ‘manufaeturing technologies for large martensitic stainless steel castings, and the manufacturing technologies for low carbon, sustainable economic development will face new opportunities and challenges. References [i] China Machinery Industry Federation (CMIF). Acceptance Report on Complete Devices of China Three Gorges Project, 2008. (in Chinese} [2]. Institute of Metal Research Chinese Academy of Sciences (IMR), Martensitc Stainless Steel Casting Specticatio for 700 MW Hydropawer Turbine of Three Gorges Project, 2008, 7. (a Chinese) The 69th WFC Paper mmm [a] Zhang Zhongalu, Lou Yanchun, Li Xinya. Advances in Research ‘of Nirogen Contained Stainless Stes, In: Procaodings ofthe ‘5h WFC, Korea, 2002 [4]. Zhang Zhongelu, Li Xnya, Phase Transformation Contaling and Stress Analysts for Large Blades of Mantonsitc Stainless ‘Stool In: Proceedings of the 57th WFC, Osaka Japan, 1980: 222-228 {5}, Lou Yanchun, Zhao Fangxin, Yu Bo. Etfect of Variation of Chromium on the Characteristic and Regulation of Heat ‘Trwatment for CrNi Hycraule Turbine Matera. Foundry, 2004, 5: 345-349, (in Chinese) [6]. Lou Yanchun. New Martenstc Stinlss Cast Steel with Low Carbon for Hycraule Turbine ZGOECr10NiMo. Foundry, 2005, *t: 10731075. (in Chineso} [7] Mahnig F Rist A, War H, Strongth and Mechanical Fracture Behaviour of Cast Steel for Turbines. Water Power, 1974, 10: 338-343, {6}, Wang 2h, Zhang Znongqiu. Relationship betweon Compositon and Propertiss of Low Carbon Fe-Cr-Ni Matensitc Stainlass ‘lea. n: Proceedings of the 58th WFC, Sao Paulo, raz, 1992: 159-169. [8] Lou Yanchun, Zhao Fangxin, Yu Bo, Wang Jingcheng, Xiong ‘Yunlong, Yang Yuntao, Electrochemical Corasion and Cavitaton Erosion Behaviors of Cr-Ni Stainless Stes! as Hydraulic “Turbine Material, Jounal of Chinese Society fr Corresion and Protection, 2006, 5: 312-318. (n Chinese) [10] Wu Ying, Study of Martonsitc Stainless Stes! Blade Casting for Large-Sized Water Turbine. Foundry, 2008, 8: 820-822. (in Chinese) (The paper was presented at the 69th World Foundry Congress (WFC), Hangzhou China 2010, republished in China Foundry with the author's kind permission) 391