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An Alloy Design Concept for Better Matching of Strength and Toughness in Pipeline SteelsIts Development and Application

Pascoal Bordignon1, Klaus Hulka2

(1. Companhia Brasileira de Metalurgia e Minerao CBMM, Brazil; 2. Niobium Products Company GmbH NPC, Germany) Abstract: The metallurgy of niobium microalloyed steels became to be better understood and spread worldwide in the 1970s. Based on industrial trials in the 1970s and 1980s, an industrial demonstration heat was produced in 1985. It allowed intensifying the deformation in the non-recrystallization region of austenite at higher rolling temperatures and thus, it was called the HTP (High Temperature Processing) concept. The extended delay in austenite recrystallisation, obtained by the strong effect of niobium, allowed more flexible rolling schedules in plate mills, making it possible to obtain high toughness levels, in addition to high strength, even in plate mills with power limitation and having relatively low separating forces. In more recent years, with further development of technology in the steel industry, very low carbon levels, well below 0.10%, became possible for applications like in line pipe steels. Under this condition, the HTP steels combine an additional effect of niobium by lowering the transformation temperature, promoting bainitic microstructures with excellent toughness and weldability at very high strength levels. As a result, the HTP steels became a reality in the market, where combination of several properties at high levels are desired. For instance, those steels have been applied in important pipeline projects, including the recently concluded, over 4,000 km long, West-East Pipeline in China. This paper summarizes the development of the HTP steels, describing the metallurgical concept, more flexibility in thermomechanical processing conditions, final product alloy design, microstructure and mechanical properties as well as its application in pipeline projects. Key words: niobium, microalloying, thermomechanical rolling, high temperature processing, pipeline steel

1 Introduction
World energy consumption is continuously increasing and in the next decades two thirds of the total demand still have to be covered by crude oil and natural gas. The most economic way of transportation from the well to the end user is via pipelines. Since new wells are often located in arctic regions or offshore and new resources can contain high amounts of H2S or CO2, new demands in the material for large diameter pipelines arose, such as high toughness at low temperatures, thick wall and sour gas resistance. Furthermore, the economy of a pipeline asks for high transportation capacity and thus higher strength of the steel in combination with a higher Charpy-V-notch energy at operating temperature, in order to avoid long running ductile cracks[1]. Starting already in the 1970s, but for sure since the 1980s, the most relevant pipe steel grades are X 65 and X 70. With the new demands mentioned before, this steel grade had to be modified and also steel grades with higher strength, such as X 80 are considered in new pipeline projects.

2 Metallurgical Background
Thermomechanical rolling is the standard means to produce plate or strip for high strength large diameter line pipe in order to fulfil the economic demands and safety requirements of pipelines. It relies on processing austenite in the temperature region of nonrecrystallisation and is the most efficient method for achieving grain refinement and thus both, higher strength and toughness. All these steels are niobium microalloyed. If the amount of solute niobium is increased, retardation of austenite recrystallisation is observed at significantly higher temperatures, Figure 1[2], thereby allowing the thermo-mechanical rolling to occur already at higher temperatures. Several metallurgical mechanisms, such as grain refinement, solid solution, dislocation or precipitation hardening, but also the carbon and the free nitrogen content influence the yield strength and the toughness of steel. Figure 2[3] shows some of the factors for a steel with 0.08 %C 1.50 %Mn. The role of niobium is to prepare a finer grain size and to reduce the free

Fig.1 Retardation of austenite recrystallisation by microalloying

Fig.2 Mechanical properties of a 0.08 %C 1.50 %Mn steel as a function of niobium content and finish rolling temperature

nitrogen content. It is assisted or can be substituted to a certain extent by lower finish rolling temperatures. With this base composition the positive role of niobium gets diminished at levels higher than about 0.05 % and in order to achieve high strength and good low temperature toughness, low finish rolling temperatures in the lower austenite region are needed. However, there are metallurgical situations or facility limitations, where the necessary processing at temperatures of the metastable austenite is not feasible or advisable. As already shown in figure 1, the best possibility to carry out the austenite conditioning at higher temperatures is to increase the amount of niobium in solid solution. For a given reheating temperature, this is possible by lowering the carbon content and by fixing the nitrogen by titanium, an element, which shows a higher affinity to nitrogen than niobium as described already elsewhere [4]. In the following, steel with niobium levels above 0.07 % (most typical 0.10 %), carbon levels below 0.06 % (most typical 0.03 %) and a Ti/N treatment will be called HTP steel (HTP = high temperature processing). Modern high strength low alloy (HSLA) steel typically comprise carbon levels, which avoid the peritectic reaction during solidification, which may be responsible for surface cracks formed already in the crucible during continuous casting[5]. The lowering of the carbon content has also a positive

influence on the homogeneity of the microstructure. Figure 3 describes the tendency for segregation by means of the Fe-C diagram: The peritectic reaction, where the liquid steel and the already formed -ferrite will be transformed into -iron, is connected with an additional shrinkage and causes an interdendritic inclusion of the remaining liquid, which is enriched with alloying elements. This inhomogeneous distribution of alloying elements, especially in manganese, is the origin of banded microstructures in the final product. This is another reason, why low carbon levels are aimed for. If the carbon content is below the threshold value of 0.09 %, the solidification goes via the -ferrite phase. In this case not only any indendritic segregation is avoided, but also the crystal segregation gets reduced with lower the carbon content: The smaller interval of the liquidus to the solidus temperature results in reduced crystal segregation during solidification and the bigger interval in the -region facilitates the post solidification homogenization by diffusion. It is well known that with lower carbon content many properties are being improved, such as the ductilebrittle fracture transition temperature, the impact energy, the ductility and formability and last but not least the weldability. Furthermore, the improved homogeneity itself has a positive effect on the resistance against hydrogen induced cracking.

toughness, figure 4, even when the finish rolling temperature is 150 C higher than typical. A small impairment in the Batelle drop weight tear test transition temperature is observed in that case, but the absolute value is still outstanding. Furthermore, by finish rolling in the two-phase region + the strained ferrite brings up a huge strength increase, and X 80 properties are achieved. By this approach the BDWTT transition temperature is not impaired only a certain reduction in the Charpy-V-notch energy at subzero temperatures occurs owing to separations.

Fig.3 Part of the Fe-C diagram with classification of the segregation severity

3 Results of a Demonstration Heat

Based on experience of earlier trials, an industrial demonstration heat according to the HTP concept with the chemical composition given in Table 1 was produced in 1985. Since sour gas resistance was also aimed for, the sulphur content was kept below 10 ppm and proper calcium treatment was also applied.
Table 1 Chemical composition of an HTP demonstration heat Chemical composition in wt.% C 0.028 Cu 0.29 Si 0.24 Cr 0.27 Mn 1.77 Ni 0.17 P 0.007 Nb 0.100 S 0.0008 N 0.0035 Al 0.030 Ti 0.014

Fig.4 Influence of finish rolling temperature on the mechanical properties of air-cooled plate

Slabs of this heat have been distributed to many experienced pipe plate and strip producers, who rolled this material according to their experience and needs. The results have already been published[4] and just a few are being summarized here again. If air-cooling is applied after thermomecha-nical rolling, one obtains X 70 properties with excellent

It is worth mentioning that the described results were based on a rolling schedule, where the final deformation started with a sheetbar thickness of 3.5 times the final plate thickness. If the total deformation during finish rolling is lower, e.g. 3.0 times the final thickness, then both, the yield strength and the transition temperature are impaired, barely sufficient to guarantee X 70 properties[6]. Other than in conventional pipe plate with higher carbon content, this alloy allows a relevant amount of niobium to stay in solid solution at finish rolling temperature and dependent on the processing conditions up to 50 % of the niobium content are not precipitated. The amount of niobium in solution is higher with higher finish rolling temperature,

promoting a higher volume fraction of bainite, figure 5. This explains one result shown in Figure 4, i.e. a certain strength increase is observed with higher finishing temperatures. In all cases the microstructure consists of poligonal ferrite and low carbon bainite (=acicular ferrite) only, and this in different portions dependent on the processing conditions, but no pearlite or martensite at all.

Fig.6 Influence of cooling conditions during and after to transformation on the mechanical properties

Fig.5 Correlation between niobium in solid solution, cooling rate and microstructure

If accelerated cooling is applied - a typical cooling rate for 18 mm plate is around 15 C/s - the microstructure is almost 100 % bainitic, with the result that the yield strength is higher than 600 MPa I and also the low temperature toughness is further improved, figure 6. Since niobium in solid solution is even more effective in lowering the transformation temperature when involving accelerated cooling, the HTP alloy design is especially suitable for that production route[7]. With higher cooling rates, such as 50 C/s, even higher strength is achieved[8]. Niobium in solid solution can also add to further strength increase by precipitation hardening the ferrite after transformation. If a slow cooling rate at 550 to 500 C is applied (stack cooling or coiling), this strength increase amounts to about 50 MPa.

4 Pipe Forming, Welding and HICResistance

Plate with (partial) bainitic microstructure exhibits almost no Lders elongation in the stress-strain curve. Therefore also the drop in yield strength, often observed in pipe forming - the Bauschinger effect -, is not observed with this steel; in most cases the involved cold deformation even results in a small yield strength increase. Welding simulation of the grain-coarsened heat affected zone (HAZ) showed, that one obtains a bainitic microstructure for a wide range of cooling rates (=welding processes). The low carbon bainitic microstructure guarantees excellent toughness. This is in line with fundamental considerations, figure 7[9], showing that besides the dominating influence of the carbon content, also the overall alloy content determines the HAZ toughness. Since higher alloy content lowers the transformation temperature, the final microstructure changes from coarse ferrite side plates, via granular bainite to acicular bainite, corresponding to a continuously finer effective grain. However, when the alloy content gets too high, martensite islands may be formed, impairing the toughness. The HTP alloy concept corresponds to a chemical composition guaranteeing the optimum HAZ toughness for a big variety of welding processes, including submerged arc welding and field welding. Test results of submerged arc weldments confirm the

Fig.7 Impact toughness in the simulated HAZ Fig.9 Results of HIC testing in pH=3.2 solution

excellent toughness data in the base metal and the heat affected zone. The relatively lowest toughness occurs in the weld metal, figure 8. These data show that the best results were obtained with a wire guaranteeing a bainitic microstructure used together with an alumina based basic flux, suitable to pick up the base composition. When the necessary low sulphur content and the correct Ca/S-treatment are guaranteed, the low carbon content of HTP steel should be beneficial avoiding hydrogen induced cracks (HIC). Test results shown in Figure 9 confirm, that even prolonged testing conditions (typical are 96 hours) do not lead to any cracks.

5 Recent Experience in Pipeline Projects

In the recent years several of large diameter pipe projects applied the HTP concept. In this context it should be mentioned, that already in 1971/72 a 0.04 %C 1.60 %Mn - 0.25 %Mo 0.06 %Nb steel had been used for a Canadian pipeline[10]. However, most of the actual application differ from this historic example by the fact that plate production made use of the installed accelerated cooling device. Table 2 gives an overview about pipeline projects applying the HTP concept and the chemical composition used. In 1997/98, Pemex applied this concept for an 84 km offshore gas pipeline in the Gulf of Mexico, the Cantarell project, which had to guarantee HIC resistance. The production of these pipes involved various companies, with Ispat Mexicana for steelmaking, Bethlehem Steel (US) for plate rolling and the Mexican pipe mill PMT [8]. Remaining slabs from this order were distributed by CBMM to a large number of clients around the world, who developed their own experience with this alloy concept. The results were collected and data regarding the influence of the carbon and manganese content and the processing conditions have been summarized[8]. A Chinese pipeline was built in the early 2000s, bringing natural gas from Tarim in the West of China over 4,000 km to Shanghai. Several companies were involved in supplying longitudinal or spiral welded pipes. The 26.6 mm thick wall pipes were supplied by Europipe, with steelmaking and plate had some

Fig.8 Toughness of submerged arc weldment

specific demands: for the first time the microstructure was defined to be acicular rolling at the shareholders Dillinger Htte and Mannermannrhrenwerke[11]. The project had some specific demands: for the first time the microstructure was defined to be acicular ferrite and also the demands in toughness for the HAZ and

the weld metal were higher than typical for X70 onshore lines. The suppliers decided to follow the HTP concept instead of adding either Mo or Cu+Ni to a 0.045 % Nb steel, since the overall properties were better and the small increase in niobium was also the cheaper solution.

Table 2 Examples of HTP projects Project Cantarell Steel grade X 70 sour gas wall mm 22.9 26.6 11.8 30.9 28.0 WestEast China X 70, high weldment toughness Cheyenne Plains Independence Trail Clad plate X 80 X 70 offshore X 65 without heat treatment C 0.028 0.050 0.050 0.060 0.030 Si 0.16 0.25 0.15 0.25 0.33 Mean Chemical Composition in % Mn 1.46 1.68 N 0.0042 0.0050 Ti 0.011 0.018 0.012 0.011 0.011 Nb 0.100 0.077 0.095 0.080 0.087 0.16 0.25 0.25 0.15 Cu 0.27 Cr 0.27 Ni 0.16

1.58 <0.0070 1.65 <0.0070 1.58 0.0042

In 2003/04 Colorado Interstate Gas built the first X 80 pipeline in the US. The total length of this project, called Cheyenne Plains, was 380 miles, asking for 180,000 tonnes of pipes. Two different suppliers delivered the pipes. The chemical composition shown in Table 2[12] was melted at Ispat Mexicana, rolled at Oregon Steel and piped at NAPA pipe mill, both in the US. The second supplier was the Canadian IPSCO, who also produced the properties with a low carbon bainitic microstructure, but with the help of molybdenum additions. Actually the Independence Trail Project is under construction in the Gulf of Mexico. This 135 miles long heavy wall pipeline asks for CTOD values in the HAZ at 0 C to be > 0.38 mm. The plates have been produced at Asovstal in the Ukraine[13] and the pipes are fabricated at Welspun in India. Processing HSLA steel at high temperatures is a necessity for clad plate and pipe, in order to guarantee the required corrosion resistance of the high alloy cladding material. A solution treatment and quenching plus tempering is the alternative traditional method. With the HTP concept such heat treatments can be avoided[14, 15]. In the recent years the Austrian company Voestalpine has carried out a major steel optimization for this application and the example shown in table 2 is a result of this work[16].

6 Summary and Outlook

The demand in higher transportation capacities asks for higher strength pipeline steels. Furthermore, new property demands arise with new resources, such as resistance against hydrogen induced cracking, high toughness at arctic temperatures or thick wall pipe. These often cannot be fulfilled with the traditional thermomechanically rolled ferritic-pearlitic X 65/X 70 pipe steel and bainitic microstructures are needed. With low carbon bainitic microstructures, an excellent combination of strength, toughness, formability and especially weldability can be obtained. The homogeneous microstructure of these steels guarantees also resistance against HIC. When accelerated cooling is applied, one can reduce the addition of expensive alloying elements such as molybdenum or nickel. Since low carbon steel can make use of higher niobium contents than traditional HSLA steels, levels up to 0.10 %Nb have been applied successfully. With higher niobium content the thermomechanical rolling can be carried out at higher temperatures, allowing also plate mills with relatively low installed rolling forces to produce modern pipe steel. Since a relevant portion of niobium remains in solid solution at finish rolling temperature, further strength increase by promoting finer ferrite and more bainite and some precipitation hardening in ferrite occurs. HTP steel has been successfully applied in several pipeline projects and also as HSLA strip with a

minimum yield strength of 550 MPa for the automotive industry[17], guaranteeing a narrow scatterband of mechanical properties and the excellent hole expansion behaviour as result of the homogeneous microstructure. The excellent property combination and the ease of fabrication allows the assumption that the HTP concept will be used more extensively in the near future. The application might spread to thick plates and shapes for welded construction and also to new welding processes such as laser or electron beam welding.

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[6] K. Hulka, J.M. Gray and F. Heisterkamp, Pipeline Technology,Volume II, Brgge (Belgium), 2000. [7] S. Okaguchi, T. Hashimoto and H. Ohtani, Thermec 88, ISIJ, Tokyo (Japan), 1988, p. 330. [8] K. Hulka, P. Bordignon and J.M. Gray, Niobium Technical Report No 1-04, CBMM, Sao Paulo (Brazil), August 2004. [9] K. Hulka and F. Heisterkamp, HSLA Steels 95, The Chinese Society of Metals, Beijing (China), 1995, p. 543-551. [10] R.L Cryderman et al., Proceedings of the 14th Mechanical Working and Steel Processing Conference, AIME, 1972, p. 114 . [11] M. Grf, J. Schrder, V. Schwinn and K. Hulka, Pipe Dreamers Conf. Proc., Yokohama (Japan), 2002, p.323. [12] D. Stalheim, private communication, Dec. 2003 to May 2004. [13] O.A. Bagmet and Yu.I. Matrosov, private communication in 2005. [14] H. Tamehiro et al., OMAE 1993, ASME, New York (NY), 1993, Vol. V, p. 319. [15] K. Hulka, H.G. Hillenbrand, F. Heisterkamp and K. Niederhoff, Microalloying 95, ISS, Warrendale (Pa), 1995, p. 235. [16] R. Grill and R. Schimbck, private communication 2003. [17] W. Hnsch and C. Klinkenberg, TMP 2004 Conference Proceedings, Verlag Stahleisen, Dsseldorf (Germany), p. 115.