Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada

IPC2012-90412

CHARACTERIZATION OF X80 GRADE LINEPIPE STEEL COIL WITH 24 MM THICKNESS

Nuria Sanchez* OCAS NV, ArcelorMittal Global R&D Gent, Belgium Nenad Ili ArcelorMittal Bremen Bremen, Germany

Martin Liebeherr OCAS NV, ArcelorMittal Global R&D Gent, Belgium

ABSTRACT High strength and high toughness at low temperatures on heavy wall thickness skelp is required to build high pressure gas transportation pipelines. Detailed mechanical and microstructural characterization was carried on 24mm thick ArcelorMittal X80 coils in order to identify the microstructure control required to reach high toughness as determined by the shear fracture appearance after DWTT testing. Detailed microstructural characterization through thickness reveals that the microstructure gradient described by a systematic increase of the average grain size between surface and middle thickness of the strip and the increment of the volume fraction of M/A (martensite/ retained austenite) are the key microstructural parameters to control in order to ensure the adequate toughness of the material. The obtained high toughness of the coils indicates that the microstructure, controlled by an optimized rolling and cooling practice, is homogeneous through thickness of heavy wall linepipe grades.

For this application, spiral welded pipes represent an economical solution since the hot strip coil processing and pipe production are continuous processes characterized by high productivity. High strength microalloyed steels have been commonly used over the past decades for the production of welded pipes dedicated to oil and natural gas transportation. Nevertheless, as the market requests continuous improvements on the transport efficiency, the use of higher strength steel grades that in return enables higher operating pressure and higher gas transmission rates is generalized. Simultaneously, low temperature toughness became fundamental to ensure the integrity of pipelines operating in arctic regions. Hence, continuous optimization of the steel grades is required. Alloying designs and process parameters have been continuously optimized in order to meet the high strength and high toughness requirements demanded for the high wall thickness spiral welded pipes. Toughness of linepipe steel grades determines the fracture propagation behavior of pipelines. Consequently the steel grades used in low temperature environments should present transition temperatures low enough to prevent abrupt brittle fracture, commonly determined by the shear fracture appearance after drop weight tear testing (DWTT) at the minimum service temperature. At the same time the material needs to absorb energy, high enough to prevent unstable ductile fracture propagation, characterized by the absorbed energy during Charpy impact testing. However, there are many microstructural parameters that control toughness and strength such as

INTRODUCTION The increasing energy demand and particularly the natural gas demand, being the worlds fastest-growing fossil fuel energy source, with an estimated consumption increase of 1.6 percent per year [1] has promoted the exploitation of gas and oil fields located in remote arctic areas with extreme weather conditions. Still, large diameter pipes remain the most cost effective transportation means, particularly in land locked areas.

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type of microstructure, grain size, distribution and volume fraction of phases [2-4] that need to be characterized. The control of the fracture behavior in the transition temperature region is generally attributed to the distance between cleavage fracture facets and is closely related to the effective grain size as defined crystallographically by the grains limited by high angle grain boundaries [4 -7]. The intention of this study is first to identify and, secondly, quantify the microstructural parameters that control the toughness, in particular the DWTT of X80 grade linepipe steel with large wall thickness.

Precipitate size distribution analysis was performed by transmission electron microscopy (TEM) on carbon replicas. An energy dispersive X-ray detector (EDX) was used to analyse the chemical composition of the particles.

RESULTS AND DISCUSSION Mechanical properties required for the steel grade X80/L555 according the API5L-ISO3183 were fulfilled in both evaluated coils. However a remarkable difference on the low temperature toughness, e.g. at a temperature considerably below -10 was observed (cf. Figure 1). C, Detailed microstructural characterization, intended to identify the key microstructural parameters which explain such different toughness behavior, was performed on the studied coils.
Shear fracture appearance % after DWTT at low temperature 100

EXPERIMENTAL Two industrially processed ArcelorMittal hot rolled coils, coil A and Coil B, of linepipe steel grade X80/L555 with actual wall thickness of 24mm were evaluated during this investigation. The coils have been produced in the framework of industrial trials testing the performance of the newly installed heavy crop shear, with capability to crop transfer bar thickness up to 76 mm. The chemical composition is presented in Table 1.

Grade X80

C <0.07

Mn >1.6

V+Nb +Ti <0.15

Ni+Cu+ Mo+Cr >0.6

Ceq (IIW) <0.44

Pcm <0.19

Table 1. Chemical composition of ArcelorMittal X80 coils

0 Coil A Coil B

The mechanical properties of coil A and B were determined using standard specimens taken from the coil transverse direction, i.e. API tensile and DWTT samples, and using standard practice. Microstructural characterization was performed at different positions through the thickness in longitudinal cross sections. Evaluation of the grain size, distribution of second phases and presence of inclusions, are obtained by means of optical microscopy. The specimens have been previously embedded, mechanically polished and etched with (i) Nital 2% for 10s, (ii) Picral 4% for 30s followed by Sodium metabisulfite 10% for 7s and (iii) sodium metabisulfite 10 % for 5 seconds and Klemms for 60 seconds. Microstructure and microtexture was further quantified by electron backscattered diffraction (EBSD) after conventional mechanical polishing and oxide polishing. The determination of the fraction of precipitates was conducted by means of inductively coupled plasma mass spectrometry (ICP-MS) after electrolysis;

Figure 1. Difference in the shear fracture appearance after DWTT at low temperature The microstructure observed in both coils is significantly different. Figure 2 and Figure 3 present optical and SEM micrographs of the microstructures of both coils in a longitudinal cross section at the quarter thickness position. The microstructure of coil A, which has the better toughness, is composed predominantly of low carbon bainite microstructure with different bainite morphologies: fine and elongated bainitic ferrite grains (BF) and presence of coarser granular bainite (GB) (cf. Figure 2 (a)). In contrast, the microstructure of coil B consists mainly of polygonal (PF) and quasi-polygonal ferrite (QPF), with coarse grains of granular bainite (GB) (cf. Figure 2 (b)). Presence of other phases such as martensite (M), retained austenite (RA) and complex martensite-austenite (M/A) constituents was evidenced by means of dedicated colour etching using Klemms and Picral combined with Sodium metabisulfite. Significant amounts of second phases were observed in quarter thickness position of coil

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B, whereas the amount was negligible in coil A (cf. Figure 2 (c) through (f)). Both etchings, Klemms and Picral / sodium metabisulfite, revealed that the second phase in coil B at quarter thickness mainly concerns carbon rich phases.

QPF

GB GB PF BF

(a) Coil A

(b) Coil B

RA

(c) Coil A

(d) Coil B

M/A

(e) Coil A

(f) Coil B

Figure 2. Optical micrograph at strip thickness after Nital 2% etching (a) and (b), after Klemms etching (white phase is retained austenite) (c) and (d), after Picral and Sodium metabisulfite (dark phase is M/A) (e) and (f)

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GB

GB

M/A

UB

BF

(a) Coil A at quarter thickness

(b) Coil B at quarter thickness

BF M

GB

(c) Coil A at middle thickness

(d) Coil B at middle thickness

Figure 3. SEM micrograph after Nital 2% etching at quarter strip thickness (top) and middle thickness (bottom)

Further evaluation by SEM revealed fine and elongated bainitic ferrite grains with irregular grain boundaries, dispersed carbides and retained austenite surrounding the bainitic grains in coil A (cf. Figure 3 (a)). Coil B presents coarser granular bainite grains and carbide rich phases, which revealed black in optical microscopy (cf. Figure 2 (b)), could be identified by SEM as carbon rich upper bainite (cf. Figure 3(b)). Presence of carbon rich upper bainite was not detected in coil A, although some presence of fine and dispersed M/A constituents, not detected by optical microscopy, were observed at higher resolution in SEM (cf. Figure 3 (a)). This difference in volume fraction of carbon rich phases is more pronounced in the middle thickness position, where coil A reveals some fine M/A constituents (cf. Figure 3 (c)), whereas coil B exhibits coarser grains of martensite and M/A constituents (cf. Figure 3 (d)).

A negative effect of coarse GB grains on low temperature toughness was previously reported. Hang et al [5] correlated the increment of GB volume fraction present in X80 grades with the detriment observed in the absorbed energy and particularly pronounced in the ductile to brittle transition temperature in Charpy impact testing. At the same time, the observed negative effect of the hard, carbon rich phases such as upper bainite, martensite or M/A on low temperature toughness is generally confirmed, in particularly when hard phases are formed in coarse morphology, because they act as stress concentrators [9]. However, some positive effect of carbon rich phases has also been reported. Shanmugam et al [10] attributed Charpy impact toughness improvement observed in a Nb microalloyed steel to the presence of degenerated pearlite.

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EBSD evaluation allowed to determine quantitatively the grain size, shape and orientation (cf. Figure 4). The band contrast map reveals a similar picture from the microstructure as the Nital etched micrographs. The contrast of the bands corresponds to the sharpness of the Kikuchi pattern, which in turn depends on the density of lattice defects in the beam-material interaction volume. High lattice misorientations caused by lattice defects (grain boundaries, high dislocation density, strain accumulation, martensite) display blurred patterns whereas the dislocation free zones, such as ferrite in recrystallized steel display clear patterns. Therefore, the grain boundaries, high dislocation densities and other lattice defects are revealed in darker grey on the band contrast map (cf. Figure 4 (a)). The inverse pole figure map Figure 4 (b) reveals the crystal orientations of the grains. The polygonal ferrite grains can be distinguished from the elongated bainitic ferrite and granular ferrite by the colour difference inside the grains. While polygonal ferrite exhibits a uniform colour inside the individual grains due to the virtual absence of dislocations (cf. Figure 4 (c)), bainitic grains are revealed by the colour gradients which is caused by the higher dislocation density and the sub-structure inside the single individual grains (cf. Figure 4(d)). The considered cut off criteria for the grain boundary quantification was a minimum grain boundary angle misorientations of 15 generally considered the bo undary , angle corresponding to the crystallographic domains defined as effective grain size, closely related with the unit crack path, which is the distance between cleavage fracture facets [4, 5, 8, 11]. A grain boundary map is presented in Figure 4 (e), black lines correspond to high angle grain boundaries (threshold angle 15 and re d lines ) correspond to low angle grain boundaries (threshold angle 4 Note that the elongated bainitic grains genera lly ). display a pronounced sub-grain structure (i.e. red lines inside the black delimited lines), while the polygonal grains are free of sub-grain structure. EBSD investigations also revealed low band contrast areas in the band contrast map corresponding with the carbon rich phases, upper bainite and martensite, observed by SEM in coil B. No evidence of carbon rich phases were found in coil A, since no low band contrast phases were observed (cf. Figure 5). Grain size quantification evidenced further differences between the two coils. Grain refinement is considered the only strengthening mechanism that improves at the same time the strength and toughness of the steel. In fact, the DWTT has been related to the effective grain size defined as crystallographic domains limited by high angle grain boundaries (HAGB>15 degrees) [4, 5, 8, 11]. The grain size distribution was determined from EBSD scans of a 200m by 300m area measured with a step size of 0.2m using the area fraction of crystallographic domains

surrounded by HAGB. The grain size was defined by the diameter of circular areas equivalent to the grain area as defined in Eq. 1, where di is the equivalent diameter of one grain, ai is the corresponding area and at is the total scanned area.

d i ai

at
Eq. 1

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GB

GB

PF

PF

(a) Band contrast map

(b) Inverse pole figure map

GB (c) Detail polygonal ferrite: Equiaxed grain with no orientation gradient within the grain

(d) Detail bainitic grain: elongated grain with high orientation gradient inside the grain (e) Grain boundary map Figure 4. EBSD maps from coil A at strip thickness.

(a) Coil A

(b) Coil B

Figure 5. Band contrast map from EBSD measurement at strip thickness, (a) coil A, (b) coil B

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(a) Coil A

(b) Coil B

Figure 6. Grain size area fraction distribution at strip thickness, (a) coil A, (b) coil B

Grain size D, m (Av area)

Figure 6 shows the grain size distribution in thickness position of the investigated coils, evidencing a quite large spread of the grain size. Grain size distributions expressed as area fractions of equivalent circular grain areas revealed at quarter thickness position the presence of grains larger than 66m in coil B, whereas the maximum equivalent diameter in coil A corresponded to 55m. The corresponding average grain size was also larger in coil B, i.e. 18m versus 15m in coil A. The difference observed in the grain size of both coils appears more obvious in Figure 7, were the cumulative distribution function of the grain size of both coils is plotted. Similar grain size distribution is observed below 20m, however the coarser grains (>20m) are more significant in coil B, with poorer toughness.

The grain size distribution was also measured on a longitudinal section at different thickness positions between the strip surface and the strip middle thickness. At each position, relatively large areas were scanned by EBSD (600m // ND x 250m // RD with a step size of 1m). The obtained results reveal a systematic increase of the average grain size between surface and core of the sheet: from 10m close to the surface to 15m in the middle thickness (cf. Figure 8).

16 15 14 13 12 11 10
Surface Middle

Av GS coil A

100 Cumulative grain size distribution (%)

Coil A

80 60 40 20 0 0.1

Coil B

0.5

2 3.5 5 6.5 8 9.5 11 Thickness position, mm

10

100

Figure 8. Grain size gradient between surface and middle thickness of coil A

Grain size (m)

Figure 7. Comparison of the grain size of both coils

Taken into account the elongated shape of the grains, a second calculation was made based on the thickness of the pancake structure. The pancake thickness of equivalent elliptical areas was determined for both coils to

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estimate the grain pancake thickness. As usual, grains were defined with the grain boundary angle cut off criteria of 15 Taking into account the area and shape of e ach . grain, the average aspect ratio extracted from the EBSD scans at quarter thickness was 3.5 in coil A and 3.4 in coil B. The average pancake thickness (balance by the area of each grain) was 8 m, and the maximum pancake thickness 20m in coil A whereas in coil B, both average and maximum thickness quantification were larger, 10 and 30m respectively. The larger average pancake thickness of coil B indicate that the grains in this coil are generally more polygonal than in coil A, which is in agreement with the earlier observed larger volume fraction of polygonal and quasi-polygonal ferrite in coil B. Table 2 summarizes the quantification related the grain size and aspect ratio in both coils.

Figure 9. TEM micrograph on carbon replica coil A at quarter strip thickness Coil A Average equivalent diameter (m) Maximum equivalent diameter (m) Average pancake thickness (m) Maximum pancake thickness (m) Average pancake length (m) Average aspect ratio 15 55 8 25 28 3.5 Coil B 18 66 10 30 34 3.4

Table 2. Aspect shape of the evaluated coils

Precipitation analyses conducted at quarter and middle thickness position by means of carbon replica in TEM indicates that the precipitates present in the evaluated coils consist mainly of Nb-rich and Nb-Ti carbides. A high concentration of medium size precipitates can be observed on the bright field image on carbon replica presented in Figure 9. The corresponding EDS spectrum is presented in Figure 10. Small differences in the particle size distribution were detected on the different thickness position and between the two evaluated coils. The particle size distribution presented in Figure 11 revealed slightly coarser particles at middle thickness of the coils. The mean particle diameter is between 20nm and 60nm. A few larger particles (>150nm) were also observed.

Figure 10. Corresponding precipitate EDS spectrum

On the other hand, the amount of precipitated Nb is significantly lower in coil B as compared to coil A, both in the quarter thickness and middle thickness (cf. Table 3). In coil A, about 50% of the Nb was precipitated, both in quarter and middle thickness position. In contrast, coil B showed only 45 and 30% Nb precipitated in quarter and middle thickness position, respectively. This gradient observed in the Nb precipitation indicates a gradient on the strain accumulation during finishing rolling, which is also in agreement with the observed grain size gradient. Despite the fact that this gradient was observed in both coils, the differences are more significant in coil B, which had significantly lower shear fracture appearance after DWTT.

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100 80 Frequency 60 40 20 0
30 90 10 50 70

Coil A Q Coil A M Coil B Q Coil B M

Particle size, m
Figure 11. Precipitates size distribution at quarter thickness (Q) and at middle thickness (M)

The crystallographic texture observed in quarter thickness position corresponds to a weak hot rolling transformation texture, with intensities of 2 times random located on the components resulting from the transformation from deformed austenite components (Cu {112}<111>, Goss {110}<001>, Br {110}<112> and S {123}<634>): {225}<110> , {112}<131>, {332}<113> and {001}<110>. Maximum intensity of 2.5 times random corresponds to the component {332}<113> which is a component favored by variant selection for low temperature transformation; however the intensity differences of this component is not significantly higher than that of the other components. Main components are highlighted with grey squares in Figure 12. Small differences in the crystallographic texture are observed between the 2 coils at quarter thickness position (cf. Figure 12(a) versus Figure 12 (b)). Both exhibit weak transformation textures with the higher intensity located around the same components. The only difference is given by the weaker {332}<113> component in coil B. The numerous EBSD measurements performed throughout the sheet thickness did not evidence a significant texture gradient. All evaluated positions revealed a weak transformation texture with intensities located on the components transformed from deformed austenite {225}<110>, {112}<131>, {332}<113> and {001}<110>. The intensities vary between 1.5 and 2. Despite the similarities of all ODFs, the gradual increment of the rotated cube, i.e. {001}<011> component towards the middle thickness should be emphasized. This particular component appears as a result of the transformation of both deformed and recrystallized austenite. Therefore, this slight texture gradient could be an indication of a decreasing deformation accumulated towards the middle thickness during hot rolling in the finishing mill. However, it should be recalled that the textures are in general weak, indicating an overall low level of strain accumulation.

Coil A

Middle Quarter Middle Quarter thickness thickness thickness thickness % Nb precipitated 55% 49% 47% 30%

Table 3. Percentage of Nb precipitated in the quarter and middle thickness of the evaluated coils
The determination of the crystallographic texture at different thickness position also provides the possibility to evaluate the strain accumulation gradient through the thickness by comparing the intensity of the different crystal orientations through the thickness and considering the corresponding parent austenite orientations (according to the crystallographic correspondence between the parent fcc phase and the product bcc phase).

11 0 13 0 15 0
Coil B

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0 0

{001}<110>

90

2=45

0 0

{001}<110>
1 1.5 2 2.5

{001}<110>

90 {001}<110>

{225}<110> {112}<131>

{225}<110> {112}<131>

{332}<113>

{332}<113>

90

90

(a) Coil A at quarter thickness

(b) Coil B at quarter thickness

Figure 12. 2=45 section of the ODF from (a) coil A at quarter thickness and (b) coil B at quarter thickness

Figure 13. Texture gradient through thickness of coil A (2=45 sections of the ODF)

CONCLUSIONS
The intention of this study is to determine a correlation of microstructure and shear fracture appearance after DWTT at low temperature. Two X80 hot rolled coils with 24 mm thickness have been selected with the same chemical composition and produced with variation of the process parameters during industrial trials at ArcelorMittal. The microstructure of the coils was thoroughly

characterized: grain size, grain size gradient through thickness, presence of second phases, precipitates. The present evaluation reveals a significant effect of the type of microstructure. Fine and elongated bainitic ferrite grains have been identified as more beneficial to DWTT toughness than polygonal or quasi polygonal ferrite grains. The presence of coarse granular bainite grains was identified as detrimental to toughness. At the same

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time the presence of hard, carbon rich phases was observed in the coil with lower toughness. Systematic increase of the average grain size from the surface to the middle thickness position was observed, indicating a reduction of the strain accumulation through the thickness during finishing rolling. This observation was confirmed with the quantification of the Nb-rich precipitates at different thickness positions, some reduction of volume fraction of Nb-rich precipitates was observed in the middle thickness of the coil with poor toughness. Some extra indication of the limited strain accumulation on the middle thickness position was also indicated by the observation of the crystallographic texture on different thickness positions. Rotation of the weak texture towards the rotate cube component at middle thickness indicates a larger presence of recrystallized austenite grains in the middle thickness as compared with the quarter thickness were the deformed austenite grains would be predominant.

3. Ming-chun Zhao, Ke Yang, and Yi-yin Shan. Materials Letters, 57 (2003), 1496 1500. 4. S Yong, B Hwang, S Lee, N J Kim, and S Soo. Materials Science and Engineering A, 458 (2007), 281-289 5. Seung Youb Han, Sang Yong Shin, Chang-hyo Seo, Hakcheol Lee, Jin-ho Bae, Kisoo Kim, Metallurgical and Materials Transactions A, 40 (2009) 6. M Liebeherr, N Bernier, D. Lbre, N. Ili, D Quidort, IPC2010- 31250 7. Ryan W. Regier, John G. Speer, David K. Matlock, Jong-Kyo Choi. International Symposium on the Recent Developments in Plate Steels 2011. 8. W Wang, W Yan, L Zhu, P Hu, Y Shan and K Yang, Materials and Design, 30 (2009), 34363443. 9. B. Hwang, S. Lee, Y. M. Kim, N. J Kim, Metallurgical and Materials Transactions A, 36 (2005). 10. S. Shanmugam, R.D.K. Misra, T. Mannering, D. Panda, S.G. Jansto. Materials Science and Engineering A 437 (2006) 436445

REFERENCES
1. International Energy Outlook September 2011. US Energy information administration. 2. Y M Kim, S K Kim, Y J Lim, and N J Kim. ISIJ International, Vol. 42 (2002), No. 12, pp. 1571 1577

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