http://dx.doi.org/10.2139/ssrn.

4084614

Abnormal growth mechanism of the austenite grains in long-term,

high-temperature served Super304H heat resistant steel tube

Xianqiang Zhan a, Yue Wu b, c, Run Liu a, Junjian Liu b, c, Wanli Wang b, Yan Wang c,

Wenming Tang a, *

(a. School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009,

China

b. Datang Boiler and Pressure Vessel Testing Center Co Ltd, Hefei 230088, China;

c. Datang East China Electric Power Test and Research Institute, Hefei 230088, China)

Abstract: Abnormal austenite grain growth was detected in outer wall of the long-term

served Super304H superheater steel tubes of an ultra-supercritical unit, however, the

mechanism is unclear and confusing. In this study, microstructures of the as-supplied/-

served Super304H steel tubes were contrastively investigated through OM, SEM,

EBSD and TEM to reveal the abnormal grain growth (AGG) mechanism. The results

show that the low-energy coincident site lattice boundaries and sub-boundaries are

small in amount, and the texture intensity is weak on the whole cross section of the as-

supplied steel tube. Non-uniform distribution of the secondary-phase particles is not

detectable in the as-supplies/-served steel tubes. However, that of the residual strain in

outer wall of the as-supplied steel tube was detected, bringing about a high distortion

energy difference. In the long-term, high-temperature service process, the low-

distortion austenite grains annex the neighboring high-distortion ones to induce the

* Corresponding author. Tel. & Fax: +86 551 62901362.

E-mail address: wmtang@hfut.edu.cn (Wenming Tang).
1

Electronic copy available at: https://ssrn.com/abstract=4084614

AGG, following the strain induced grain boundary migration mechanism. Meanwhile,

the faceted grain boundaries in outer wall of the as-supplied steel tube also promote the

AGG via the two-dimensional step mechanism.

Keywords: Super304H steel tube; Abnormal grain growth; Residual strain; Strain

induced grain boundary migration; Faceted grain boundary

Electronic copy available at: https://ssrn.com/abstract=4084614

1. Introduction

Ultra-supercritical (USC) power generation is one of the most effective technologies

to improve fossil energy utilization, and to reduce emissions in current thermal power

units [1]. With the improvement of operating parameters of the USC boilers, ever-rising

steam temperature results in the wall-temperature of the superheater and reheater tubes

approaching and even exceeding 680 °C. Therefore, it is crucial to develop new heat-

resistant steels of high strength and oxidation, creep resistance in order to satisfy such

operating parameters [2-6]. Based on the traditional TP304H steel, a new Super304H

heat-resistant steel has been successfully developed by increasing the C content,

reducing the Mn content, and adding about 3 wt% Cu, 0.45 wt% Nb and trace N,

respectively [7]. During long-term, high-temperature annealing, the structural stability

and mechanical properties of the steel can be significantly improved in terms of

successive precipitation of the secondary-phases such as Cu-rich phase, M23C6 (M

mainly refers to Cr, Ni and Fe), MX (Nb(C,N), NbCrN) and so on. Nowadays, the

Super304H heat-resistant steel has become one of the preferential high-temperature

materials of the superheater and reheater tubes in the USC units [8, 9].

The rated steam pressure and temperature of the Super304H steel superheater tubes

in a certain normally-operated USC unit are 25 MPa and 580 °C, respectively. After the

tubes running for 40,000 h, a coarse grain area about 2 mm in thickness from the outer

wall was detected. Such a phenomenon is rarely reported, during operational

supervision of the in-service Super304H steel tubes. The abnormal grain growth (AGG)

mechanism is still unclear and confusing. In our previous study [10], it was

Electronic copy available at: https://ssrn.com/abstract=4084614

preliminarily confirmed that the AGG was harmful to the room-/high-temperature

mechanical properties of the in-service Super304H steel tubes. Therefore, it is of great

significance to reveal the AGG mechanism. On this basis, active methods should be

figured out to prohibit the harmful microstructural change, and further to improve safety

and service life of the Super304H steel tubes.

The AGG has been widely reported in some face center cubic (fcc) metals, including

austenitic steels as well as Ni, Al and Cu and their alloys, during annealing in high

temperature [11-14]. According to these wonderful works, the AGG mainly results

from the following factors:

1) Nonuniformly pinning of the secondary-phase precipitates [15-17]. During long-

term annealing these materials at high temperature, coarsening and inhomogeneous

distribution of the secondary-phase precipitates take place to produce the nonuniformly

pinning effect on the austenite grains. As a result, preferential growth of some austenite

grains achieves, characterizing by a bimodal distribution of the austenite grain size.

2) Dragging of the solute atoms [18-20]. Generally, solute atoms preferentially

segregate at grain boundaries, due to a low atom density. As the annealing temperature

is high enough, the driving force of grain boundary migration is greater than the

dragging effect of solute atoms, as a result, the grain growth rate increases greatly. Such

a phenomenon has been demonstrated via the phase field simulation [20].

3) Textures [14, 21, 22]. Sometimes, the AGG takes place in the materials having

apparent textures, because the grain boundary mobility is limited among the grains of

the similar orientation, on the contrary, it is accelerated among the grains of different

Electronic copy available at: https://ssrn.com/abstract=4084614

texture orientations. For example, the AGG in the Al alloy is attributed to

inhomogeneous distribution of the cubic recrystallization texture [14].

4) Grain boundary anisotropy and faceting [23-25]. Monte Carlo simulation shows that

a strong grain boundary anisotropy can induce the AGG [24, 25]. In the AGG process,

migration of the specific grain boundaries is accelerated by the faceted grain boundary

via the two-dimensional nucleation mechanism, as demonstrated in Cu, Ni and their

alloys [13, 23].

5) Coincident site lattice (CSL) boundaries and sub-boundaries enhanced solid-state

wetting (SSW) [26-30]. The Zener pinning force at the CSL boundaries is rather low,

due to the low energy of the CSL boundaries. And thus, the CSL boundaries have a

high mobility in the alloys containing the secondary-phase precipitates, which provides

some convenience for the AGG [26-28]. In addition, the sub-boundary enhanced SSW

can also induce the AGG. If a certain grain has the sub-boundaries with extremely low

energy, the AGG of the grain is of a high probability by SSW along the grain boundary

triple junctions [29, 30].

6) Plastic deformation [31-36]. After deforming at a low critical strain range, the AGG

of some grains takes place in the subsequent annealing process, which is different from

the AGG in the usual sense, also named as secondary recrystallization. In this situation,

the heterogeneity of the distortion energy distributed in the grains and the nucleation

sites limited recrystallization are two competitive mechanisms of the AGG [33].

It is worth noting that most of the studies mentioned above are mainly implemented

under laboratory conditions, concerning one certain factor. However, the fabrication

Electronic copy available at: https://ssrn.com/abstract=4084614

process and service status of the Super304H steel tubes are so complicated that the

AGG of outer-wall of the in-service Super304H steel tubes may not result from one

factor. Unfortunately, studies on this issue are still limited so far. In this work, the AGG

mechanism of the in-service Super304H steel tubes was carefully clarified by

investigation on microstructures of the as-supplied/-served Super304H steel tubes.

2. Experimental

2.1 Materials

The in-service Super304H steel tubes running for about 40,000 h were sampled from

a superheater bank of tubes in a USC unit, and the as-supplied Super304H steel tubes

were from the spare materials of the same batch in the solid solution treatment state.

The specification of the steel tubes is 51 mm in outer diameter and 9.5 mm in wall

thickness. The chemical composition of them is listed in Table 1.

Table 1 Chemical composition of the Super304H steel tube (wt%)

C Mn Si Cr S P Ni Nb N Al B Cu Fe

0.08 0.66 0.2 18.3 0.004 0.017 8.72 0.52 0.1 0.008 0.005 3.02 Bal.

2.2 Characterizations

The samples were taken along the radial direction of the as-supplied/-served

Super304H steel tubes using wire cutting, respectively (Fig. 1). After mechanically

grinding and polishing, the samples were etched in aqua regia, and finally observed

under an MR-3000 type optical microscope (OM) and a Regulus 8230 type scanning

electron microscope (SEM). Micro-zone compositions were tested using a Bruker

Electronic copy available at: https://ssrn.com/abstract=4084614

XFlash 60 type X-ray energy dispersive spectrometer (EDS). A Gemini 500 type SEM

equipped with an Oxford C-Swift type electron backscatter diffraction (EBSD) system

was used to conduct the grain orientation and residual stress distribution of the samples.

The ND-TD plane of the sample was detected, as shown in Fig. 1. After polishing, the

EBSD samples were electropolished for 30 s at room temperature in a 10 vol%

perchloric acid ethanol solution, and the voltage and current density were set as 8 V and

0.2 A/mm2, respectively.

The circular sheets of 3 mm in diameter and 200 µm in thickness were cut from the

different areas of the as-supplied/-served Super304H steel tubes, ground to 40-50 µm,

and then recessed to about 10 µm in thickness using a Gatan dimple meter, respectively.

Finally, the sheets were thinned using a Gatan-691 type ion beam thinner till perforation.

A JEM-2100F type field emission transmission microscope (TEM) was used to identify

the microstructural characteristics of austenite grains and their boundaries.

Fig. 1 Schematic illustration for sampling the EBSD specimen

3. Results and discussion

3.1 Microstructures

Electronic copy available at: https://ssrn.com/abstract=4084614

 Fig. 2 OM cross-sectional images showing microstructures of outer-wall (a), (b)

and (c), (d) other area of the as-supplied Super304H steel tube (a), (c) Low-

magnification images; (b), (d) High-magnification images

The as-supplied Super304H steel tubes are generally prepared through a complicated

process scheme, i.e., melting plus secondary refining in an electric arc furnace or a

converter, solid-solution softening at a temperature above 1230 °C, cold rolling, and

finally solid solution treatment at a temperature above 1050 °C. As shown in Fig. 2, the

austenite grains in them are uniform and equiaxed with an average size of 20 μm (grade

8-9), however there is also an obvious difference in microstructure between the outer

wall and the other area. Parts of the grains in the outer wall area are dark (Fig.2a),

resulting from the deformation twin bands in them. More specifically, these twin bands

have different orientations and therefore intersect to form the twin grids in the austenite

Electronic copy available at: https://ssrn.com/abstract=4084614

grains (Fig.2b). In the other area, light and dark contrast is not detectable, and almost

no deformation twin bands exist in the austenite grains (Fig.2c, d).

Generally, after cold-rolling the Super304H steel tubes, the deformation degree of

austenite grains is different, owing to nonuniform plastic deformation of the tube and

anisotropy of the austenite grains. A greater strain exists in the austenite grains having

a larger plastic deformation and a more preferential grain orientation, vice versa,

resulting in an uneven strain distribution. The outer wall of the Super304H steel tube

directly undertakes the rolling force, and therefore has a higher plastic deformation.

Even after the subsequent solution treatment, recrystallization of the deformed austenite

grains is not fulfilled, and the cold-deformation structure is remained. As a result, the

nonuniform microstructure still exists in the outer wall of the steel tube (Fig. 2a, b). On

the contrary, the microstructure in the other area of the steel tube is much more uniform

(Fig. 2c, d).

Electronic copy available at: https://ssrn.com/abstract=4084614

 Fig. 3 OM cross-sectional images showing microstructures of outer-wall (a), (b) and

(c), (d) other area of the as-served Super304H steel tube (a), (c) Low-magnification

images; (b), (d) High-magnification images

As shown in Fig. 3, after running for 40,000 h, the microstructure of the Super304H

steel tube is significantly changed. The austenite grains in the outer wall grow

abnormally to form about 1.8 mm thick coarse grain zone (Fig. 3a). The maximum grain

size of them is up to 300 μm. Generally, a large grain always annexes its neighboring

small grains via grain-boundary movement towards their curvature centers, till the grain

boundary tends to be straight [17]. In the coarse grain zone, the annexing of the

abnormal austenite grains is near to completion, some large grains connect with each

other (Fig.3b). Some residual grain-boundary segments in the large grains are

observable, possibly because these segments are pinned by the secondary-phase

precipitates, and thus have a small migration rate. However, in the area approach to the

inner wall of the steel tube, the AGG is active to form the mixed grain zone in which

the average grain size is lower and the grain boundaries are more curved, than the coarse

grain zone (Fig.3a). In the fine grain zone away from the outer wall, no abnormal

austenite grain growth takes place, the austenite grain size is uniform, approximately

10

Electronic copy available at: https://ssrn.com/abstract=4084614

the same as that of the as-supplied super304H steel tube (Fig.3c, d).

3.2 Secondary-phase precipitates

Fig. 4 SEM cross-sectional images and EDS spectra of the as-supplied Super304H

steel tube (a) Outer-wall area; (b) Other area; (c) EDS spectrum of points 1, 2, 4, 5

and 6 in Fig. a, b; (d) EDS spectrum of point 3 in Fig. a, b

11

Electronic copy available at: https://ssrn.com/abstract=4084614

Fig. 5 SEM cross-sectional images and EDS spectra of the as-served Super304H steel

tube (a) Outer-wall area; (b) Other area; (c) EDS spectrum of points 1, 2, 4, 5 and 7 in

Fig. a, b; (d) EDS spectrum of points 3and 6 in Fig. a, b

Nonuniform pinning of the secondary-phase particles is often regarded as the likely

factor to induce the AGG. As shown in Fig. 4, the secondary-phase precipitates are

rarely found at the grain boundaries of the as-supplied Super304H steel tube. There are

several big particles of NbC distributed in the austenite grains or along the grain

boundaries (Fig. 4a, b). Moreover, there are high-density MX precipitates, evenly

distributed in the austenite grains. As for the as-served Super304H steel tube, more

secondary-phase particles precipitate in the austenite grains and grain boundaries. The

M23C6 particles almost continuously distribute at the austenite grain boundaries, and

the MX, Cu-rich and M23C6 particles disperse in the austenite grains. It is concluded

that the nonuniform pinning effect of the secondary-phase precipitates on the austenite

grain boundaries is not evidential for the Super304H steel tube in the service process.

For this reason, the underlying cause of the AGG is not lain in the service process of

the Super304H steel tube, but in the as-supplied one. The long-term, high-temperature

running process only make the phenomenon more apparent.

12

Electronic copy available at: https://ssrn.com/abstract=4084614

3.3 Grain boundaries

13

Electronic copy available at: https://ssrn.com/abstract=4084614

 Fig. 6 Inverse pole figures (a, c, e, g) and (b, d, f, h) grain boundary maps of the

Super304H steel tubes (a, b) As-supplied, outer-wall area; (c, d) As-supplied, other

area; (e, f) As-served, outer-wall area; (g, h) As-served, other area

Table 2 Special CSL grain boundary proportions of the as-supplied/-served Super304H steel tubes (%)

Σ1 Σ3 Σ9+Σ27 Low-ΣCSL

As-supplied, outer-wall area 5.8 44.4 3.0 50.8

As-supplied, other area 3.8 48.2 3.8 57.6

As-served, outer-wall area 10.2 39.2 1.4 42.9

As-served, other area 5.1 41.0 2.0 44.3

By comparing Fig. 6a, c and Fig. 6e, g, the austenite grains of the as-supplied

Super304H steel tube are fine and uniform. However, for the as-served Super304H steel

tube, the austenite grains in the outer wall grow significantly, though those in the other

area are still fine. The color distributions of the austenite grains in the whole as-

supplied/-served Super304H steel tubes are random, indicating no obvious grain

preferred orientation existed. Based on the Brandon deviation, the characteristic

distributions of austenite grain boundaries in these four samples are statistically

analyzed, as shown in Fig. 6b, d, f and h, in which the yellow, red, green, blue and black

lines represent Σ1, Σ3, Σ9, Σ27 and random grain boundaries, respectively. The

proportions of these grain boundaries are listed in Table 2. It was found that there was

no obvious difference in the austenite grain boundary proportion between the outer wall

area and the other area of the as-supplied Super304H steel tube. The Σ3 twin boundaries

have the biggest fraction of the main grain boundary feature. The (Σ9+Σ27) grain

boundaries have a high mobility, and usually act as the bridging segments for

regenerating the Σ3 twin boundaries. However, its proportion is rather low, only about
14

Electronic copy available at: https://ssrn.com/abstract=4084614

3%. The fraction of sub-boundaries in the outer wall is also low, though it is slightly

higher than that in other area. Moreover, the other low-CSL grain boundaries across the

whole section of the steel tube are low in proportion as well. It was confirmed that the

formation of low-ΣCSL grain boundaries, especially the Σ3n (n =1, 2, 3) grain

boundaries, was associated with the abnormal grain growth [37]. The Zener pinning

force of the precipitates to the CSL boundaries is relatively weak, due to low energy of

the CSL boundaries, therefore, the CSL boundaries have a high mobility in the service

process of the steel tube. In addition, based on the theory of the AGG induced by solid-

state wetting enhanced at sub-boundaries, the wetting is also enhanced at the CSL

boundaries between the abnormally growing grains and the matrix ones, due to their

low energy. As reported by Randle, et al. [38, 39], the aggregation of some special-type

CSL grain boundaries in the outer wall of the austenite stainless steel tube results in the

AGG. However, for the as-supplied Super304H steel tube employed in this work, the

low-energy CSL grain boundaries and sub-boundaries are very small in proportion, and

they are not apparently varied in the outer wall and the other area too. If they would be

the essential factor for the AGG, it seems hard to be explained that the AGG is only

detected in the outer wall of the as-served Super304H steel tube. However, it is

undeniable that the enhancing wetting effect of some special-type CSL grain boundaries

and sub-boundaries may also play an important role in the AGG.

3.4 Textures

15

Electronic copy available at: https://ssrn.com/abstract=4084614

 Fig. 7 Pole figures of the as-supplied Super304H steel tube (a) Outer-wall area; (b)

Other area

Strong textures may also be the factor inducing the AGG [14]. A few grains having

a different orientation from the main texture can grow more rapidly, since they likely

have high-angle grain boundaries, and hence exhibit a higher grain boundary mobility.

Such a phenomenon can only be observed in the materials of a strong texture [40]. As

shown in Fig. 7, for the outer wall and the other area of the as-supplied Super304H steel

tube, the maximums of pole density intensity are both low (2.36 and 2.29, respectively),

without obvious texture type difference. It was concluded that the AGG in the outer

wall area of the as-served Super304H heat-resistant steel tube was highly improbably

induced by the texture effect.

3.5 Residual strain

16

Electronic copy available at: https://ssrn.com/abstract=4084614

Fig. 8 Local misorientation maps of the outer-wall area (a) and other area (b), and (c)

misorientation distribution curves of the as-supplied Super304H steel tube (the EBSD

test step = 1 μm)

The residual strain is usually induced by incomplete recrystallization of the deformed

metal, which likely distributes nonuniformly. It attributes to the different dislocation

annihilation rate in anisotropy grains. Some local areas of a higher residual strain

certainly have a higher dislocation density (distortion energy), and hence they are

thermodynamically changed to be the areas of lower residual strain and dislocation

density (distortion energy). Such an energy difference acts as the driving force for grain

growth. Therefore, even after the incomplete recrystallization, the driving force of the

process, named strain induced grain boundary migration, still exists.

17

Electronic copy available at: https://ssrn.com/abstract=4084614

 In an EBSD local misorientation map, the homogenization degree of plastic

deformation is displayed. The area of a high misorientation angle has high defect

density and distortion energy. Compared with the other area, the outer wall area of the

as-supplied Super304H steel tube overall has a higher local misorientation. Even in the

outer wall area, the color distribution is nonuniform, as shown in Fig. 8a, b. That is, the

residual strain in the outer wall area is higher, but unevenly distributed, meanwhile, the

residual strain in the other area is in a lower level, and overall is uniformly distributed

(Fig. 8b). It was concluded that the recrystallization of the deformed austenite grains

was more incomplete, and more distortion energy was contained in the outer wall of the

as-supplied Super304H steel tube.

According to the local misorientation test results, the distortion energy (E) can be

calculated in the formula as following [41]:

αθGb
E=
2d
where, α is a constant depending on the grain boundary type, θ is the average local

misorientation, G is the shear modulus, b is modulus of the Burgers vector, and d is the

test step, respectively. The α values are 2, 4 and 3, as the grain boundary types are the

tilt, twist and mixed ones, respectively. In this study, α is 3, G is 78 GPa, b is 0.25 nm

[42], and d is 1 μm, respectively. The E value of the outer wall of the as-supplied

Super304H steel tube was calculated as 8.5 × 105 J /m3, significantly higher than that

of the other area (5.7 × 105 J/m3). Accordingly, the outer wall is more likely to satisfy

the thermodynamic condition for AGG.

This point mentioned above can be further confirmed by the microstructural

18

Electronic copy available at: https://ssrn.com/abstract=4084614

characteristics of the as-supplied Super304H steel tube. As shown in Fig. 9a, high-

density dislocations are distributed in some austenite grains in the outer wall area, and

they are disorderly tangled to form the dislocation cell sub-grains of an extremely high

distortion energy. However, it was also found that even in the outer wall, some austenite

grains of a rather low dislocation density exist, as shown in the in Fig. 9b. They

apparently contain a low distortion energy, and thus the distortion energy difference

produces, and then promotes rapid growth of the austenite grains with low distortion

energy by annexing the neighboring ones with high distortion energy. As for the other

area of the as-supplied Super304H steel tube, the dislocations are low-density and

uniformly distributed (Fig.9c), meaning that the distortion energy there is small and

uniformly distributed. As a result, no distortion energy difference produces to induce

the abnormal austenite grain growth.

19

Electronic copy available at: https://ssrn.com/abstract=4084614

 Fig. 9 TEM images showing dislocation distributions in the as-supplied Super304H

steel tube (a) High distortion area of Outer-wall; (b) Low distortion area of Outer-

wall; (c) Other area

3.6 Faceted grain boundary

Fig. 10 TEM image showing the faceted grain boundary in the outer-wall area of the

as-supplied Super304H steel tube

The faceted grain boundary migration mechanism has been widely reported in

some fcc metals and their alloys [43-47]. They confirmed that the AGG could occur at

relatively low temperature. In the occurrence of the AGG, most of the grain boundaries

have the faceted hill-and-valley structure, and the faceted grain boundaries are expected

to migrate by the two-dimensional step mechanism. The migration velocity of them

varies nonlinearly with the driving force arisen from the grain size difference, and thus

only a few austenite grains can grow at an acceleration rate to cause the AGG [43].

However, with the increase of annealing temperature, especially at a high temperature

close to the melting point, the grain boundaries are defaceted in a smoothly curved

shape. It indicates that the atoms can easily cross the rough grain boundary, leading to

20

Electronic copy available at: https://ssrn.com/abstract=4084614

the continuous grain boundary movement, and hence the normal grain growth [13].

As shown in Fig. 10, the faceted grain boundary was also detected in the outer wall

area of the as-supplied Super304H steel tube. It is zigzag in shape without any

secondary-phase particles at each step, indicating that faceting takes place in the as-

supplied Super304H steel tube after solution treatment at 1100 °C. And in the long-

term service, the actual temperature of the steel tube is less than 700 °C, which is far

lower than the temperature required for the faceting-defaceting transition of the grain

boundaries [44, 45]. So, the faceted grain boundaries may exist stably, and contribute

to the AGG via the two-dimensional nucleation mechanism. Besides, the extrinsic

dislocations originated from small deformation produce a non-equilibrium structure at

the austenite grain boundaries, accelerating the faceted grain boundary migration, and

hence promoting the AGG [46]. In this study, the high-density dislocations can also be

observed in the out wall of the as-supplied Super304H steel tube, which may also

accelerate migration of the faceted grain boundaries to a certain extent.

3.7 Abnormal grain growth mechanism

Fig. 11 Strain induced grain boundary migration in the outer-wall of the as-supplied

21

Electronic copy available at: https://ssrn.com/abstract=4084614

 Super304H steel tube

As mentioned in sections 3.2-3.6, the possible reasons for the AGG in the outer wall

of the as-served Super304H steel tube have been investigated. Out of them, the high

and nonuniformly-distributed residual strain is the most likely reason for inducing the

AGG in the outer wall of the as-supplied steel tube. Even though the solid solution

treatment after cold rolling of the as-supplied Super304H steel tube is executed, the

residual strain in the outer wall is remained, partly because of the very short heat

treatment time in order to obtain the ultra-fine austenite grains. In this case, the AGG

in the outer wall occurs in the long-term, high-temperature service process of the as-

supplied Super304H steel tube, similar with the AGG of some fcc metals, during

annealing after a critical deformation [17].

Two competing growth mechanisms of the grains suffering the critical deformation

(critical strain) are well developed and widely accepted [33]. One is the nucleation sites

limited recrystallization. It means that a few recrystallization nuclei are stabilized in the

deformed austenite matrix, and grow abnormally by annexing the neighboring grains

till they contact each other [36]. The another is the heterogenous distribution of

distortion energy. In this case, the AGG does not originate from the grain nucleation

and growth, but the migration of the low-distortion grains to the neighboring high-

distortion grains, thermodynamically driven by the distortion energy difference.

Meanwhile, these growing grains have a smaller grain-boundary curvature than the

neighboring deformed grains, as a result, this grain-boundary curvature difference also

acts as a new driving force to accelerate the grain growth [48, 49]. In this study, if the

22

Electronic copy available at: https://ssrn.com/abstract=4084614

AGG in the outer wall of the as-served Super 304H steel tube would result from

nucleation and growth of the recrystallization grains, the grains without any distortion

should be obtained. However, as shown in Fig.3a and b, many residual grain-boundary

segments in the large grains, i.e., the remnants formed by grain annexation, are

observable (Fig. 3b), indicating that the AGG is likely the result of direct growth of

some grains.

The strain induced grain boundary migration (SIBM) mechanism plays an important

role in the AGG. As shown in an arrow in Fig. 11, a grain boundary bulge exists in the

outer wall of the as-supplied Super304H steel tube. In the austenite grains on both sides

of the grain boundary bulge, significant difference of the dislocation density (distortion)

is presented, which acts as the thermodynamic driving force to the grain growth. The

low-distortion grain grows into the high-distortion one, possibly develops into a coarse

grain. Under the conditions of nonuniform distribution of the distortion energy and no

existence of recrystallization, the grain growth behavior is revealed by Wang, et al. in

terms of the phase field simulation [33]. It was found that some large grains existed in

the border region having an apparent distortion energy gradient, which was consistent

with the AGG in the outer wall of the as-served Super 304H steel tube. Meanwhile, as

shown in a box in Fig. 11, the faceted grain boundary exists, indicating that two-

dimensional step migration mechanism of the faceted grain boundary may be another

route in service to the AGG, besides the SIBM mechanism.

In summary, the distortion energy difference exists in the outer wall of the as-

supplied Super304H steel tube manifested by the high-distortion austenite grains and

23

Electronic copy available at: https://ssrn.com/abstract=4084614

nonuniformly-distributed residual strain, which provides the thermodynamic driving

force to the AGG via the SIBM mechanism. Meanwhile, the two-dimensional step

mechanism of the faceted grain boundary is also employed to speed the AGG process.

On the contrary, the residual strain cannot induce the SIBM in the other area of the as-

supplied Super304H steel tube, because of a low and uniformly-distributed distortion

energy. And, in the service of the Super304H steel tube, the secondary-phase

precipitates considerably inhibit the grain boundary migration. So, the austenite grain

size in this area is nearly equivalent to that of the as-supplied Super304H steel tube.

4. Conclusions

Aiming at the AGG in the outer wall of the 40,000 h served Super304H steel tube in

an USC unit, microstructural characteristics of the as-supplied/-served Super304H steel

tube were contrastively studied by means of OM, SEM, EBSD and TEM to figure out

the AGG mechanism. The main conclusions were drawn as following:

1) In the as-supplied Super304H steel tube, the CSL boundaries of a high fluidity and

the sub-boundaries are small in amount, and the texture intensity is weak. And, their

distributions on the whole cross section of the steel tube are not different. Moreover, no

obvious nonuniform distributions of the secondary-phase particles at the austenite grain

boundaries are detected on the whole cross sections of the as-supplied/-served Super

304H steel tubes. So, none of them is response for the AGG.

2) The dislocation density and distortion energy in the outer wall of the as-supplied

Super304H steel tube are high and nonuniformly distributed. the low-distortion

24

Electronic copy available at: https://ssrn.com/abstract=4084614

austenite grains annex their neighboring high-distortion ones via the SIBM mechanism.

It is the most likely factor to induce the AGG.

3) The faceted austenite grain boundaries exist in the outer wall of the as-supplied

Super304H steel tube. During long-term, high-temperature running of the steel tube,

they migrate rapidly via the two-dimensional step mechanism. So, this mechanism also

possibly promotes the AGG.

Acknowledgements

This work was supported by Datang Boiler and Pressure Vessel Testing Center Co

Ltd [grant number DTGJ-WW-20211017].

25

Electronic copy available at: https://ssrn.com/abstract=4084614

References

[1] G. Xu, C. Xu, Y.P. Yang, Y.X. Fang, Y.Y. Li, X.N. Song, A novel flue gas waste heat recovery

system for coal-fired ultra-supercritical power plants. Appl, Therm. Eng. 67(2014) 240-249. https:

//doi.org/10.1016/j.applthermaleng.2014.03.038

[2] A. Phongphiphat, C. Ryu, Y.B. Yang, K.N. Finney, A. Leyland, V.N. Sharifi, J. Swithenbank,

Investigation into high-temperature corrosion in a large-scale municipal waste-to-energy plant,

Corros. Sci. 52(2010) 3861-3874. https: //doi.org/10.1016/j.corsci.2010.07.032

[3] G.R. Holcomb, B.F. McGhee, A.T. Fry, N.J. Simms, K. Davis, H.S. Shim, S.J. Bullard, Boiler

corrosion and monitoring, Mater. High Temp. 30(2014) 271-286. https:

//doi.org/10.3184/096034013X13813935093793

[4] S.M. Jiang, H.Q. Li, J. Ma, C.Z. Xu, J. Gong, C. Sun, High temperature corrosion behaviour of

a gradient NiCoCrAlYSi coating II: Oxidation and hot corrosion, Corros. Sci. 52(2010) 2316-2322.

https: //doi.org/10.1016/j.corsci.2010.03.032

[5] R. Viswanathan, W. Bakker, Materials for ultrasupercritical coal power plants—boiler materials:

part 1, J. Mater. Eng. Perform. 10(2001) 96-101. https: //doi.org/10.1361/105994901770345402

[6] R. Viswanathan, J.F. Henry, J. Tanzosh, G. Stanko, J. Shingledecker, B. Vitalis, R. Purgert, US

program on materials technology for ultra-supercritical coal power plants, J. Mater. Eng. Perform.

14(2005) 281-292. https: //doi.org/10.1361/10599490524039

[7] X. Huang, Q.W. Zhou, W. Wang, W.S. Li, Y. Gao, Microstructure and property evolutions of a

novel Super304H steel during high temperature creeping. Mater. High Temp. 35(2017) 438-450.

https: //doi.org/10.1080/09603409.2017.1376831

[8] T. Dudziak, E. Rzd, G. Golański, M. Solecka, Ł. Boroń, P. Wieczorek, Effect of aging process

26

Electronic copy available at: https://ssrn.com/abstract=4084614

on steam oxidation behavior of austenitic steels Super 304H and HR3C, Int. J. Pres. Ves. Pip.

191(2021) 104344. https: //doi.org/10.1016/j.ijpvp.2021.104344

[9] H. Ma, Y. Wang, Z. Liang, Q. Zhao, Z. Ke, Investigation on high temperature corrosion

characteristic of Super304H, TP347H, and HR3C Steel in an ultra-supercritical coal-fired boiler,

Fuel Cells, 21(2021) 24-30. https: //doi.org/10.1002/fuce.202000031

[10] J.J. Liu, R. Liu, W.L. Wang, Y. Wu, Y. Wang, W.M. Tang, Effect of abnormal grain growth

on mechanical properties of serviced Super304H steel tube, Trans. Mater. Heat Treat. 42(2021) 125-

131. https: //doi.org/10.13289/j.issn.1009-6264.2020-0426

[11] M. Shirdel, H. Mirzadeh, M.H. Parsa, Abnormal grain growth in AISI 304L stainless steel,

Mater. Charact. 97(2014) 11-17. https: //doi.org/10.1016/j.matchar.2014.08.022

[12] A.F. Padilha, R.L. Plaut, P.R. Rios, Annealing of cold-worked austenitic stainless steels, ISIJ

Int. 43(2003) 135-143. https: //doi.org/10.2355/isijinternational.43.135

[13] J.B. Koo, D.Y. Yoon, M.F. Henry, The effect of small deformation on abnormal grain growth

in bulk Cu, Metall. Mater. Trans. 33 A (2002) 3803-3815. https: //doi.org/10.1007/s11661-002-

0253-8

[14] H.C. Kim, C.G. Kang, M.Y. Huh, O. Engler, Effect of primary recrystallization texture on

abnormal grain growth in an aluminum alloy, Scr. Mater. 57(2007) 325-327. https:

//doi.org/10.1016/j.scriptamat.2007.04.023

[15] M. Maalekian, R. Radis, M. Militzer, A. Moreau, W.J. Poole, In situ measurement and

modelling of austenite grain growth in a Ti/Nb microalloyed steel, Acta Mater. 60(2012) 1015-1026.

https: //doi.org/10.1016/j.actamat.2011.11.016

[16] T. Gladman, On the theory of the effect of precipitate particles on grain growth in metals, Proc.

27

Electronic copy available at: https://ssrn.com/abstract=4084614

R. Soc. 294 A (1966) 298-309. https: //doi.org/10.1098/rspa.1966.0208

[17] F. Humphreys, M. Hatherly, Recrystallization and Related Annealing Phenomena, 2nd ed.,

Elsevier, UK, 2004. https://doi.org/10.1016/B978-0-08-044164-1.X5000-2

[18] G.D. Hibbarda, V. Radmilovic, K.T. Aust, U. Erb, Grain boundary migration during abnormal

grain growth in nanocrystalline Ni, Mater. Sci. Eng. 494A (2008) 232-238. https:

//doi.org/10.1016/j.msea.2008.04.054

[19] J.W. Rutter, K.T. Aust, Grain boundary migration motivated by substructure in high purity

metal crystals, Acta Metall. 6(1958) 375-377. 10.1016/0001-6160(58)90076-2

[20] L.M. Fu, H.R. Wang, W. Wang, A.D. Shan, Austenite grain growth prediction coupling with

drag and pinning effects in low carbon Nb microalloyed steels, Mater. Sci. Technol. 27(2011) 996-

1001. https: //doi.org/10.1179/1743284711Y.0000000001

[21] G. Riontino, C. Antonione, L. Battezzati, F. Marino, M.C. Tabasso, Kinetics of abnormal grain

growth in pure iron, J. Mater. Sci. 14(1979) 86-90. https: //doi.org/10.1007/BF01028331

[22] J.J. Petrovic, L.J. Ebert, Abnormal grain growth in TD-nickel, Metall. Trans. 3(1972) 1131-

1136. https: //doi.org/10.1007/BF02642444

[23] G.D. Hibbard, J.L. McCrea, G. Palumbo, K.T. Aust, U. Erb, An initial analysis of mechanisms

leading to late stage abnormal grain growth in nanocrystalline Ni, Scr. Mater. 47(2002) 83-87. https:

//doi.org/10.1016/S1359-6462(02)00098-2

[24] B. Radhakrishnan, R.G. Thompson, Kinetics of grain growth in the weld heat-affected zone of

alloy 718, Metall. Mater. Trans. 24A (1993) 2773-2785. https: //doi.org/10.1007/BF02659501

[25] A.D. Rollett, D.J. Srolovitzz, M.P. Anderson, Simulation and theory of abnormal grain

growth—anisotropic grain boundary energies and mobilities, Acta Metall. 37(1989) 1227-1240. http:

28

Electronic copy available at: https://ssrn.com/abstract=4084614

//dx.doi.org/10.1016/0001-6160(89)90117-X

[26] C.S. Park, H.K. Park, H.S. Shim, T.W. Na, C.H. Han, N.M. Hwang, New understanding of the

role of coincidence site lattice boundaries in abnormal grain growth of aluminium alloy, Phil. Mag.

Lett. 95(2015) 220-228. https: //doi.org/10.1080/09500839.2015.1033027

[27] F. Shuang, Y. Dong, S. Wang, The abnormal grain growth of P/M nickel-base superalloy: strain

storage and CSL boundaries. Adv. Mat. Res. 1064(2015) 49-54. https:

//doi.org/10.4028/www.scientific.net/AMR.1064.49

[28] H. Chun, S.M. Na, C. Mudivarthi, A. Flatau, The role of misorientation and coincident site

lattice boundaries in Goss-textured Galfenol rolled sheet, J. Appl. Phys, 107(2010) 09A960. https:

//doi.org/10.1063/1.3371686

[29] C.S. Park, T.W. Na, H.K. Park, B.J. Lee, C.H. Han, N.M. Hwang, Three-dimensional Monte

Carlo simulation for the effect of precipitates and sub-boundaries on abnormal grain growth, Scr.

Mater. 66(2012) 398-401. https: //doi.org/10.1016/j.scriptamat.2011.11.045

[30] H.K. Park, S.D. Kim, S.C. Park, J.T. Park, N.M. Hwang, Sub-boundaries in abnormally

growing Goss grains in Fe–3% Si steel, Scr. Mater. 62(2010) 376-378. https:

//doi.org/10.1016/j.scriptamat.2009.11.025

[31] D.A. DeMania, Recovery and Recrystallization in Nickel-based Superalloy Rene ´ 88 DT, Ph.

D dissertation, UVA, 2002.

[32] S. Mahalingam, P.E.J. Flewitt, J.F. Knott, Effect of pre-strain on grain size distributions in

316H austenitic stainless steel, J. Mater. Sci. 47(2012) 960-968. https: //doi.org/10.1007/s10853-

011-5875-z

[33] X. Wang, Z.W. Huang, B. Cai, N. Zhou, O. Magdysyuk, Y.F. Gao, S. Srivatsa, L.M. Tan, L

29

Electronic copy available at: https://ssrn.com/abstract=4084614

Jiang, Formation mechanism of abnormally large grains in a polycrystalline nickel-based superalloy

during heat treatment processing, Acta Mater. 168(2019) 287-298. https:

//doi.org/10.1016/j.actamat.2019.02.012

[34] Y.K. Cho, D.Y. Yoon, M.F. Henry. The effects of deformation and pre-heat-treatment on

abnormal grain growth in RENE´88 superalloy, Metall. Mater. Trans. A 32(2001) 3077-3090. https:

//doi.org/10.1007/s11661-001-0182-y

[35] X.Q. Fu, Y.C. Ji, X.Q. Cheng, C.F. Dong, Y. Fan, X.G. Li, Effect of grain size and its

uniformity on corrosion resistance of rolled 316L stainless steel by EBSD and TEM, Mater. Today

Commun. 25(2020) 101429. https: //doi.org/10.1016/j.mtcomm.2020.101429

[36] V.M. Miller, A.E. Johnson, C.J. Torbet, T.M. Pollock, Recrystallization and the development

of abnormally large grains after small strain deformation in a polycrystalline nickel-based superalloy,

Metall. Mater. Trans. 47A (2016)1566-1574. https: //doi.org/10.1007/s11661-016-3329-6

[37] M. Shimada, H. Kokawa, Z.J. Wang, Y.S. Sato, I. Karibe, Optimization of grain boundary

character distribution for intergranular corrosion resistant 304 stainless steel by twin-induced grain

boundary engineering, Acta Mater. 50(2002) 2331-2341. https://doi.org/10.1016/S1359-

6454(02)00064-2

[38] V. Randle, A. Brown, Development of grain misorientation texture, in terms of coincident site

lattice structures, as a function of thermomechanical treatments. Philos. Mag. 59A (2006) 1075-

1089. https: //doi.org/10.1080/01418618908209838

[39] V. Randle, A. Brown, The effects of strain on grain misorientation texture during the grain

growth incubation period, Philos. Mag. 58A (2006) 717-736.

https://doi.org/10.1080/01418618808209949

30

Electronic copy available at: https://ssrn.com/abstract=4084614

[40] M. Mujahid, C.A. Gater, J.W. Martin, Microstructural study of a mechanically alloyed ODS

superalloy, J. Mater. Eng. Perform. 7(1988) 524-532. https:

//doi.org/10.1361/105994998770347684

[41] Y. Takayama, J.A. Szpunar, Stored energy and Taylor factor relation in an Al-Mg-Mn alloy

sheet worked by continuous cyclic bending, Mater. Trans. 45(2005) 2316-2325. https:

//doi.org/10.2320/matertrans.45.2316

[42] W. Feng, Research on Dependence of the Evolution of Grain Boundary Structure on Grain Size

and Deformation Conditions in 304 Austentic Stainless Steel, Ph. D dissertation, Nanjing Univ. Sci.

Technol. 2018.

[43] S.B. Lee, D.Y. Yoon, N.M. Hwang, M.F. Henry, Grain boundary faceting and abnormal grain

growth in nickel. Metall. Mater. Trans, 31A (2000) 985-994. https: //doi.org/10.1007/s11661-000-

1016-z

[44] H. Gleiter, The mechanism of grain boundary migration, Acta Metall. 17(1969) 565-573. https:

//doi.org/10.1016/0001-6160(69)90115-1

[45] Y.J. Park, N.M. Hwang, D.Y. Yoon, Abnormal growth of faceted (WC) grains in a (Co) liquid

matrix, Metall. Mater. Trans. 27 A (1996) 2809-2819. https: //doi.org/10.1007/BF02652373

[46] J.S. Choi, D.Y. Yoon, The temperature dependence of abnormal grain growth and grain

boundary faceting in 316L stainless steel, ISIJ Int. 41(2007) 478-483. https:

//doi.org/10.2355/isijinternational.41.478

[47] R.Z. Valiev, V.Y. Gertsman, O.A. Kaibyshev, The role of non-equilibrium grain boundary

structure in strain induced grain boundary migration (recrystallization after small strains), Scr.

Metall. 17(1983) 853-856. https: //doi.org/10.1016/0036-9748(83)90248-X

31

Electronic copy available at: https://ssrn.com/abstract=4084614

[48] W.J. Tu, Deformation Mechanisms and strain storage during forging of powder-metallurgy

Nickel-base turbine disk alloy, Ph. D dissertation, University of Michigan, 2010.

[49] L. Tan, Z. Huang, F. Liu, G. He, X. Wang, L. Huang, Y. Zhang, L. Jiang, Effects of strain

amount and strain rate on grain structure of a novel high Co nickel-based polycrystalline superalloy,

Mater. Des. 131 (2017) 60-68. https: //doi.org/10.1016/j.matdes.2017.06.004

32

Electronic copy available at: https://ssrn.com/abstract=4084614

 Figure captions

Fig. 1 Schematic illustration for sampling the EBSD specimen

Fig. 2 OM cross-sectional images showing microstructures of outer-wall (a), (b) and

(c), (d) other area of the as-supplied Super304H steel tube (a), (c) Low-magnification

images; (b), (d) High-magnification images

Fig. 3 OM cross-sectional images showing microstructures of outer-wall (a), (b) and

(c), (d) other area of the as-served Super304H steel tube (a), (c) Low-magnification

images; (b), (d) High-magnification images

Fig. 4 SEM cross-sectional images and EDS spectra of the as-supplied Super304H steel

tube (a) Outer-wall area; (b) Other area; (c) EDS spectrum of points 1, 2, 4, 5 and 6 in

Fig. a, b; (d) EDS spectrum of point 3 in Fig. a, b

Fig. 5 SEM cross-sectional images and EDS spectra of the as-served Super304H steel

tube (a) Outer-wall area; (b) Other area; (c) EDS spectrum of points 1, 2, 4, 5 and 7 in

Fig. a, b; (d) EDS spectrum of points 3and 6 in Fig. a, b

Fig. 6 Inverse pole figures (a, c, e, g) and (b, d, f, h) grain boundary maps of the

Super304H steel tubes (a, b) As-supplied, outer-wall area; (c, d) As-supplied, other area;

(e, f) As-served, outer-wall area; (g, h) As-served, other area

Fig. 7 Pole figures of the as-supplied Super304H steel tube (a) Outer-wall area; (b)

Other area

Fig. 8 Local misorientation maps of the outer-wall area (a) and other area (b), and (c)

misorientation distribution curves of the as-supplied Super304H steel tube (the EBSD

test step = 1 μm)

33

Electronic copy available at: https://ssrn.com/abstract=4084614

Fig. 9 TEM images showing dislocation distributions in the as-supplied Super304H

steel tube (a) High distortion area of Outer-wall; (b) Low distortion area of Outer-wall;

(c) Other area

Fig. 10 TEM image showing the faceted grain boundary in the outer-wall area of the

as-supplied Super304H steel tube

Fig. 11 Strain induced grain boundary migration in the outer-wall of the as-supplied

Super304H steel tube

34

Electronic copy available at: https://ssrn.com/abstract=4084614

 Tables

Table 1 Chemical composition of the Super304H steel tube (wt%)

C Mn Si Cr S P Ni Nb N Al B Cu Fe

0.08 0.66 0.2 18.3 0.004 0.017 8.72 0.52 0.1 0.008 0.005 3.02 Bal.

Table 2 Special CSL grain boundary proportions of the as-supplied/-served Super304H steel tubes (%)

Σ1 Σ3 Σ9+Σ27 Low-ΣCSL

As-supplied, outer-wall area 5.8 44.4 3.0 50.8

As-supplied, other area 3.8 48.2 3.8 57.6

As-served, outer-wall area 10.2 39.2 1.4 42.9

As-served, other area 5.1 41.0 2.0 44.3

35

Electronic copy available at: https://ssrn.com/abstract=4084614