Scripta Materialia 48 (2003) 12011206 www.actamat-journals.

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Evolution of precipitates in the NbTiV microalloyed HSLA steels during reheating

S.G. Hong
a

a,b

, H.J. Jun

a,*

, K.B. Kang b, C.G. Park

Department of Materials Science and Engineering and Center for Advanced Aerospace Materials, Pohang University of Science and Technology, Pohang 790-784, South Korea b Technical Research Laboratories, POSCO, Kwangyang 545-090, South Korea

Received 3 September 2002; received in revised form 18 November 2002; accepted 20 November 2002

Abstract In as-cast slab steel, dendritic Nb-rich (Ti,Nb)(C,N) carbonitrides were observed which have a thermodynamically stable chemistry at lower than 1000 C. These dendritic carbonitrides were dissolved and then re-precipitated to two kinds of carbonitrides, Ti- and N-rich and Ti- and C-rich (Ti,Nb)(C,N) carbonitrides during reheating. 2003 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.
Keywords: Steels; Precipitates; Reheating; Transmission electron microscopy (TEM)

1. Introduction There is a substantial interest in the development and use of high-strength steels for automotive applications with the goal to decrease vehicle weight. Over the last 30 years, high-strength lowalloy (HSLA) steels containing microalloying elements such as Ti, Nb, and V have become widely used in the automotive sector and also for pipeline applications [13]. These microalloying elements yield a signicant improvement in mechanical properties through grain renement, solid solution hardening, and precipitation hardening. Multimicroalloying can lead to the formation of compounds with complex chemical compositions,

which further inuences the mechanical properties of the steels [48]. Therefore, an improved understanding of the sequence of the precipitation of complex precipitates is clearly important to microstructural control during hot rolling processing. The purpose of the present study is, thus, to identify the evolution of precipitates in NbTiV microalloyed steels during the reheating process, which is an important process, based on both TEM observation and chemical analysis of carbonitrides.

2. Experimental procedure The chemical composition of the NbTiV steel examined in this study is given in Table 1. The specimens were supplied by POSCO (Pohang Iron & Steel Co. Ltd.) in the form of slab. Reheating simulations were performed in the temperature

* Corresponding author. Tel.: +81-542792826; fax: +81542792399. E-mail address: jhj@postech.ac.kr (H.J. Jun).

1359-6462/03/$ - see front matter 2003 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved. doi:10.1016/S1359-6462(02)00567-5

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Table 1 Chemical composition of the steel examined in the present study (wt.%) C Slab steel 0.06 Si 0.16 Mn 1.53 V 0.03 Nb 0.039 Ti 0.018 N 0.004

range of 11001400 C for 1 h after which reheated specimens were water-quenched for chemical and TEM analysis. The equilibrium composition of complex precipitates in austenite has been predicted assuming compositional homogeneity in austenite by using Thermo Calc program. The morphology and distribution of precipitates, which were extracted from the reheated specimens, were examined using FEG-TEM (JEM2010F). In addition, chemical analysis for the precipitates was performed by using both nano-beam EDS analysis on Al-replicas and induction coupled plasma (ICP) analysis with dissolved and ltered precipitates.

3. Results 3.1. Analysis of carbonitrides observed in slab steel Prior to the analysis of precipitates formed during reheating, TEM observations for as-cast slab

steel were performed. Fig. 1 shows aluminum replicas extracted from the as-cast slab steel, showing dendritic precipitates. These dendritic precipitates were identied as (Ti,Nb)(C,N) carbonitrides. The chemistries of both the center (marked A) and wing parts (marked as B) in these dendritic carbonitrides were investigated by using nano-EDS analysis (Fig. 1(c) and (d)). The center parts revealed higher Ti and N contents than wing parts. Most of all, it is important that these dendritic carbonitries were not Ti-rich carbonitrides but Nbrich carbonitrides. That is, it is generally believed that these Nb-rich carbonitrides are stable in the low-temperature range of austenite. Especially, it was easily predicted that the chemistries of these carbonitrides are stable at lower than 1000 C as shown in the equilibrium chemistries of complex carbonitrides in NbTiV steel calculated by using Thermo Calc (Fig. 2). That is, these dendritic carbonitrides are no longer stable above 1000 C. Zhou and Priestner [9] reported that these Nb-rich dendritic (Ti,Nb)(C,N) carbonitrides can precipi-

Fig. 1. Aluminum extraction replicas showing (a) the distribution and (b) morphology of precipitates in slab steel. Characteristic EDS spectra of (c) A and (d) B parts.

S.G. Hong et al. / Scripta Materialia 48 (2003) 12011206

Wt.% of alloy elements in MX carbonitrides(x10-3)

1203

40

NbCN

Dendritic (Ti,Nb)(C,N)

30

VCN
20

NbCN Ti CN VCN CCN NCN

of as-cast slab steel. In addition, any other precipitates containing V were not observed in as-cast slab steel. 3.2. Evolution of precipitates during reheating In order to investigate the dissolution and reprecipitation behavior of these carbonitrides during reheating process, we examined the distribution and morphology of precipitates after reheating at various temperatures. After reheating in the temperature range of 11001400 C for 1 h, the dendritic Nb-rich (Ti,Nb)(C,N) carbonitrides, which resulted from non-equilibrium cooling, disappeared, and new cubic shape precipitates formed along austenite grain boundaries (for the case of reheating at 11001400 C) and within austenite grain (for the case of reheating at 11001250 C) (as shown in Fig. 3). At the 1100 C reheating

TiCN CCN NCN

10

600

800

1000

1200

1400

1600

Temperature( C)

Fig. 2. The equilibrium chemistries of complex carbonitrides in NbTiV steel at 6001600 C (calculated by using Thermo Calc).

tate at the low-temperature (less than 1000 C) range of austenite during non-equilibrium cooling

Fig. 3. Aluminum extraction replicas exhibiting the distribution of precipitates in slab steel reheated at (a,b) 1100 C, (c,d) 1150 C, (e,f) 1200 C, and (g,h) 1250 C.

Fig. 4. Aluminum extraction replicas exhibiting the distribution of precipitates in slab steel reheated at (a) 1300 C and (b) 1400 C.

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condition, there were both cubic shape precipitates and irregular shape precipitates. It is believed that the former are re-precipitated carbonitrides, and the latter are undissolved carbonitrides observed during reheating process. After reheating above 1300 C, however, only large cubic precipitates were observed along grain boundaries as shown in Fig. 4.

4. Discussion It is well known that Ti added to Nb or NbV microalloyed HSLA steels restricts eectively the grain growth of austenite during reheating process by forming stable nitrides or carbonitrides and nally results in ne-grained steel. However, the formation mechanism of these Ti-nitrides or Ti-carbonitrides during reheating process is not clearly identied. It is not clear when these cubic shape Ti-precipitates easily observed in hot rolled steel form during cooling of slab steel or reheating process. In addition, the distribution and size of Ti-precipitates formed during reheating process can play important roles not only on pinning of austenite grain during reheating, but on precipitation kinetics of Nb-precipitates [8]. Especially, in the previous result [8], we found that these Tiprecipitates observed after reheating process acted as preferred nucleation sites for NbC carbides during hot deformation. That is, we can easily predict that the precipitation kinetics of NbC
0.045

carbides, which are well known as eective precipitates for inhibition of recrystallisation of austenite, can be inuenced by the distribution and size of Ti-rich precipitates after reheating process. Therefore, in order to identify systematic precipitation process of cubic shape Ti-precipitates, the chemical analysis for Ti-precipitates observed in as-slab steel and after reheating at various temperatures were conducted. First, we examined the total amount of Ti and Nb precipitated in as-slab and reheated steels by using dissolution and ltration method. As shown in Fig. 5(a), electrolytic dissolution and ltration results revealed that almost all the Nb and Ti contents (0.039 and 0.017 wt.%, respectively) added during steel making process precipitated as dendritic Nb-rich (Ti,Nb)(C,N) carbonitrides. As reheating temperature increased from 1050 to 1400 C, Nb content within precipitates decreased, while Ti content did not change to 1250 C. Above 1300 C, Ti started to dissolve into the austenite matrix. Fig. 5(b) shows the atomic ratio of Ti or Nb to total Ti and Nb content contained within (Ti,Nb)(C,N) carbonitrides. The composition of precipitates changed from Nb-rich (Ti,Nb)(C,N) carbonitrides in as-cast slab steel to Ti-rich (Ti,Nb)(C,N) carbonitrides in reheated steel. In addition, as reheating temperature increased, atomic ratio of Ti to total Ti and Nb content increased, simultaneously. As shown in thermodynamic equilibrium of Ti, Nb and V containing
1.0

Atomic ratio( Ti or Nb/(Ti+Nb))

0.040 0.035 0.030

TiCN NbCN

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 Slab 1100 1200 1300 1400
Ti Nb

Slab

w t.%

0.025 0.020 0.015 0.010 0.005 0.000 1000 1100 1200 1300 1400 1500

(a)

Reheating temp.( C)

(b)

Reheating temp.( C)

Fig. 5. (a) Amount of Ti and Nb, and (b) atomic ratio of Ti and Nb within precipitates observed in slab steel reheated at 10501400 C (dissolution and ltration results (ICP)).

S.G. Hong et al. / Scripta Materialia 48 (2003) 12011206

1.0 0.8
Ti Nb C N
Ti Nb C N

1205

1.0 0.8

Atomic ratio

0.6 0.4 0.2 0.0 Slab 1100 1200 1300 1400

Atomic ratio

0.6 0.4 0.2 0.0

1050

1100

1150

1200

1250

(a)

Reheating Temperature ( C)

(b)

Reheating Temperature ( C)

Fig. 6. Atomic ratio of (a) coarse and (b) ne precipitates observed in slab steel reheated at various temperatures (TEM nano-EDS results).

precipitates (Fig. 2), we can predict that nonequilibrium dendritic (Ti,Nb)(C,N) carbonitrides are not stable any more during reheating and changed to equilibrium carbonitrides. In order to examine the composition of Tiprecipitates observed both along austenite grain boundaries and within austenite, respectively, the nano-chemistries of cubic shape Ti-carbonitrides

were investigated by using nano-EDS analysis. As shown in Fig. 6, the large carbonitrides along austenite grain boundaries were identied as nitrogen-rich carbonitrides except for 1100 C and the atomic ratio of nitrogen to carbon increased as reheating temperature increased. The small carbonitrides within the austenite matrix, however, were carbon-rich carbonitrides and the atomic

Fig. 7. (a) Carbon extraction replica showing the distribution of carbonitrides in slab after reheating at 1250 C for 1 h, and schematic diagrams showing (b) dendritic carbonitrides in slab, and (c,d) the formation process of cubic carbonitrides located in grain boundaries and matrix during reheating treatments.

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ration of nitrogen to carbon was not changed regardless of reheating temperature. As shown in Fig. 7(a), there was precipitates free zone between the large N-rich (Ti,Nb)(C,N) and the small C-rich (Ti,Nb)(C,N). Therefore, from the results of nano-chemistries and this characteristic distribution of precipitates, it is believed that during reheating process, dendritic carbonitrides which precipitated during non-equilibrium cooling (Fig. 7(b)), dissolved and Ti and Nb solutes near austenite grain boundaries diffused primarily into austenite grain boundaries. In addition, N and C solutes diused from the austenite matrix into austenite grain boundaries, and formed Ti- and N-rich (Ti,Nb)(C,N) carbonitrides (Fig. 7(c)), which were stable chemistries at reheating temperatures as known in Fig. 2. On the other hand, Ti and Nb within austenite matrix, which did not diuse into austenite grain boundaries, formed the small Ti- and C-rich (Ti,Nb)(C,N) carbonitrides (Fig. 7(d)). Especially, these small carbonitrides did not reveal the chemistries predicted from Thermo Calc. That is, these precipitates were C-rich (Ti,Nb)(C,N), not N-rich (Ti,Nb)(C,N). It is believed that because N solutes within austenite matrix primarily diused into austenite grain boundaries during reheating process, and formed large N-rich carbonitrides, N content within the austenite matrix was too low to form N-rich (Ti,Nb)(C,N) carbonitrides. Consequently, we can conclude that ne Tiprecipitates observed within austenite are attributed to non-equilibrium precipitates, that is, dendritic Nb-rich (Ti,Nb)(C,N) carbonitrides formed during cooling of slab steel. Dendritic Nbrich (Ti,Nb)(C,N) carbonitrides dissolved into austenite during reheating process and reprecipitated simultaneously as stable Ti-rich (Ti,Nb) (C,N) carbonitrides. Especially, these ne (Ti,Nb) (C,N) carbonitrides observed within austenite will be not eective on restriction of grain growth of austenite during reheating. From our previous results [8], we would rather predict that these ne (Ti,Nb)(C,N) showing uniform distribution within

austenite can have reverse eects on inhibition of recrystallisation of austenite.

5. Conclusion 1. In as-cast slab steel, dendritic Nb-rich (Ti,Nb) (C,N) carbonitrides were observed which have a thermodynamically stable chemistry at lower than 1000 C. 2. These dendritic carbonitrides were dissolved and then re-precipitated to two kinds of carbonitrides, Ti- and N-rich and Ti and C-rich (Ti,Nb)(C,N) carbonitrides during reheating. 3. During the reheating process, stable Ti- and Nrich (Ti,Nb)(C,N) precipitated primarily along austenite grain boundaries, followed by precipitation of Ti- and C-rich (Ti,Nb)(C,N) within austenite grain, where N solutes were depleted.

Acknowledgement The authors thank Pohang Iron and Steel Co. (POSCO) for nancial support.

References
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