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Preparation and mechanical properties of Fe3 Al(Ti)/TiC composites

Jia Li a, , Qiang Liu b , Rui-xia Shi a , Yu Wen a , Yan-sheng Yin c
Department of Material Science and Engineering, Jinan University, Jinan 250022, China Key Laboratory For Liquid Structure and Heredity of Ministry of Education, Engineering Ceramics Key Laboratory of Shandong Province, Shandong University, Jinan 250061, China c School of Materials Science and Engineering, China Ocean University, Qingdao 266003, China
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Near fully dense Fe3 Al(10Ti)/TiC composites were synthesized by MA and hot-pressing sintering methods. Based on the Orowan strengthening effect offered by the nano-TiC particles, higher three-point bending strength and hardness values, 1310 MPa and 90 HRA, were achieved in Fe3 Al(10Ti)/40 vol%TiC composite. The addition of Ti favored the improvement of hardness and room temperature bending strength of composites by the ordering strengthening effect and solid solution hardening effect. The microstructures of as-synthesized composites were investigated by XRD, SEM and TEM. Fe3 Al particles had equiaxed morphol-

Received 2 April 2007 Received in revised form 11 October 2007 Accepted 23 December 2007

Keywords: TiC Fe3 Al Composites Mechanical properties

ogy. TiC particles with grain size ranging from 50 to 200 nm were homogeneously dispersed in Fe3 Al matrix. The larger TiC particles with sub-micrometer were mainly located at grain boundaries and the smaller ones were within matrix grains. 2008 Elsevier B.V. All rights reserved.

1.

Introduction

Recently, intermetallic matrix composites reinforced with carbides, nitrides or borides, which are expected to combine the high-temperature and wear resistance properties of ceramic with the engineering properties of intermetallics, have received a great deal of attentions (Subramanian and Schneibel, 1997; Krasnowski and Kulik, 2003; Ko and Hanada, 1999; Tiegs et al., 1996). Iron aluminides intermetallic (Fe3 Al) are considered to be a good material for the matrix in such composites due to their excellent oxidation and sulphidation resistance at elevated temperature, and good fatigue and creep strength (Stoloff, 1998; Yin et al., 1995). Furthermore, they also offer advantages over many varieties of stainless steels in terms of density, cost and reduced consumption of chromium. In some early reports, TiC reinforced Fe3 Al intermetallic

composites with improved mechanical properties were manufactured by hot-pressing, pressureless melt-inltration and pulse discharge sintering (Schneibel et al., 1997; Subramanian et al., 1996; Ko et al., 2002). The improved mechanical properties can be further obtained by decreasing the grain size of both the matrix and the reinforced phase to the nanometer scale. The process that combine mechanical alloying (MA) and hot-pressing sintering is seems to be a promising way to achieve effects of rening grain size and reducing ordering degree simultaneously. In this paper, the ease of processing of Fe3 Al(Ti)/TiC nanocomposites by MA and hot-pressing sintering to nearly full density was demonstrated. Ti was chosen as the ternary alloying element since it was reported that Ti favored the improvement of the mechanical properties of Fe3 Al matrix (Zhu et al., 2000). The typical microstructure and mechanical

Corresponding author. Tel.: +86 531 82767616; fax: +86 531 87974453. E-mail address: mse lij@ujn.edu.cn (J. Li). 0924-0136/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.jmatprotec.2007.12.137

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Fig. 1 (a) TEM image and electron diffraction patterns (insert) of the Fe28Al powder milled for 50 h and (b) XRD pattern of as-annealed powder.

properties such as fracture toughness, hardness and bending strength as well as the strengthening mechanisms were also investigated in this work.

2.

Experiment procedure

Commercial TiC powder (Zhangjiakou Easter Special Ceramic Material Co., Ltd., PR China) with a purity of 99.8% and average grain size of 50 nm was used in this study. Elemental powder mixtures with suitable proportions (Fe-25 at% Al10Ti) were direct-mechanically milled in a planetary ball mill (Model QM1SP2, Nanjing University Instrument Plant, Nanjing, China) at room temperature. The milling process was conducted under a high-purity argon atmosphere for 50 h and at a rate of 360 rpm (rotations per minute). Details of the mechanical alloying can be found elsewhere (Li et al., 2005). The as-milled powders were subjected to heat treatment at 750 C in a multipurpose high-temperature furnace (Fujidenpa Kogyo Co., Ltd., Osaka, Japan) under high-vacuum (3 103 Pa) to from ordered Fe3 Al structure. The TEM image of as-annealed powder is shown in Fig. 1(a). The grain size of as-annealed powder ranged from 10 to 100 nm. The XRD pattern of as-annealed powder shown in Fig. 1(b) indicates that the as-annealed powder is cubic Fe3 Al with DO3 structure. Volume fractions ranging from 10 to 50 vol% of TiC nano-particles were added to the Fe3 AlTi starting powders. The mixtures were ultrasonically dispersed and ball-milled for 10 h, and then placed into a graphite die and hot-pressed at 13001550 C in Ar atmosphere under 40 MPa for 30 min. The dimensions of the hot-pressed specimens were 38 mm diameter and 6 mm thick. Densities of the specimens were measured by the Archimedes immersion technique. Microstructural investigations were performed by using scanning electron microscopy (SEM, Hitachi S-2500, Japan) and transmission electron microscopy (TEM, Model JEM2000FX, JEOL, Tokyo, Japan). TEM specimens were mechanically ground to a 150 m thickness, dimpled to 30 m, and then thinned to perforation by an argon-ion beam. Fracture toughness and bending strength were measured on the polished surfaces of the samples. Fracture toughness test was performed by the single-edge notched-beam (SENB) method (specimens size:

2 mm 4 mm 36 mm, loading rate: 0.5 mm/min and span: 20 mm). A straight-through notch with a relative length, a (notch depth)/W(total length) = 0.5 was introduced at the center of the specimens by a diamond blade. Bending strength was measured by the three-point test (specimens size: 3 mm 4 mm 36 mm, total of six measurements were made and the average value was obtained). Hardness tester (Model HD-187.5, JingHong Accurate gangti, WuXi, China) was used to test hardness.

3.

Results and discussion

XRD patterns of the sintered composites are shown in Fig. 2. It clearly shows that all diffraction peaks matched well with cubic Fe3 Al (JCPDS 45-1203) and cubic TiC (JCPDS 74-1219), and no reaction phase was detected. The superlattice peaks of DO3 structure Fe3 Al were very weak, indicating the low order degree of Fe3 Al matrix. The characteristic diffraction peaks for Ti did not present in Fig. 1, indicating that Ti might solid solved in Fe3 Al matrix (Luu et al., 2005). It also reveals that the intensity of superlattice peaks (1 1 1) of Fe3 Al slightly increased with increasing Ti content, indicating that the addition of Ti enhanced the order degree of the Fe3 Al matrix. Fig. 3(a) shows the SEM micrographs of polished and thermally etched specimens. No obvious intergranular pores and voids were observed

Fig. 2 XRD patterns of the Fe3 Al/TiC composites.

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Fig. 3 (a) Typical SEM micrograph of Fe3 Al(10Ti)/15 vol%TiC composite and (b) corresponding EDS spectrum.

under SEM. The bright particles were estimated as TiC by the EDS spectrum shown in Fig. 3(b). TiC particles with nanometer grain size were homogeneously dispersed within Fe3 Al matrix. Further TEM investigations of Fe3 Al(10Ti)/40 vol%TiC composite hot-pressed at 1450 C was made and the result is shown in Fig. 4. TiC particles with grain size ranging from 50 to 200 nm were homogeneously dispersed in Fe3 Al matrix. The larger TiC particles with sub-micrometer were mainly located at grain boundaries and the smaller ones were within matrix grains. Using the line intercept method, the average grain size of the TiC was 120 nm and that of Fe3 Al was 800 nm under the measurements of 20 grains. It is interesting to note that most of Fe3 Al matrix had an equiaxed morphology, which was much different from FeAl/TiC composites with continuous Fe3 Al lms around the TiC particles prepared by pressureless melt-inltrationin method (Schneibel et al., 1997). In this study, the temperature for densication (1450 C) was lower than the melting point of Fe3 Al (1540 C) (Stoloff, 1998), so solid phase sintering rather than liquid phase sintering took place during densication, thus resulting in the formation of regular morphology of Fe3 Al.

Fig. 5 The mean grain size for Fe3 Al(10Ti) matrix as a function of TiC content.

Fig. 4 (a) TEM micrographs of the Fe3 Al(10Ti)/30 vol%TiC composite, (b) and (c) the elected diffraction patterns of Fe3 Al and TiC, respectively.

Fig. 5 shows the average matrix grain size as a function of TiC content. Composite with higher TiC content had smaller mean grain size of Fe3 Al matrix, revealing that the grain growths of Fe3 Al matrix were suppressed by the ne TiC particles located at grain boundaries during densication. Hardness results of the composites with 2040 vol% of TiC are shown in Fig. 6. The values for composites without adding of Ti are also shown for comparison. It can be seen that the hardness increased obviously with increasing TiC content. Moreover, the addition of Ti favored the enhancing of the hardness of Fe3 Al/TiC composites. The hardness increased from 87 HRA of Fe3 Al(0Ti)/40 vol%TiC to 90 HRA of Fe3 Al(10Ti)/40 vol%TiC composite. The variations of the bending strength with sintering temperature are shown in Fig. 7. The bending strength of the composites all initially increased with increasing sintering temperature, and then decreased after reaching their maximum values. Moreover, the bending strength increased with the increasing TiC content. Theoretically, there are three factors inuencing the bending strength of composites, namely a strengthening effect due to the addition of TiC, a densication effect and a grain size effect of the composites. The presence of TiC particles at the grain boundaries inhibited the grain growth of Fe3 Al. This caused a rened grain

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Fig. 6 The hardness for Fe3 Al/TiC composites as a function of TiC content.

structure of composites, and consequently provided an additional contribution to the bending strength. In the rst stage (before the sintering temperature corresponding to maximum values of bending strength), the densication effect was dominant and the bending strength was enhanced. In the second stage, the grain size of composites further increased with the increasing sintering temperature. The bending strength was reduced as the grain size effect was in turn becoming dominant. Furthermore, as can be seen from Fig. 7, the addition of Ti favored the inprovement of bending strength, which was consistent with the work reported by Zhu et al. (2000). The increment of bending strength by adding Ti mainly resulted from the both effects of solid solution hardening and ordering strengthening. The dislocation substructure developed in Fe3 Al/40 vol%TiC composites after bending strength test is shown in Fig. 8. It can be seen that the dislocation density was much higher near the particles, and the tangled dislocations were also observed around the TiC particles. It has been well demonstrated that, for nanocomposites, if the particles are assumed to be equiaxed and small enough (<1 m) then the bending strength is basically related to the particulate-dislocation interaction by means of the Orowan bowing mechanism (Kang and Chan, 2004; Kudashov et al., 2004). For the present materials, TiC particles could act as

Fig. 8 Orowan strengthening mechanism of dislocations moving around TiC particles.

Fig. 9 The fracture toughness for Fe3 Al monolith and Fe3 Al/TiC composites as a function of sintering temperature.

Fig. 7 The bending strength for Fe3 Al monolith and Fe3 Al/TiC composites as a function of sintering temperature.

obstacles for dislocation movement during deformation, resulting in a reinforcing effect in the Fe3 Al matrix. The variations of the fracture toughness with sintering temperature are shown in Fig. 9. Similar to the results of bending strength, the fracture toughness of composites increased with the increasing sintering temperature due to the densication effect. Moreover, as shown in Fig. 9, the fracture toughness of composites decreased with the increasing TiC content due to the suppression of ductility by brittle TiC. Fig. 10(a) and (b) shows the fracture surfaces of Fe3 Al(10Ti)/15 vol%TiC and Fe3 Al(10Ti)/30 vol%TiC composites,

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Fig. 10 (a) Fracture surface of Fe3 Al(10Ti)/15 vol%TiC and (b) Fe3 Al(10Ti)/30 vol%TiC.

respectively. The fracture surface of Fe3 Al(10Ti)/15 vol%TiC composite displayed a typical brittle fracture mixing of intergranular rupture and transgranular rupture. Also, the intergranular fracture area was bigger than the transgranular fracture area. The fracture mode transformed from mixing of intergranular and transgranular to intergranular manner as the TiC content increased from 15 to 30 vol%. This change might arise from the thermal expansions mismatch between the Fe3 Al matrix and nano-TiC particles. The thermal expansions mismatch produced tensile residual stresses in grains and grain boundaries, and thus generated dislocations around the particles. These dislocations served as origins of stress concentrations, and created small nanocracks in a vicinity of a main crack tip, thus inducing the change of fracture mode.

Shandong Province (Grant No. 2006BS04028) and Young Scientist Fund of Shandong Province (Grant No. 2006BS04037).

references

4.

Summary

Sub-micrometer Fe3 Al(Ti) intermetallic reinforced by nanometric TiC can be manufactured by MA and hot-pressing sintering methods. TiC particles with grain size ranging from 50 to 200 nm were homogeneously dispersed in Fe3 Al matrix. The larger TiC particles with sub-micrometer were mainly located at grain boundaries and the smaller ones were within matrix grains. High three-point bending strength and hardness values, 1310 MPa and 90 HRA, respectively were achieved in Fe3 Al(10Ti)/40 vol% TiC composites. The Orowan strengthening effect offered by the nano-TiC particles was the main strengthening mechanism of composites. The addition of Ti favored the improvement of hardness and room temperature bending strength of composites by the ordering strengthening effect and solid solution hardening effect.

Acknowledgements
This work is supported by the National Natural Science Foundation of China (Grant No. 50572034), Young Scientist Fund of

Kang, Y.C., Chan, S.L., 2004. Tensile properties of nanometric Al2 O3 particulate-reinforced aluminum matrix composites. Mater. Chem. Phys. 85, 438443. Ko, S.H., Hanada, S., 1999. In-situ production and microstructures of iron aluminide/TiC composites. Intermetallics 7, 947955. Ko, S.H., Park, B.G., Hashimoto, H., 2002. Effect of MA on microstructure and synthesis path of in-situ TiC reinforced Fe28 at.%Al intermetallic composites. Mater. Sci. Eng. A. 329331, 7883. Krasnowski, M., Kulik, T., 2003. FeAlTiN nanocomposite produced by reactive ball milling and hot-pressing consolidation. Scripta Mater. 48, 14891494. Kudashov, D.V., Baum, H., Martin, U., Heilmaier, M., Oettel, H., 2004. Microstructure and room temperature hardening of ultra-ne-grained oxide-dispersion strengthened copper prepared by cryomilling. Mater. Sci. Eng. A 387389, 768771. Li, J., Yin, Y.Y., Tan, X.Y., 2005. A ZrO2 (3Y) matrix composite toughened with Fe3 Al intermetallic. J. Am. Ceram. Soc. 88, 235238. Luu, W.C., Chiang, W.C., Wu, J.K., 2005. Effect of Cr and Ti additions on the corrosion behavior of Fe3 Al alloys in chloride-containing sulfuric acid solutions. Mater. Lett. 59, 32953298. Schneibel, J.H., Carmichael, C.A., Specht, E.D., Subramanian, R., 1997. Liquid-phase sintered iron aluminide-ceramic composites. Intermetallics 5, 6167. Stoloff, N.S., 1998. Iron aluminides: present status and future prospects. Mater. Sci. Eng. A 258, 114. Subramanian, R., Schneibel, J.H., 1997. FeATiC cermets-melt inltration processing and mechanical properties. Mater. Sci. Eng. A 239240, 633639. Subramanian, R., Schneibel, J.H., Alexander, K.B., 1996. Iron aluminidetitanium carbide composites by pressureless melt inltrationmicrostructure and mechanical properties. Acta Metall. 35, 583588. Tiegs, T.N., Alexander, K.B., Plucknett, K.P., 1996. Ceramic composites with a ductile Ni3 Al binder phase. Mater. Sci. Eng. A. 209, 243247.

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Yin, Y.S., Wang, W.X., Shi, Z.L., 1995. Analysis of valence electron structures (VES) of intermetallic Fe3 Al compounds. Mater. Chem. Phys. 39, 243247.

Zhu, S.M., Tamura, M., Sakamoto, K., 2000. Characterization of Fe3 Al-base intermetallic alloys fabricated by mechanical alloying and HIP consolidation. Mater. Sci. Eng. A 292, 8389.