Elsevier Editorial System(tm) for Materials Letters Manuscript Draft Manuscript Number: MLBLUE-D-12-02087 Title: Evaluation of microstructure and

mechanical properties of bulk nanostructured Ti5Si3 and Ti5Si3-Al2O3 nanocomposite Article Type: Letter Keywords: Nanocomposite; Intermetallic alloys and compounds; Indentation and hardness, powder technology; Sintering Corresponding Author: Mr, Soheil Sabooni, Ph.D Student Corresponding Author's Institution: Isfahan university of technology First Author: Soheil Sabooni, Ph.D Student Order of Authors: Soheil Sabooni, Ph.D Student; Fathallah Karimzadeh, Associated professor; Mohammad H Abbasi, Professor Abstract: Mechanical alloying and sintering have been used to produce bulk nanostructured Ti5Si3 and Ti5Si3-15Wt.% Al2O3 nanocomposite. X-Ray diffraction (XRD), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) were used to study the microstructural characteristics of the samples. Indentation method was used to calculate hardness, elastic modulus and fracture toughness of bulk samples. The results showed that in-situ synthesis of Ti5Si3-Al2O3 nanocomposite can lead to distribution of nanometric Al2O3 particles in the matrix. Consolidated compounds with nanometric grains were obtained by sintering process. Nanohardness, elastic modulus and fracture toughness of Ti5Si3-15Wt.% Al2O3 nanocomposite were calculated as 1660 HV, 238 GPa and 5.5 MPa.m1/2 that is higher than monolithic Ti5Si3 and other Ti5Si3-based nanocomposites. Suggested Reviewers: Mohammad H Enayati Ph.D associated professor, Departement of materials engineering, Isfahan university of technology ena78@cc.iut.ac.ir experts in synthesis and characterization of nanocomposites Majid Tavoosi Ph.D Assistant professor, Departement of materials engineering, Malek ashtar university of technology ma.tavoosi@gmail.com experts in synthesis and characterization of nano materials and amorphous materials Hyoung Seop Kim Ph.D Professor, Departement of materials science and engineering, Pohang university of technology hskim@postech.ac.kr Nanocrystalline materials characterization

Cover Letter

Professor T.G.Nieh The editor,

Materials letters 2012-05-16 Dear Prof T.G.Nieh I would like to submit our paper titled as Evaluation of microstructure and
mechanical properties of bulk nanostructured Ti5Si3 and Ti5Si3-Al2O3 nanocomposite for publishing in your journal. I appreciate it if you could kindly

let me know of suitability of the paper for your journal. I look forward to hearing from you. Best regards, S.Sabooni Ph.D Student, Department of Materials Engineering, Isfahan University of Technology, Isfahan,
Iran

s.sabooni@ma.iut.ac.ir

Highlights (for review)

Highlights Bulk nanostructured Ti5Si3 and Ti5Si3-Al2O3 nanocomposite were synthesized by mechanochemical reactions during mechanical alloying and subsequent sintering. Hardness, elastic modulus and fracture toughness of compounds were evaluated using nanoindentation methods. Ti5Si3- Al2O3 nanocomposite showed higher fracture toughness compared with other synthesized Ti5Si3 based nanocomposite. Crack deflection and crack bridging were evaluated as important factors for fracture toughness increase in Ti5Si3- Al2O3 nanocomposite.

*Manuscript: Text only or Including all items Click here to view linked References

Evaluation of microstructure and mechanical properties of bulk nanostructured Ti5Si3 and

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

Ti5Si3-Al2O3 nanocomposite S.Sabooni*, F.Karimzadeh, M.H.Abbasi

Department of Materials Engineering, Isfahan University of Technology, 84156-83111, Isfahan, Iran

Corresponding author email: s.sabooni@ma.iut.ac.ir

Abstract: Mechanical alloying and sintering have been used to produce bulk nanostructured Ti5Si3 and Ti5Si315Wt.% Al2O3 nanocomposite. X-Ray diffraction (XRD), Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) were used to study the microstructural characteristics of the samples. Indentation method was used to calculate hardness, elastic modulus and fracture toughness of bulk samples. The results showed that in-situ synthesis of Ti5Si3-Al2O3 nanocomposite can lead to distribution of nanometric Al2O3 particles in the matrix. Consolidated compounds with nanometric grains were obtained by sintering process. Nanohardness, elastic modulus and fracture toughness of Ti5Si3-15Wt.% Al2O3 nanocomposite were calculated as 1660 HV, 238 GPa and 5.5 MPa.m1/2 that is higher than monolithic Ti5Si3 and other Ti5Si3-based nanocomposites. Keywords: Nanocomposite; Intermetallic alloys and compounds; Indentation and hardness, powder technology; Sintering

1. Introduction: Silicide compounds have many desirable properties such as high melting point, relatively low density, and high corrosion, wear and creep resistance. In recent years, refractory metal silicides such as Ti5Si3 have attracted much interest among various kinds of silicides [1-2]. Monolithic Ti5Si3 has been successfully fabricated by various methods such as arc melting [3], Shock assisted synthesis [4], self propagating high temperature synthesis (SHS) [5], etc. Limitations such as poor ductility and toughness are serious problems to be overcome in monolithic Ti5Si3. Several methods exist for

toughening this compound. Grain size reduction and composite formation are the most promising
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

approaches to increase fracture toughness of structural intermetallics. Li et al [6] studied the microstructure and mechanical properties of Ti5Si3-TiC nanocomposite and reported improvement of room temperature ductility and high temperature strength. Mean while, not much improvement was observed in the fracture toughness of bulk nanostructured Ti5Si3 produced by counihan etal [7] due to the oxygen and nitrogen contamination of powders. Compatibility between reinforcement particles and matrix and uniform distribution of reinforcements are also important issues in composite forming. In-situ synthesis of reinforcement phase in the matrix has advantage over other synthesis routes due to its capability to produce chemical compatible phase as well as nanosized structure with high uniformity [8]. So, the aim of this research was the synthesis and characterization of bulk nanostructured Ti5Si3 and bulk Ti5Si3-15Wt.% Al2O3 nanocompsoite by mechanochemical reaction and sintering and comparison of their microstructure and mechanical properties. 2. Materials and methods High purity Ti, Si, Al and TiO2 were used as initial materials. A mixture of Ti-18TiO2- 22Si-8Al (Wt.%) were used to synthesize in-situ produced Ti5Si3-15Wt.% Al2O3 nanocomposite. Also Ti26Wt.% Si was milled to synthesize nanostructured Ti5Si3. In all mechanical alloying runs the ball to powder weight ratio and rotational speed were 10:1 and 500 rpm, respectively. Mechanically alloyed powders after 60h of MA were cold pressed at a pressure of 700 Mpa and sintered at 1400 0C for 90 min to obtain bulk nanostructured compounds. The structural features of powder particles and bulk samples were studied by X-Ray diffraction, Scanning electron microscope and Transmission electron microscope. Hardness, elastic modulus and fracture toughness of sintered samples were also evaluated by indentation methods. 3. Results and discussion

Fig.1 shows the XRD patterns of Ti5Si3-15Wt.% Al2O3 nanocomposite after 60h of milling and subsequent sintering. XRD patterns of this nanocomposite after 60h of milling include only Ti5Si3 peaks that is due to the poor crystallization and/or nanometric size of in-situ produced Al2O3. Nanometric scale of in-situ produced Al2O3 phase after reduction of TiO2 by Al was previously observed by TEM in Ti5Si3-50Wt.% Al2O3 nanocomposite synthesized in our previous investigation

(Fig.2(a)) [9]. The crystallite size of Ti5Si3-15Wt.% Al2O3 nanocomposite after 60h milling and
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

subsequent sintering was about 15nm and 73 nm, respectively. Actually the presence of fine Al2O3 particles in the structure, retentions grains by pinning the grain boundaries and prevents excess grain growth [10]. The porosity of this nanocomposite after sintering was found about 9Wt.%. Fig.2 (b) also shows the TEM image of Ti-26Wt.% Si after 60h of milling. Nanometric grains are obviously seen in the TEM image. Further information about formation mechanism of nanostructured Ti5Si3 powders can be found in our previous investigation[11]. The porosity of nanostructured Ti5Si3 after sintering was about 12Wt.%.

Fig.1: XRD pattern of Ti5Si3-15Wt.% Al2O3 after 60h of MA and subsequent sintering

Fig.2: TEM images of (a) 60h milled Ti5Si3-15Wt.% Al2O3 nanocomposite (b) 60h milled nanostructured Ti5Si3

Nanoindentation study (Olivier and Pharr method) was used to determine hardness and elastic modulus of Bulk samples [12]. Fig.3 shows the load- displacement curves for the Nanostructured Ti5Si3 and Ti5Si3-15Wt.% Al2O3 nanocomposite. The maximum force applied for these experiments

was 30mN. The difference between hardness of the samples was obviously detectable from their
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

penetration depth difference.

Fig.3: Nanoindentation load- displacement curves for the Ti5Si3-15Wt.% Al2O3 nanocomposite (ID 1) and nanostructured Ti5Si3 (ID 2)

Many investigators have used rule of mixtures for determining elastic modulus of intermetallic matrix nanocomposite to be used in indentation fracture toughness formula. The elastic modulus of Ti5Si3-15Wt.% Al2O3 obtained from nanoindentation tests (238 GPa) were completely different from that obtained from rule of mixtures (155 GPa). This shows unsuitability of using rule of mixtures for determining elastic modulus of intermetallic based nanocomposites. There is high differences between reported hardness values reported for Ti5Si3 that maybe due to the grain size of synthesized Ti5Si3. Rosenkranz [13] reported hardness of 968HV for Ti5Si3 produced by reaction sintering and hot pressing. Mean while Chon etal [14] reported hardness of about 1180 HV for electro discharge sintered Ti5Si3. The lower crystallite size of nanostructured Ti5Si3 synthesized by MA and sintering in this research is a reason for the higher hardness. The fracture toughness of bulk samples in this study were determined by both Evans and Niihara formulas [6,15]. KIC = P (C)-1.5 Cot (Evans Formula) (Niihara formula)

KIC = 0.0309 (E/H)0.4 p/c1.5

Where P is applied load, = 680, E is elastic modulus, H is hardness and 2C is the length of crack.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

Minimum five indentations were carried out for determining the fracture toughness. Fig.4 (a) shows the extension of cracks in Ti5Si3-15Wt.% Al2O3 nanocomposite. The fracture toughness of nanostructured Ti5Si3 and Ti5Si3-15Wt.% Al2O3 nanocomposite were calculated as about 4 and 5.5 Mpa.m1/2, respectively according to Evans formula. Table 1 shows grain size dependence of fracture toughness of Ti5Si3 and Ti5Si3-based nanocomposite.

Fig.4: (a) Extension of cracks in Ti5Si3-15Wt.% Al2O3 nanocomposite (b) Crack deflection as a mechanism for fracture toughness increase in Ti5Si3-Al2O3 nanocomposite Table 1: Grain size dependence of fracture toughness of Ti5Si3 and Ti5Si3-based nanocomposite

Fracture toughness Composition (Mpa.m1/2) Synthesis method Reference

Ti5Si3 (Grain size: 20-50 m)

2.1

Vacuum reaction sintering Dynamic densification of

13

Ti5Si3 (grain size: 50-150 nm)

2-3 amorphous Ti-Si powder

Nanostructured Ti5Si3 Ti5Si3- 14Vol.%TiC Ti5Si3- 35Vol.%TiC Ti5Si3- 15Wt.% Al2O3

4 3 0.2 4.2 0.2 5.5 0.5

Mechanical alloying Hot reaction pressing Hot reaction pressing Mechanical alloying

This work 6 6 This work

Many investigators studied the effect of grain size on the fracture toughness of brittle ceramic and
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

intermetallics. Rice etal. [16] Reported significant dependence of fracture toughness on grain size of dense sintered body with non-cubic crystal structures, but the dense polycrystalline bodies with cubic crystal structure showed no significant dependence of fracture energy on grain size. So, with respect to the hexagonal crystal structure of Ti5Si3, decreasing of grain size could affect the fracture toughness of this material significantly. Nanostructured Ti5Si3 synthesized in this work showed fracture toughness increase by the order of 2 compared to coarse grain Ti5Si3. Also Ti5Si3-15Wt.% Al2O3 nanocomposite had higher fracture toughness compared to monolithic Ti5Si3 and other Ti5Si3-based nanocomposites. It is well known that fracture toughness of a material not only depends on composition but also the ability of its microstructure to dissipate deformation energy without propagation of cracks. Toughening mechanism of crack deflection and crack bridging were identified as important reasons for fracture toughness increase in Ti5Si3-Al2O3 nanocomposite (Fig.4 (b)). Besides the high melting point and high hardness of Ti5Si3-Al2O3 nanocomposite, higher fracture toughness of this material compared to other Ti5Si3-based composites makes this nanocomposite a suitable material for aerospace industry applications. Fracture toughness of nanostructured Ti5Si3 and Ti5Si3-15Wt.% Al2O3 were also calculated as 3 and 4.2 Mpa.m1/2 by Niihara method using the hardness and elastic modulus calculated from nanoindentation tests. It can be seen that these two methods of calculating fracture toughness show almost similar fracture toughness that can confirm the elastic modulus obtained from nanoindentation tests. 4. Conclusions Bulk nanostructured Ti5Si3 and Ti5Si3-15Wt.% Al2O3 nanocomposite with suitable density were successfully fabricated by mechanical alloying and subsequent sintering. The results showed that insitu fabrication of Al2O3 phase via reduction of TiO2 by Al, led to distribution of Al2O3 nanoparticles in the matrix which results in better mechanical properties compared to monolithic Ti5Si3. Nanohardness, elastic modulus and fracture toughness of Ti5Si3-15Wt.% Al2O3 nanocomposite were

determined as 1660 HV, 238 Gpa and 5.5 Mpa.m1/2, respectively. Toughening mechanisms based on
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

crack deflection and crack bridging were determined as responsible factors for fracture toughness increase of this nanocomposite. 5. References [1] Westbrook JH., Fleischer RL., Structural application of 7ntermetallic compounds , wiley, 2000. [2] Sauthoff G, Intermetallics, VCH Verlagsgesellschaft, Weinheim (Federal Republic of Germany), 1995. [3] Zhang l, Wu J, Ti5Si3 and Ti5Si3 based alloys: alloying behavior, microstructure and mechanical property evaluation, Acta Mater. 1998; 46(10): 3535-46. [4] Thadhani NN, Namjoshi S, Counihan PJ, Crawford A, Shock assisted synthesis of Ti5Si3 intermetallic compound, Journal of materials processing technology 1999; 85: 74-8 [5] Yeh CL, Chen WH, Hsu CC, formation of titanium silicides Ti5Si3 and TiSi2 by self propagating combustion synthesis, journal of alloys and compounds 2007; 432: 90-5. [6] Li J, Jiang D,Tan Sh, Microstructure and mechanical properties of in situ produced Ti5Si3/TiC nanocomposites, Journal of the European Ceramic Society 2002; 22; 551-8. [7] Counihan PJ, Crawford A, Thadhani NN, Influence of dynamic densification on nanostructure formation in Ti5Si3 intermetallic alloy and its bulk properties, Materials Science and Engineering A 1999; 267: 26-35. [8] M. Khodaei, M.H. Enayati, F. Karimzadeh, The structure and mechanical properties of Fe3Al30 vol.% Al2O3 nanocomposite, J Alloy Compd., 2009; 488: 134-7. [9] Sabooni S, Karimzadeh F , Abbasi MH, A study on the mechanochemical behavior of TiO2Al Si system to produce Ti5Si3Al2O3 nanocomposite, Advanced Powder Technology (2011), doi:10.1016/j.apt.2011.02.004. [10] Mousavi T, Karimzadeh F, Abbasi M.H, Mechanochemical assisted synthesis of NiTi intermetallic based nanocomposite reinforced by Al2O3, J Alloy Compd., 2009; 467: 173-8.

[11] Sabooni S, Karimzadeh F, Abbasi M.H, Thermodynamic aspects of nanostructured Ti5Si3

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65

formation during mechanical alloying and its Characterization, Bulletin of materials science, In Press. [12] Oliver WC, Pharr GM, An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments, J. Mater. Res.,1992; 7: 1564-83. [13] Rosenkranz R, Frommeyer R, Smarsly W, Microstructures and properties of high melting point intermetallicTi5Si5 and TiSi2 compounds, Mater. Sci. Eng. A, 1992; 152: 288-294. [14] Cheon YW, Jo YJ, Lee CM, Jang HS , Kim KB, Lee WH, Consolidation of mechanical alloyed Ti 37.5 at.% Si powder mixture using an electro-discharge technique, Mater. Sci. Eng.A, 2007; 467: 89-92. [15] Niihara K, Morena R, Hassleman DPH, Evaluation of KIC of brittle solids by the indentation method with low crack - to - indent ratios , J. Mater. Sci. Lett., 1982; 1: 13-6. [16] Rice RW, Freiman SW, Becher PF, Grain-size dependence of fracture energy in ceramics: I, Experiment and II: a model for non-cubic materials, J. American Ceram. Soc., 1981; 64:345-355.