International Journal of Metallurgical & Materials Science and Engineering (IJMMSE) ISSN 2278-2516 Vol.

2 Issue 4 Dec - 2012 21-30 TJPRC Pvt. Ltd.,

DEVELOPMENT OF SILICONIZED IRON (III) OXIDE NANOPARTICLES REINFORCED UNSATURATED POLYESTER TOUGHENED EPOXY NANOCOMPOSITES
1 1

S. JULYES JAISINGH, 2V. SELVAM, 3M. SURESH CHANDRA KUMAR & 4K. THYAGARAJAN
2,3

Department of Mechanical Engineering, St. Xaviers Catholic College of Engineering, Nagercoil - 629 003, India Polymer Nanocomposite Centre, Department of Chemistry & Research Centre, Scott Christian College, Nagercoil - 629 003, India

Department of Mechanical Engineering, Noorul Islam College of Engineering, Kumaracoil - 629 180, India

ABSTRACT
Diglycidyl ether of bisphenol A based epoxy resin (DGEBA, LY 556) was toughened with 5%, 10% and 15% (by wt.) of unsaturated polyester (UP) using benzoyl peroxide as radical initiator and 4,4-diaminodiphenylmethane (DDM) as curing agent. The 3-aminopropyltrimethoxysilane modified iron (III) oxide nanoparticles reinforced UP toughened epoxy nanocomposites also prepared. Iron (III) oxide and siliconized iron (III) oxide nanoparticles were characterized by FT-IR, XRD and TEM. The homogeneous morphologies of the UP toughened epoxy and siliocnized iron (III) oxide reinforced UP toughened epoxy hybrid systems were ascertained from scanning electron microscope (SEM).

KEYWORDS: Siliconized Iron (III) Oxide Nanoparticles Reinforced UP Toughened Epoxy, FTIR Spectroscopy,
Morphology

INTRODUCTION
Epoxy resin has been widely used in composites, laminates, construction materials, surface coating, adhesives, automotive, electronics, aircraft and spacecraft industries owing to their high strength and stiffness, low viscosity, volatile and shrinkage during cure, low creep and good adhesion to many substrates and easy process ability under various conditions (Lee et al., 1967; Yanfang et al., 1999; Robert et al., 1998; Masaahi et al., 1999; Bar-Long et al., 1999). However due to their highly cross-linked density, they exhibit a low impact strength, a poor resistance to crack propagation and a small elongation at break, i.e. they are inherently brittle. In the last few decades, efforts have been taken for the improvement of the fracture toughness of epoxy resin aiming at enlarging their field of applications. Approaches to improve the epoxy resin fracture toughness include the incorporation of elastomer or flexible thermoplastics. It was noticed that, the reactive rubber toughening of epoxy using ATBN, CTBN and other elastomers always associated with a decrease in modulus and Tg. (Kinloch et al., 1983; Sanjana et al., 1985; Wise et al., 2000; Kunz et al., 1982; Levita et al., 1985). The use of rigid, thermoplastics such as polysulphones, polyether sulphones and polyether imides to toughen epoxy has been attempted, where the related toughening mechanism was proposed. These studies show good improvement in thermal and mechanical properties. However, these polymers show poor solubility in organic solvents leading to difficulties in processing (Hedrick et al., 1985; Bucknal et al., 1983; Hourston et al., 1991; Rong et al., 1997; Li et al., 1999). Hence, selection of suitable polymeric material is essential to improve the impact strength with retaining stiffness, glass transition temperature and thermal stability of the epoxy matrix. Development of an intercross-linked polymer network of thermoset - thermoset blends have been developed to achieve the enhanced mechanical properties. Among the various thermoset modifiers, unsaturated polyester (UP) resin seems to be the most attractive modifier because of their versatile behavior like flexibility, high

22

S. Julyes Jaisingh, V. Selvam, M. Suresh Chandra Kumar & K. Thyagarajan

thermal stability, heat resistance, low water absorption, chemical resistance and competitive cost and ease of processing (Ramakrishn et al., 2006). The nanoparticles reinforced polymer composites have shown great potential for applications including aircraft, spacecraft, magnetic hard disks, and the magnetic bars of credit card. Among the composites, the magnetic nanopowder reinforced polymer nanocomposites exhibit magnetic properties and wear properties superior to those of other composites (Gould et al., 2006; Zhang et al., 2001; Goodwin et al., 1999; Zhang et al., 2007; Chertok et al., 2008; Hong et al., 2007; Birsan et al., 2009). Magnetic nanopowder reinforced polymer nanocomposites suffer from some problems, for example, the interfacial bonding between polymer resin and reinforced powder is weak, and dispersion of magnetic powders in organic media is difficult (Guo et al., 2007). For this reason, magnetic powders are agglomerated in the polymer and become defects in the magnetic/polymer nanocomposites. Moreover, under force, cracks propagate from those defective sites. Therefore, much research has sought to develop effective methods for the dispersion of magnetic powders in the polymer matrix. In the present work, Iron (III) oxide nanoparticles were modified with 3-aminopropylsilane by solvent method. The obtained siliconized iron (III) oxide reinforced UP toughened with epoxy nanocomposites were developed. The obtained iron (III) oxide, siliconized iron (III) oxide nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), XRD, TEM. Morphology of the composites were studied by Scanning electron microscopy (SEM).

EXPERIMENTAL
Materials Diglycidyl ether of bisphenol-A (DGEBA) based epoxy resin, LY 556, having epoxy equivalent of about 180-190 and 4, 4diaminodiphenylmethane (DDM), epoxy hardner were purchased from Ciba-Geigy Ltd., India. Unsaturated polyester (UP) resin (phthalic acid, maleic anhydride and propylene glycol with 25% styrene having the average molecular weight 2,3002,600 g/mol and viscosity of 600 cP) was procured from Naphtha Resins and Chemicals, India. 3aminopropyltrimethoxysilane having boiling point 217 oC, density 0.946 g.cm-3, Mw 221.3 was purchased from Aldrich, USA. Iron (III) oxide (Fe2 O3) nanoparticle (<50 nm) having m.p 565 oC, density 5.12 was procured from Sigma Aldrich Inc., India. Benzoyl peroxide was obtained from Merck India Ltd., India. Preparation of Siliconized Iron (III) Oxide Nanoparticles The siliconization of iron (III) oxide nanoparticles with 3-aminopropyltrimethoxysilane was carried out in a 250 ml 3-necked flask, equipped with a reflux condenser, nitrogen inlet tube, dropping funnel, on a thermostated silicone bath. The reactions were performed in inert atmosphere, at dichloroethane reflux temperature (810C) for 24 h. 20 ml dichloroethane, 0.3 g dibutyltindilaurate (catalyst), 0.6367g iron (III) oxide nanoparticles (2.7 mmol) and 4.73 g 3aminopropyltrimethoxysilane (21.4 mmol) were added. The unreacted solvent and monomers were separated by vacuum distillation on a rotavapor at 35oC. Siliconized iron (III) oxide nanoparticles, washed with small amounts of toluene for the removal of siloxane oligomers formed during the reaction and with acetone for the separation of catalyst, were dried in vacuum at 350C for 24 h (Scheme 1).

Development of Siliconized Iron (III) Oxide Nanoparticles Reinforced Unsaturated Polyester Toughened Epoxy Nanocomposites

23

Scheme 1: Preparation of Siliconized Iron (III) Oxide Nanoparticles Development of Unsaturated Polyester Toughened Epoxy Unsaturated polyester toughened epoxy resin was developed by blending calculated amount of unsaturated polyester (5,10,15 wt.%) relative to the epoxy resin (100 w/w), stiochiometric amount of 4,4-diaminodiphenylmethane (27.2 g) with respect to epoxy resin and benzoyl peroxide (2 wt%) using a high speed stirrer at 80 oC for 10 minutes with constant stirring. The hybrid product was then degassed to remove the entrapped air and then transferred into a preheated mould and kept at 100 oC for 4 h and post cured at 140 oC for 3 h and finally removed from the mould and characterized Preparation of Siliconized Iron (III) Oxide Unsaturated Polyester Toughened Epoxy Nanocomposites A fixed amount of epoxy resin (100 g), known amount of unsaturated polyester resin (10 g), calculated amount of siliconized iron (III) oxide (1,3,5 g), a stoichiometric amount of 4,4-diaminodiphenylmethane (27.2 g) with respect to epoxy resin and benzoyl peroxide (2 wt.%) were mixed at 80 C for 10 min. with constant stirring. The hybrid product was then degassed to remove the entrapped air and was then transferred into a preheated mould kept at 100 C for 4 h and post-cured at 140 C for 3 h (Scheme 2).

Scheme 2: Reaction between Siliconized Iron (III) Oxide Nanoparticle and Epoxy Resin

TEST METHODS
TEM Analysis Transmission electron microscope (TEM) was used to characterize the morphology (size and shape) of the iron (III) oxide and siliconized iron (III) oxide nanoparticles. TEM was carried out in a JEM 100CX (JEOL) with an accelerating voltage of 100 keV.

24

S. Julyes Jaisingh, V. Selvam, M. Suresh Chandra Kumar & K. Thyagarajan

XRD Analysis Wide angle X-ray scattering (WAXS) were recorded at room temperature by using X-Pert Pro diffractometer with CuK radiation, 40kV, 100mA made by PANalytical, The Netherlands. The diffraction patterns were determined over a range of diffraction 2 = 0 100o. FT-IR Spectroscopy The IR spectra were recorded on a Perkin-Elmer FT-IR spectrometer, with KBr pellets, for solid samples. Morphology Surface morphology of fractured surface of the samples was performed using scanning electron microscope (SEM; JEOL JSM Model 6360). The fractured surface of the samples was coated with gold before scanning.

RESULTS AND DISCUSSIONS

TEM Analysis TEM study on the iron (III) oxide and siliconized iron (III) oxide nanoparticles were done to know the morphology of the particles.TEM images shown in Figure. 1a and 1b confirmed the presence of well-dispersed nano-sized spherical particles of iron (III) oxide and siliconized iron (III) oxide nanoparticles with diameters ranging from 14 to 20 nm. The size determined from TEM.

Figure 1a: Iron (III) Oxide Nanoparticles

Figure 1b: Siliconized Iron (III) Oxide Nanoparticles

Development of Siliconized Iron (III) Oxide Nanoparticles Reinforced Unsaturated Polyester Toughened Epoxy Nanocomposites

25

XRD Analysis The size of iron (III) oxide nanoparticles before and after surface modification also investigated by XRD analysis. Figure. 2 a,b shows XRD results of unmodified and siliconized iron (III) oxide nanoparticles. As shown in the figures, the main peaks of siliconized iron (III) oxide nano particles coincide with those of iron (III) oxide nanoparticles. The main peaks occur at 2 = 30.26 , 35.48 , 43.26 , 51.32 , 56.68 , and 62.66 , which correspond to (2 2 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0), respectively. The size of iron (III) oxide and siliconized iron (III) oxide nano particles were

determined from Scherrers equation (M. Wan etal.,1998). These results show that the size of iron (III) oxide nano particles was not affected by surface modification and ranged from 14 nm to 17 nm, which agrees with TEM.

Figure 2: (a) Iron (III) Oxide Nanoparticles, (b) Siliconized Iron (III) Oxide Particles FT-IR Spectroscopy Figure 3. Shows characteristic FT-IR absorptions of iron (III) oxide and siliconized iron (III) oxide nanoparticles. Iron (III) oxide nanoparticles spectrum (Figure 3a) presents the characteristic absorption bands of Fe-O at 640.39, 563.23 and 440 cm-1, a broad band at 3448.84 cm-1 due to Fe-OH and a deformation vibration of OH bond at 1635.65 cm1

(Durdureanu-Angheluta et al., 2008; Harabagiu et al., 2009). The covalent bonding of aminopropylsilane group is mainly

due to their self-polycondensation leading to core-shell nanoparticles. The presence of Fe-O-Si bonds cannot be seen in the FT-IR spectrum because it appears at around 640.39 and 563.23 cm1 and therefore overlaps with the FeO vibration of iron (III) oxide nanoparticles, however, the bands were wider and sharper than iron (III) oxide nanoparticles alone (Feng et al., 2008; Ma et al., 2003). But, the adsorption of silane polymer onto the surface of iron (III) oxide nanoparticles (Figure. 3b) was confirmed by bands at 1114.89 and 1047.2 cm1 which correspond to the Si-OH and SiOSi groups (Ma et al., 2003). The absorption bands at 890.4 cm1 and 780 cm1 are due to the stretching of SiOH and vibrations of -OH on the surface of iron (III) oxide nanoparticles. Furthermore, the two broad bands at 3448.84 cm1 and 1635.69 cm1 can be ascribed to the NH stretching vibration (White et al., 2000; Heiney et al., 2000). These results indicate the formation of siliconized iron (III) nanoparticles.

26

S. Julyes Jaisingh, V. Selvam, M. Suresh Chandra Kumar & K. Thyagarajan

Figure 3: FT-IR Spectra of (a) Iron (III) Oxide (b) Siliconized Iron (III) Oxide

MORPHOLOGY
The SEM micrographs of fractured surfaces of the unmodified epoxy system indicated smooth, glassy and homogeneous microstructure (Figure 4a.). This supports brittle nature and poor impact strength of unmodified epoxy system. The micrograph of the fractured surface of UP toughened epoxy system shows a homogeneous structure (Figure 4b.) which confirms the chemical interaction between unsaturated polyester and epoxy resin. This further supports that there is no phase separation between the two components.

Figure 4a: SEM Photograph of Epoxy

Figure 4b: SEM Photograph of 10% UP Toughened Epoxy

Development of Siliconized Iron (III) Oxide Nanoparticles Reinforced Unsaturated Polyester Toughened Epoxy Nanocomposites

27

Figure 4c. depicts the iron (III) oxide nanoparticles reinforced UP toughened epoxy nanocomposites. The nanoparticles are observed to aggregate in the form of clusters at a micrometric scale with many voids (air gap) among the clusters, indicating a poor adhesion between the nanoparticles and the polymer matrix. However, in nanocomposites containing the siliconized iron (III) oxide nanoparticles shown in Figure 4d. more uniformly dispersed nanoparticles are observed; indicating that nanoparticles surface functionalization using silane improved the nanoparticles dispersion in the polymer matrix. No observable void indicates a strong chemical interaction between the nanoparticles and polymer matrix. Thus, particle surface treatment causes the particle to disperse more uniformly in the polymer matrix, and the formed chemical bonding between the nanoparticles and polymer matrix favours a more compact solid structure without obvious gas gaps.

Figure 4c: SEM Photograph of 10% UP toughened 3% iron (III) Oxide Nanoparticles Reinforced Epoxy

Figure 4d: SEM Photograph of 10% UP toughened 5% Siliconized Iron (III) Oxide Nanoparticles Reinforced Epoxy

CONCLUSIONS
The siliconized iron (III) oxide nanoparticles filled unsaturated polyester toughened epoxy nanocomposites were developed. The siliconized iron (III) oxide nanoparticles were characterized by FTIR. The iron (III) oxide and siliconized iron (III) oxide nano particles were studied by XRD and TEM. The thermal and morphological aspects of different composition of unsaturated polyester toughened epoxy reinforced siliconized iron (III) oxide nanocomposites were studied.

28

S. Julyes Jaisingh, V. Selvam, M. Suresh Chandra Kumar & K. Thyagarajan

Homogeneous microstructures of SEM confirmed the effective interaction of siliconized iron (III) oxide nanoparticles with UP toughened epoxy matrix.

REFERENCES
1. 2. Lee H., Neville K. (1967). Handbook of Epoxy Resins, McGraw-Hill, New York. Yanfang L., Shigang S., Yanfang L., Jugang G. (1999). Kinetics of 4,4-diaminodiphenyl methane curing of bisphenol-S epoxy resin, J Appl Polym Sci, 73, 17991803 3. Robert V., Istvan C., Gabor T., Istvan R., Attila I., Andras V. (1998). A study of epoxy resin-acrylated polyurethane semi-interpenetrating polymer networks, J Appl Polym Sci, 68, 111119 4. Masaahi K., Kazuhiko N., Takeshi E. (1999). Synthesis of a bifunctional epoxy monomer containing biphenyl moiety and properties of its cured polymer with phenol novolac. J Appl Polym Sci, 74, 690698 5. Bar-Long D., Yu-Shen H., Leo-Wang C., Wen-Yen C., Tseng-Rong W. (1999). The curing reaction and physical properties of DGEBA/DETA epoxy resin blended with propyl ester phosphazene. J Appl Polym Sci, 74, 229237 6. Kinloch A.J., Shaw S.J., Tod D.A., Hunston D.L. (1983). Deformation and fracture behaviour of a rubbertoughened epoxy. I. Microstructure and fracture studies. Polymer, 24, 13411354 7. Sanjana Z.N., Kupchella L. (1985). Dynamic mechanical analysis of rubber toughened epoxy resins. Polym Eng Sci, 25, pp. 11481154 8. Wise C.W., Cook W.D., Goodwin A.A. (2000). CTBN rubber phase separation in model epoxy resins. Polymer, 41, 46254633 9. Kunz S.C., Sayre J.A., Assink R.A. (1982). Morphology and toughness characterization of epoxy resins modified with amine and carboxyl terminated rubbers. Polymer, 23, 18971906 10. Levita G., Marchetti A., Butta E. (1985). Influence of the temperature of cure on the mechanical properties of ATBN/Epoxy blends. Polymer, 26, 11101116 11. Hedrick J.L., Yilgor I., Wilkes G.L., McGrath J.E. (1985). Chemical modification of matrix resin networks with engineering thermoplastics. Polym Bull, 13, 201208 12. Bucknal C.B., Partridge I.K. (1983). Phase separation in epoxy resins containing polyethersulphone, Polymer, 24, 639-644 13. Hourston D.J., Lane J.M., MacBeath N.A. (1991). Toughening of epoxy resins with thermoplastics II. Tetrafunctional epoxy-polyetherimide blends. Polym Int, 26, 1721 14. Rong M., Zeng H. (1997). Polycarbonate-epoxy semi-interpenetrating polymer network: Phase separation and morphology, Polymer, 38, 269277 15. Li S., Hsu B.L., Li F., Li C.Y., Harris F.W., Cheng S.Z.D. (1999). A study of polyimide thermoplastics used as tougheners in epoxy resins Structure, property and solubility relationships, Thermochimica Acta, 340341, 221229

Development of Siliconized Iron (III) Oxide Nanoparticles Reinforced Unsaturated Polyester Toughened Epoxy Nanocomposites

29

16. Ramakrishn H.V., Rai S.K. (2006). Effect on the mechanical properties and water absorption of granite powder composites on toughening epoxy with unsaturated polyester and unsaturated polyester with epoxy resin, J Reinf Plast Compos, 25, 17-32 17. Gould P. (2006). Nanomaterials face control measures, Nano Today, 1, 3439 18. Zhang X.H., Gates R.S., Anders S., Hsu S.M. (2001). An accelerated wear test method to evaluate lubricant thin films on magnetic hard disks, Tribol Lett, 11, 521 19. Goodwin S., Peterson C., Hoh C., Bittner C. (1999). Targeting and retention of magnetic (MTCs) enhancing intra-arterial chemotherapy, J Magn Magn Mater, 194, 132139 20. Zhang L.Y., Gu H.C., Wang X.M. (2007). Magnetite ferrofluid with high specific absorption rate for application in hyperthermia, J Magn Magn Mater, 311, 228233 21. Chertok B., Moffat B.A., David A.E., Yu F., Bergemann C., Ross B.D., Yang V.C. (2008). Iron oxide targeted carriers

nanoparticles as a drug delivery vehicle for MRI monitored magnetic targeting of brain tumors, Biomaterials, 29, 48796 22. Hong R.Y., Pan T.T., Han Y.P., Li H.Z., Ding J., Han S. (2007). Magnetic field synthesis of Fe3O4 nanoparticles used as a precursor of ferrofluids, J Magn Magn Mater, 310, 3747 23. Birsan I.G., Circiumaru A., Bria V., Ungureanu V. (2009). Tribological and electrical properties of filled epoxy reinforced composites, Tribol Int, 31, 3336 24. Guo L., Pei G.L., Wang T.J., Wang Z.W., Jin Y. (2007). Polystyrene coating of Fe3O4 particles using dispersion polymerization, Colloids Surf, A, 293, 5862 25. M. Wan, J. Li, (1998) Synthesis and electricalmagnetic properties of polyaniline composites, J. Polym. Sci. Polym. Chem. 36, 27992805 26. Durdureanu-Angheluta A,, Ardeleanua R,, Pintealaa M,, Harabagiua V,, Chiriacc H,, Simionescua B,C. (2008). Silane covered magnetite particles: Preparation and characterization, Digest journal of nanomaterials and biostructures, 3, 33-40 27. Harabagiu V., Bogdan C., Simionescu B.C, Chiriac H., Durdureanu-Angheluta A., Stoica.I, Pinteala M., Pricop L. Doroftei F. (2009). Glycidoxypropylsilane-functionalized magnetite as precursor for polymer-covered core-shell magnetic particles, High Perform Polym, 21, 548561 28. Feng B., Hong R.Y., Wang L.S., Guo L., Li H.Z., Ding J., Zheng Y., Wei D.G. (2008). Synthesis of Fe3O4/APTES/PEG diacid functionalized magnetic nanoparticles for MR imaging, Colloids Surf, A, 328, 5259 29. Ma M., Zhang Y., Yu W., Shen H., Zhang H., Gu N. (2003). Preparation and characterization of magnetite nanoparticles coated by amino silane. Colloids Surf, A, 212, 219226 30. White L.D, Tripp C.P. (2000). Reaction of (3-Aminopropyl)dimethylethoxysilane with amine catalysts on silica surfaces, J Colloid Interface Sci, 232, pp. 400407 31. Heiney P.A, Gruneberg K., Fang J. (2000). Structure and growth of chromophore functionalized (3aminopropyl)triethoxysilane self-assembled on silicon, Langmuir 16, 2651657.