International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 INTERNATIONAL JOURNAL OF ADVANCED RESEARCH IN 6480(Print),

, ISSN 0976 6499(Online) Volume 3, Number 2, July-December (2012), IAEME

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ISSN 0976 - 6480 (Print) ISSN 0976 - 6499 (Online) Volume 3, Issue 2, July-December (2012), pp. 248-256 IAEME: www.iaeme.com/ijaret.asp Journal Impact Factor (2012): 2.7078 (Calculated by GISI) www.jifactor.com

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A NEW NANO-CERIA REINFORCED EPOXY POLYMER COMPOSITE WITH IMPROVED MECHANICAL PROPERTIES
Siddhant Datta1*, B.M. Nagabhushana2, R. Harikrishna2 1 Department of Mechanical Engineering, RV College of Engineering. Bangalore. India-560 059 2 Department of Chemistry, MS Ramiah Institute of Technology. Bangalore. India-560 054 (*Corresponding author: email-siddhant.datta@gmail.com) ABSTRACT This study deals with enhancement of mechanical properties of Epoxy matrix using nanoCeria (CeO2) as particulate reinforcement. Nano-Ceria with 10-20nm crystallite size was prepared by solution combustion method using Citric acid as fuel. Epoxy matrix was a standard diglycidyl ether of bis-phenol A (DGEBA) cured with aliphatic amine hardner. Nano-Ceria was dispersed in epoxy resin by manual stirring followed by sonication at 20 Khz for 15 minutes. Amine hardner was added to the sonicated mixture and rectangular polymer composite slabs of 10x8x1.5 cm3 were cast using releasing agent coated glass moulds. Effect of varying wt% of nano-ceria filler on mechanical properties of the matrix was studied. Flexural strength, Compressive strength, Vickers Microhardness and Density were tested for polymer slabs varying in wt% of nano-ceria filler from 0 to 3 wt%. Polymer nano-composite sample containing 0.25 wt% nano-ceria exhibits 42% increase in flexural strength. Sample with 0.5 wt% nano-ceria shows increase of 42.7% in compressive strength. Microhardness increased by 29% for the sample with 1 wt% of nano-ceria. All tests were carried out according to ASTM standards. As the wt% of nano-ceria increased the mechanical properties showed improvement till a maximum value and then these properties deteriorated with further increase in nano filler content. However, density continued to increase with increase in wt% of nano-Ceria. Keywords: Epoxy, Nano-ceria, Sonication, Mechanical properties, Nano-composite. 1. INTRODUCTION Epoxy resins are well established thermosetting matrices of advanced composites, displaying a series of interesting characteristics like good stiffness and specific strength, dimensional stability, chemical resistance, ease of processing and also strong adhesion to the embedded
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reinforcement [1]. Epoxy resin is widely used as host matrix for fabricating Fiber Reinforced Polymers (FRP) with higher strength to weight ratio than steel. Commonly used Fibers in epoxy based FRPs are glass fiber, kevlar fiber, carbon fiber etc. The use of particulate fillers has been proven to improve the material properties of epoxy resins. Building on the fact that the microscaled fillers have successfully been synthesized with epoxy resin, the nano-scaled fillers are now being considered to produce high performance composite structures with further enhanced properties. Nano filler reinforced epoxy matrix can also provide superior host matrix for FRP composites. Improvements in mechanical, electrical, and chemical properties have resulted in major interest in nanocomposite materials in numerous automotive, aerospace, electronics and biotechnology applications [2]. Various kinds of ceramic materials, e.g. SiC, Montmorillonite clay, Al2O3, SiO2, WO3 and ZrO2, have been used to reinforce polymers. Superior properties of metal oxides such as high refractoriness, hardness, compressive strength, modulus of elasticity, thermal resistance and wear resistance make them suitable for use as reinforcement material in polymer matrices [3,4]. Incorporating ultra-fine particles of metal oxides can significantly improve mechanical properties of the host matrix by getting uniformly embedded in the thoroughly cross linked chains of the thermoset-polymer. Metal oxide nanoparticles possess high surface area to volume ratio which increases interfacial interaction between nano-reinforment and host polymer matrix, thus better adhesion between resin and filler is achieved. These nanoparticles present good wettabilty with the thermoset-polymer and fill in the small gaps between cross-linked polymer chains providing the chains with high resistance to deformation under stress. Nanoparticle reinforcements can reduce thermal expansion coefficient and increase thermal and wear resistance of the host matrix. By uniformly distributing these nano-reinforcement particles in epoxy resin the reinforcement material can impart superior mechanical properties to every region of the host matrix in a uniform manner [5,6]. The nanoparticles present high tendency to agglomerate under the influence of Vander Vals forces. Agglomeration of these particle in the host matrix can result to reduced interfacial interaction between resin and reinforcement. Non uniform dispersion of the reinforcement causes thermal stresses in the matrix around agglomerated nano particles due to unevenly distributed coefficient of thermal expansion within the composite matrix. Many methods can be used to infuse nanoparticles inside polymers including ultra-sonication bath, probe sonicator, high shear mixing by ball milling, high speed stirrer etc [7]. In this study the nano-CeO2 reinforced epoxy slabs were fabricated and fiber reinforcements were not added in order to clearly analyze the effect of lab synthesized nano-CeO2 particles (crystsllite size 10-20nm) on mechanical properties of epoxy resin matrix. Sample slabs with wt% of nano-CeO varying from 0 to 3wt% were fabricated and mechanical properties namely flexural strength, compressive strength, microhardness and density were tested. 2. EXPERIMENTAL

2.1 Materials used The matrix used in this work is a commercially available analar grade of diglycidyl ether of bis-phenol A ((4-(2,3 epoxypropoxy) phenyl) propane), abbreviated as DGBEA, was obtained from Huntsman Advanced Materials under the commercial name Araldite AY 105. Along with
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epoxy resin an aliphatic polyamine hardner commercially known as Aradur HY 951 was also obtained from the same company. Nano-CeO2 powder synthesized by Solution Combustion method was used as reinforcement material. 2.2 Synthesis of nano-CeO2 particles. Nano-CeO2 particles were synthesized by dissolving cerium nitrate (Ce(NO3)3.6H2O) and citric acid (C6H8O7) in minimum quantity of double distilled water in a pyrex dish. The solution is then placed in a pre-heated Muffle furnace maintained at 40010C. Solution boils and dehydration takes place followed by decomposition and evolution of gases. Then spontaneous combustion occurs with enormous swelling and porous product, CeO2 is obtained. Solution takes 5mins in Muffle furnace till the bright sparks throughout the pyrex dish are seen which indicate the occurrence of spontaneous combustion and formation of nano-Ceria. The theoretical equation of the combustion of redox mixture for the formation of CeO2 nanopowder using citric acid fuel can be represented by: 2Ce(NO3)3 (aq) + C6H8O7 (aq) 2 CeO2 + 6CO2 (g) + 4H2O (g) + 9 N2 (g)........................ (1) 2.3 Characterization of nano-CeO2 by PXRD, FTIR and SEM. The powder XRD patterns of CeO2 samples were obtained using a Philips PW/1050/70/76 Xray diffractometer which was operated at 30 kv and 20 mA using CuKa radiation with nickel filter at a scan rate of 20/min. The surface morphology of the powders was examined using JEOL (JSM-840A) scanning electron microscopy (SEM). FTIR spectra were recorded using a Nicollet IMPACT 400 D FTIR spectrometer in the range 4000-400 cm-1 using KBr pellet. 2.4 Fabrication of polymer nano composite slabs. Nano-Ceria filler was added to epoxy resin and stirred manually in a beaker using a glass rod followed by Sonication. Sonication of the mixture was done using a Probe-type Ultrasonic processor at 20 Khz frequency for a duration of 15 minutes. On/Off pulse was set to 10s to avoid over heating of the resin. Sonicated mixture was allowed to cool down following which polyamine hardner was added to cure the resin. This mixture was poured into rectangular moulds of dimension 10x8x1.5 cm3 and allowed to cure at room temperature for 48 hours. Resin to hardner weight ratio was kept 10:1 as specified. 2.5 Flexural test. Three Point Bending test was used to determine the flexural strength of the polymer composites containing different wt% of nano-ceria. Specimens with dimensions 80x10x4 mm3 were prepared for Three point bending test according to ASTM D-790-2010 standard. 2.6 Compression test. Compressive strength of the polymer composite samples was determined using Universal Testing Machine (UTM). Compression test was carried our according to ASTM D-695-2002 standard and specimens of dimensions 10x10x4 mm3 were prepared for this test.

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2.7 Microhardness test. Microhardness of polymer composites was determined using Vickers Microhardness tester with a diamond pyramid indenter. Load of 300g was applied for a duration of 20s and diagnols d 20 of the indentation were measured with an Optical Microscope with a Micrometer attachment in Microscope the eye piece.

Formula used: ......(2) ..... Where F is Load applied in N, d is the average diagonal of indentation and HV represents Vickers Hardness Number. 2.8 Density test. Density was determined using displacement method with distilled water at 23C. Test was performed according to ASTM D D-792-1998 standard. 3. RESULTS AND DISCUSSIONS 3.1 Characterization 3.1.1 Powder X-Ray Diffraction of nano Ray nano-CeO2 powder.

Figure 1 PXRD pattern for as-formed nano-ceria

Fig. 1 gives the PXRD patterns of the as as-prepared CeO2 sample, diffraction peaks, d corresponding to cubic fluorite structure (JCPDS: 43 1002) are clearly observed. By applying the 43-1002) Scherrers formula [8] to the full width at half maximum of the diffraction pe peaks, the mean crystallite sizes was calculated as 10 10-20 nm.

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3.1.2

Scanning Electron Microscopy of nano-CeO2 powder.

Figure 2 SEM image of nano-ceria

Fig 2 shows the SEM photographs of as prepared CeO2. The nano particles are agglomerated, and fluffy with porous morphology. The agglomeration of nanoparticles is usually explained as a common way to minimize their surface free energy. The voids and pores present in the sample are due to large amount of gases produced during the combustion synthesis. 3.1.3 FTIR analysis of nano-CeO2.

Figure 3 FTIR spectra of nano-ceria

Fig. 3 shows the FTIR spectra of as formed CeO2 nanopowder. The peak appearing at 400 cm , can be ascribed to the Ce-O vibration of the CeO2 nanopowder. The weak absorption peak at 3421 cm-1 corresponds to the -OH group of water adsorbed on the surface of the CeO2 powder.
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3.2 Mechanical properties 3.2.1 Flexural test Flexural tests of the samples reveal improvement in the bending strength of epoxy matrix due to addition of nano-ceria. Maximum increase of 42% in bending strength was shown by the sample containing 0.25 wt% of nano-ceria. Flexural strength of pure epoxy sample was 64.4 Mpa and increased with increase in wt% of nano-ceria till a maximum value of 91.5 Mpa was obtained for 0.25 wt% sample. Increase in wt% nano-ceria beyond 0.25% resulted in decrease in flexural strength and sample with 3 wt% ehibited lowest flexural strength of 57.6 Mpa. Relation of flexural strength to wt% of nano-ceria is shown in Fig4. Increase in flexural strength due to addition of nano-CeO2 till 0.25wt% can be attributed to resistance to crack initiation and crack growth offered by nano-ceria particles bonded strongly in the spaces between polymer chains. Due to extremely high surface area of nano-particles they adhere strongly to the epoxy matrix and fill in extremely small gaps between polymer chains owing to their nano size. The high strength of ceramic reinforcement is transmitted uniformly throughout the matrix when reinforcement is dispersed uniformly at nano scale level.[4] Presence of air bubbles in matrix can form crack initiation sites under bending stresses, formation of these air bubbles can be reduced by addition of reinforcement since reinforcement material can fill in void spaces.

Figure 4 Flexural strength vs Wt% of nano-ceria

The decrease in flexural strength when wt% is increased beyond 0.25% is due to absence of enough resin in some regions to bond with surplus reinforcement material which results in weaker regions in the matrix. Higher content of nanoparticles can hinder uniform curing of the resin and result in non uniform cross linking of the epoxy network. At higher wt% there is a possibility of agglomeration of nano-reinforcement in different regions of the matrix resulting in non uniform dispersion of reinforcement material [7,9]. Thermal stresses can be induced in regions around agglomerated nano-particles at the time of curing since there is a mismatch of thermal expansion coefficient of nano-ceria reinforcement and epoxy matrix.

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3.2.2 Compression test Compression tests reveal increase in compressive strength of epoxy matrix with increase in wt% of nano-ceria from 0 to 0.5 %. Compressive strength of pure-epoxy sample was 368 Mpa which increased to a maximum value of 525 Mpa for 0.5wt% sample. Increase in wt% beyond 0.5% caused decrease in compressive strength and 3 wt% showed compressive strength of 406 Mpa. This trend is shown in Fig 5.

Figure 5 Compressive strength vs Wt% of nano-ceria

Increase in compressive strength with increase in wt% of nano-ceria till 0.5wt% is a result of high strength of CeO2 nanoparticles which is transmitted uniformly to the host matrix due to very high interfacial area between resin matrix and nanoparticles assists in transfer of physical stress. Nanoparticles are uniformly dispersed in the matrix and occupy spaces between polymer chains decreasing mobility of the chains and increasing resistance of matrix to deformation and crack growth. Possibility of air bubbles reduces by addition of nano-ceria filler thus preventing crack initiation due to void spaces in the matrix. Decrease in compressive strength on increasing wt% beyond 0.5% was observed. This decrease can be due to agglomeration of nanoparticles and lack of resin material to accommodate high content of nano-ceria. Region around agglomerated nanopaticles develops thermal stresses during curing cycle due to mismatch of thermal expansion coefficient between resin host matrix and nano-ceria aggregate [11]. Cracks can initiate in such regions with stress concentrations present due to poorly dispersed reinforcement or lack of resin material to bond high content of reinforcement. 3.2.3 Vickers Microhardness test Microhardness of pure epoxy slab was 268.66 HV/0.3Kg and increased to a maximum value of 347.62 HV/0.3Kg for 1 wt% slab. Composite slabs with low filler content (0.1 and 0.25 wt%) do not exhibit considerable change in microhardness. Increase in nano-ceria content above 0.25 wt% showed increment in microhardness till maximum value was achieved at filler loading of 1 wt%. When filler loading was increased beyond 1 wt% a decrease in microhardness is observed and value drops down to 319.85 HV/0.3Kg for 1.5 wt% slab. Decreased mobility of polymer chains due to hard ceramic nano filler can be the reason for high microhardness exhibited by slabs at high filler content [10,12]. Higher surface area of nano-ceria reinforces larger volume of resin matrix and stress can be transferred to nanoparticles more efficiently owing to high
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 3, Number 2, July-December (2012), IAEME

interfacial area between resin and nano-Ceria. Trend of Microhardness with wt% of nano-ceria is given in Fig 6.

Figure 6 Vickers Microhardness vs Wt% of nano-ceria

More than 1 wt% nano-ceria content resulted in drop in microhardness value but still slabs with 1.5 and 3 wt% possessed significantly higher microhardness than pure epoxy slab. High hardness of ceramic filler contributes to the increase in microhardness but high content of nano-ceria results in its non uniform distribution and formation of aggregates. This can lead to non uniform reinforcement of host matrix and hindrance in curing of matrix in regions where nano-ceria aggregates are present. 3.2.4 Density test Minute increase in density was observed with increment in wt% of nano-CeO2 due to high density of Ceria particles. Density of pure epoxy casting was 1.19g/cm3 and sample with 3wt% of nano-CeO2 exhibited a density of 1.22g/cm3. Table 1 shows the trend of density of polymer castings with variation in wt% of nano-ceria. Table 1 Density with varying Wt% of nano-ceria Wt% of nano-CeO2 Density (g/cm3) 0% 1.19 0.10% 1.19 0.25% 1.20 0.50% 1.20 1.0% 1.20 1.50% 1.21 3.0% 1.22

4. CONCLUSION Nano-ceria reinforcement synthesized by combustion method significantly improved the mechanical properties of epoxy matrix. 42.6% increase in compressive strength, 42% increase in flexural strength and 29% increase in microhardness suggest that this nano-ceria reinforced epoxy can be used as host matrix for fabricating better FRPs. Enhancement of mechanical properties uniformly throughout the polymer composite slabs at filler content lower than 1 wt%
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International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN 0976 6480(Print), ISSN 0976 6499(Online) Volume 3, Number 2, July-December (2012), IAEME

suggests that sonication process successfully dispersed the nano-ceria particles in the resin matrix. Negligible increase in density was observed when filler content increased from 0 to 3 wt%. Since low nano-ceria content is needed to achieve this improvement in properties there is scope of accommodating additional reinforcement materials, e.g. carbon fiber, glass fiber, carbon nanotubes, into the epoxy host matrix.

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