72- 79 Al-Khwarizmi Engineering Journal Al-Khwarizmi Engineering Journal,Vol. 12, No. 3, P.P. 72- 79 (2016) Effect of Nano Powder on Mechanical and Physical Properties of Glass Fiber Reinforced Epoxy Composite Aseel Basim Abdul-Hussein* Fadhel Abbas Hashim** Tamara Raad Kadhim*** *,**,***Department of Materials Engineering/ University of Technology *Email: dr.material@yahoo.com (Received 16 April 2015; accepted 12 January 2016) Abstract Fiber reinforced polymer composite is an important material for structural application. The diversified application of FRP composite has taken center of attraction for interdisciplinary research. However, improvements on mechanical properties of this class of materials are still under research for different applications. In this paper we have modified the epoxy matrix by Al2O3, SiO2 and TiO2 nano particles in glass fiber/epoxy composite to improve the mechanical and physical properties. The composites are fabricated by hand lay-up method. It is observed that mechanical properties like flexural strength, hardness are more in case of SiO2 modified epoxy composite compare to other nano modifiers, were physical properties like density, water absorption are more in case of TiO2 modified epoxy composite. This may be because of smaller particle size of silica compare to others. Key word: Density, Water absorption, Hardness, Flexural Strength, Glass fibers, Composites. 1. Introduction Development of new composite materials or modification of existing composite material is the real challenge for most of the materials engineers. Epoxy base matrix composite has tremendous potential to substitute the traditional metallic materials. Polymer matrix modification is one of the approaches to develop new class of polymer structural materials. This modification can be done by addition of different ceramic powders of different sizes to achieve the required mechanical properties. McGrath et al. (2008) studied the effect of alumina powder in epoxy on mechanical properties. They found that there is a little effect on change in particle size, shape and size distribution on final properties. However the resin crosslink density and filler loading were the most critical variable, which may change all properties [1]. L.Merad.et.al, have study the mechanical properties of epoxy resin reinforced with TiO2 nanoparticles. These nanoparticle are 21nm in diameter and volume fraction (o.5, 1, 5 and 20%).The results shown that the mechanical properties like hardness and tensile strength higher than net epoxy and increased with increase addition of TiO2 nanoparticles [2]. Ikram .et. al, have studied mechanical properties of micro and nano TiO2/ epoxy composites, with epoxy volume fraction (1,2,3,4,5,6,7,10,15,20) of microparticles TiO2 (50 µ m) and nanoparticle TiO2 (50nm) the flexural strength, Young modulus and fracture toughness of nanocomposites were increased at low volume fraction (less than 7 vol%). At higher volume fraction both flexural strength and fracture toughness decrease while Young modulus still higher than that of epoxy. The flexural strength and fracture toughness of epoxy-microcomposites decreases with increasing the volume fraction of TiO2 microparticles specially at high volume fraction while Young modulus increases with increasing the volume fraction [3]. Dr.Falak O.Abas,Raghad O.Abas and Sarmad I. Aseel Basim Abdul-Hussein Al-Khwarizmi Engineering Journal, Vol. 12, No. 3, P.P. 72- 79(2016) 73 Ibrahim have studied the properties and behavior of particles on (glass, carbon, and Kevlar fiber) reinforced polyester composites. The effect of alumina (Al2O3) and silicon carbide (SiC) particles ceramic polyester composites are investigated at different additive ratios as (0.2, 0.4, 0.6, 0.8, 1.0%) volume fraction. Comparative analysis show that the bending distortion, hardness, and impact resistance are affected by the type and content of filler particles, where both impact and Hardness is increased with increasing volume fraction specially in case of (0.5%) volume fraction for both filler particles and decreased for bending distortion specially in case of glass fiber/ polyester at (0.5%) volume fraction for both filler particles [4]. Ramish k.et.al, have study the effect of epoxy modifiers (Al2O3, SiO2, TiO2) on mechanical performance of epoxy/glass fiber hybrid composite. The results shown that mechanical properties like flexural strength, and flexural modulus are more in case of SiO2 modified epoxy composite compare to other micro modifier. This is may be because of smaller particle size of silica compare to other. Alumina modified epoxy composite increase the hardness and impact energy compare to other modifiers [5]. 2. Experimental Procedure 2.1. Materials In our study, commercially available Al2O3 (45 nm), SiO2 (38 nm), TiO2 (47 nm) particles are used to modify the epoxy matrix. Nano fillers of Al2O3, SiO2 and TiO2 were purchased from nano Shell Company. Commercially available woven roving fabric E-glass fiber from the Tenax Company, England. The epoxy which is used was Euxit (50) base as the matrix from the (Al-Rakaez Building Materials) made in Egypt in the form of transparent viscous liquid at room temperature which is a thermally hardened polymers (Thermosets) with a density of (1.05 gm / cm3) 2.2 Fabrication of Hybrid FRP Composite There are three types of hybrid FRP composite with different fillers are fabricated using hand lay- up method. The volume percentage of epoxy, fiber, filler and hardener are fixed and designations of the composites are reported in Table -1. Where A, S and T indicate Al2O3, SiO2 and TiO2 modified FRP composite. Adding the powder intermittently into the mixture and stirring it for a period of (10- 15) minutes to obtain homogeneity. A rise in the temperature of the mixture will result as an indication to the beginning of the interaction process. It is very important that the mixture must have a good viscosity for the purpose of protecting the particles from precipitation which may result in the heterogeneity of the mixture that leads to the agglomeration after hardening. Pouring the mixture into the mould, then putting the glass fiber mat into the mould and continuing of mixture pouring until it covers the entire mat. Pressing the mixture with an appropriate load. For the purpose of completing the process of hardening, finally is leaving the sample in the mould for a period of (24) hour at room temperature. Samples are then extracted from the mould and then heat treated in an oven at (60Ċ) for a period of (60) minutes [6]. This process is very important for the purpose of obtaining the best cross linking between polymeric chains, and to remove the stresses generated from the preparation process and complete the full hardening of the samples. Fig. 1 shows the shape of the prepared mould. Table 1, Designation and composition of composites Fig. 1. The shape of the prepared mould. 3. Results and Discussion 3.1. XRD of Powder The X-ray powder diffraction patterns are shown in Fig. (2).For three materials, all major Designation of composites Composition A Epoxy + 3% G.F + 2, 4 and 6 % Al2O3 S Epoxy + 3 % G.F +2, 4 and 6% SiO2 T Epoxy+ 3% G.F+2, 4 and 6%TiO2 Aseel Basim Abdul-Hussein Al-Khwarizmi Engineering Journal, Vol. 12, No. 3, P.P. 72- 79(2016) 74 peaks were assigned to the crystalline structure. Al2O3 was hexagonal structure, SiO2 was cubic structure, and TiO2 was tetragonal structure. Fig. 2. The XED of nano powder. 3.2. Hardness (shore D) This test is performed by using hardness (Shore D) and according to (ASTM DI-2240) standard at room temperature. Samples have been cut into a diameter of (40mm) and a thickness of (5mm) [7]. Table (2) shows the values of hardness for the prepared (Pure Epoxy, Epoxy +3% glass fiber and nano) composites. Table 2, Hardness of Prepared Composites. Types of composites hardness shore D Ep 77 Ep +3% G.F 78 Ep + 3%G.F+2% SiO2 81.5 Ep + 3%G.F+4% SiO2 83.7 Ep + 3%G.F+6% SiO2 84.8 Ep + 3%G.F+2% Al2O3 81.2 Ep + 3%G.F+4% Al2O3 83.2 Ep + 3%G.F+6% Al2O3 84.3 Ep + 3%G.F+2% TiO2 80.5 Ep + 3%G.F+4% TiO2 82.7 Ep + 3%G.F+6% TiO2 83.9 From fig. (3) it is clear that there is a pronounced effect of the addition of 3% glass fiber volume fraction percents on the hardness of the material. This may be due to the fact that the hardness is generally considered to be a property of the surface therefore this behavior of hardness is expected. And can be seen from figure a pronounced effect of the addition of 3% glass fiber with 2%, 4%and 6% volume fraction from (nano powder) percents on the hardness of the material. It can be seen that the hardness increases with increasing volume fraction. Adding the filler particles will raise the materials hardness due to increasing in material resistance against the plastic deformation. Result had revealed that the hardness of pure epoxy alone was (77 shore D) compared to maximum value (84) at volume fraction of (6% SiO2) with particle size is (38nm). The reason of the increase in hardness is that SiO2 contains an elements harder than the pure epoxy that lead to an increase in hardness. These results become match with our work because the SiO2 have larger surface area and smaller particle size than (Al2O3and TiO2). Fig. 3.hardness of papered composite. Al2O3 SiO2 TiO2 Aseel Basim Abdul-Hussein Al-Khwarizmi Engineering Journal, Vol. 12, No. 3, P.P. 72- 79(2016) 75 3.3. Flexural Strength This test is performed according to (ASTM D790) at room temperature. Samples have been cut into the dimensions (80*3.2*2.5) mm [8]. The flexural strength are calculated according to the equations [9] … (1) Where F.S flexural strength (MPa). p force at fracture (N). L length of the sample (mm). b thickness (mm). d width (mm). Table (3) shows the values of flexural strength for all prepared composites. Table 3, Flexural strength of prepared composites. Fig.4.shows flexural strength of all prepared composites. It can be noted from this figure that the addition of 3% glass fiber with 2%, 4% and 6% volume fraction from nano powder has a significant effect on the flexural strength of the composite material. And, the flexural strength increases with increasing volume fraction and decreasing of the particle size. The flexural strength of pure epoxy reference was (149 MPa), and then an increasing was observed with increasing in volume fraction till it reached to its maximum value of (375 MPa) by the addition of (3% glass fiber) and volume fraction of (6% SiO2) with particle size is (38nm) which is (151%) higher than epoxy alone. These results match with the present because the SiO2 has particle size smaller than (Al2O3 and TiO2), this can be attributed to ductility of SiO2 which is reducing the brittleness of composite. Fig. 4. Flextural strength of papered composite. 3.4. True Density This test is performed according to (ASTM D792) standard at the room temperature [9].The samples were cut into a diameter of 40 mm and a thickness of 5 mm the measured density (ρt) is calculated from the method of immersion in water using the following relationship [10]. ρt= (Wd /Ws-Wn)*D … (2) Where: Ρt Measured density or bulk density (gm/cm3). D Density of distilled water (1 gm/cm3). Wd dry weight of sample (gm). Wn weight of the sample, a commentator and submerged with water (gm). Ws weight of the sample is saturated with water (gm). Table (4) shows the values of density for the prepared composites. Table 4, Density of prepared composites. Types of composites True density Ep 1.05 Ep +3% G.F 1.080 Ep + 3%G.F+2% SiO2 1.122 Ep + 3%G.F+4% SiO2 1.155 Ep + 3% G.F+6% SiO2 1.185 Ep + 3%G.F+2% Al2O3 1.130 Ep + 3%G.F+4% Al2O3 1.165 Ep + 3%G.F+6% Al2O3 1.197 Ep + 3%G.F+2% TiO2 1.140 Ep + 3%G.F+4% TiO2 1.178 Ep + 3%G.F+6% TiO2 1.215 Fig.5 show the true density for prepared composites. In Fig. 5 can be seen the higher true density has been found to be for the specimen (epoxy +3%G.F+6%TiO2) due the TiO2 powder have density higher than individual density when Types of composites Flexural strength Ep 149 Ep +3% G.F 158 Ep + 3%G.F+2% SiO2 325 Ep + 3%G.F+4% SiO2 349 Ep + 3% G.F+6% SiO2 375 Ep + 3%G.F+2% Al2O3 310 Ep + 3%G.F+4% Al2O3 342 Ep + 3%G.F+6% Al2O3 362 Ep + 3%G.F+2% TiO2 290 Ep + 3%G.F+4% TiO2 337 Ep + 3%G.F+6% TiO2 355 120 190 260 330 400 F le x tu ra l S tr e n g h t (M P a ) Type of Composite F le x t u r al St r en gh t Aseel Basim Abdul-Hussein Al-Khwarizmi Engineering Journal, Vol. 12, No. 3, P.P. 72- 79(2016) 76 compared with composite (Al2O3 and SiO2) nano Powder. Where the density of TiO2 (4.25 gm/cm3), Al2O3 (4.05 gm/cm3) and SiO2 (2.7 gm/cm3) .When comparing the value of true density nano composite with measured density of (pure Epoxy) can be seen higher than because the additions of reinforcement (TiO2, Al2O3, SiO2) nano powder that have higher density than matrix (pure epoxy).where density of pure epoxy (1.05 gm/cm3). Fig. 5. True density of papered composite. 3.5. Water absorption This test is performed according to (ASTM D 570) standard at room temperature [11]. Samples have been cut into a diameter of (40mm) and a thickness of (5mm). The mechanism of water absorption is explained to be the direct uptake and flow of water by capillary and transport along the reinforcement-matrix interface [12]. Water absorption percentage is calculated using (Archimedes base) according the following formula [13]. … (3) Where M (%) water absorption percentage. mo mass of specimen before immersion (g). mt: mass of specimen after immersion for seven days (g). Table (5) shows the values of water absorption for the prepared composites. Table 5, water absorption of prepared composites. Types of composites water absorption Ep 0.120 Ep +3% G.F 0.195 Ep + 3%G.F+2% SiO2 0.215 Ep + 3%G.F+4% SiO2 0.313 Ep + 3% G.F+6% SiO2 0.364 Ep + 3%G.F+2% Al2O3 0.240 Ep + 3%G.F+4% Al2O3 0.325 Ep + 3%G.F+6% Al2O3 0.378 Ep + 3%G.F+2% TiO2 0.275 Ep + 3%G.F+4% TiO2 0.340 Ep + 3%G.F+6% TiO2 0.385 In Fig. 6 shows the water absorption of all prepared composites can be seen the specimen (epoxy +3%G.F) have higher water absorption than specimen (pure epoxy), the increasing water absorption percentage with increasing volume fraction of fiber depends on the rule of mixture theory where fiber have a higher water absorption percentage than specimen pure epoxy [14]. The water absorption attacked the fiber-matrix interface, causing de-bonding of the fiber and the matrix. The failures of the composite materials were due to voids [15]. And nano composites given higher water absorption percentage than specimen pure epoxy and specimen (epoxy +3%glass fiber) composites. the higher water absorption percentage of nano composite has been found to specimen (epoxy +3%G.F+6%TiO2) while the specimen (epoxy + 3%G.F+6% SiO2) have lower than specimen of (Al2O3 and TiO2) at the volume fraction (3%) of glass fiber and (6% ) volume fraction of filler particles ( nano powder ), and the specimens (epoxy +3%G.F+2% TiO2), (epoxy +3%G.F+4% TiO2)have higher water absorption percentage while the specimen (epoxy + 3%G.F+2% SiO2), (epoxy + 3%G.F+4% SiO2) have lower than specimen of (Al2O3 and TiO2) at the volume fraction (3% ) of glass fiber and (2%,4%) volume fraction of filler particles (nano powder ).In this work the specimens of composite material filled with larger particles show a higher water absorption percentage when compared with the specimens of composite material filled with small particles because the saturation level of fillers matrix composition influenced by agglomeration that will affect the water absorption percentage of the composite material. The mean particle size of the (SiO2) is (38nm) while mean particle size of the (Al2O3) is (45 nm) and mean particle size of the (TiO2) is (48nm). Aseel Basim Abdul-Hussein Al-Khwarizmi Engineering Journal, Vol. 12, No. 3, P.P. 72- 79(2016) 77 Fig. 6.water absorption of papered composite. 3. Conclusion Non –reinforced pure Epoxy has lower physical and mechanical properties than (epoxy+3%glass fiber) composites and nano composites. The values of measured density are lower than nano composite with 3% glass fiber and 6% nano powder have the higher density when compared with other composites. Nano composite with (epoxy +3% glass fiber +6%TiO2) has the maximum density of (1.215) (gm/cm3) when compared with other composites. The values of water absorption of specimen (pure epoxy) lower than specimen (epoxy +3% glass fibers). Nano composite with 3% glass fiber and 6% nano powder have the higher water absorption when compared with specimen (pure epoxy) and specimen (epoxy +3% glass fibers) composites. Nano composite with (epoxy +3% glass fibers +6%TiO2) has the maximum water absorption of (0.385%) Result shows that the best hardness value was (84.8 shore D), Flexural strength (375MPa) at volume fraction of (3%glass fiber) with (6% SiO2). 4. References [1] McGrath Laura M. , Richard S. Parnas , Saskia H. King , John L. Schroeder , Daniel A. Fischer , Joseph L. Lenhart, 2008. Investigation of the thermal, mechanical, and fracture properties of alumina epoxy composites, Polymer 49, 999-1014. [2] L.Merad, B. Benyoucef,M.J.M abadie, J.P charles,"Characterization and Mechanical Properties of Epoxy Resin Reinforced With TiO2 Nanoparticles", Journal and Engineering and Applied Sciences,(2011), No. 3, PP.205-209. [3] Ikram A. Al-Ajaj, Muhannad M. Abd and Harith I. Jaffer,"Mechanical Properties of Micro and Nano TiO2/Epoxy Composites", international Journal of Mining & Mechanical Engineering, (2013), No. 2, Vol.1, PP.2320-4060. [4] Dr.Falak O.Abas,Raghad O.Abas and Sarmad I. I brahim , " A Comparison study of different Ceramic Filler on Mechanical and Thermal Properties of Glass, Carbon, Kevlar / Polyester composites", Eng. & Tech. Journal, (2010), No. 12, Vol. 28, PP. 2469. [5] Ramesh K. Nayak , Alina Dasha and .C.Ray,"Effect of epoxy modifiers (Al2O3, SiO2, TiO2) on mechanical performance of epoxy/glass fiber hybrid composites", ELSEVIER Journal(2014),Vol.6,PP.13591364,6 (doi:10.1016/j.mspro.2014.07.115). [6] Felix K., Sylvester A. and Edmund A.,"Storage and handling techniques of maize and groundnut", SENRA Academic Publishers, Burnaby, British Columbia, No.3, Vol.6, PP.2122, (2012). [7] Annual Book of ASTM Standard "Standard Test Method for Plastics Properties- Durometer Hardness D 2240", Vol. 09.01, (1988). [8] Annual Book of ASTM Standard, "Standard Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics ", D 790- 86, Vol. 10.01, (1986). [9] M. A. Meyers & K. K. Chawla," Mechanical behavior of materials", Prentice Hall, Inc., USA, (1999), PP. 644. [10] Annual Book of ASTM Standard, "Density and Specific Gravity (Relative Density) of Plastics by Displacement1". [11] Annual Book of ASTM Standard, "Standard Test Method for Water Absorption of Plastics D 570- 98", Vol. 08.01, (2005). [12] Mohammed Ismail, Suresha Bheemappa and N. Rajendra, "Investigations on Mechanical and Erosive Wear Behaviour of Cenosphere Filled Carbon-Epoxy Composites", International Conference on Mechanical, Automotive and Materials Engineering, Dubai,(2012) ,pp.209. [13] M.H.A Ghani & S. Ahmad, "The Comparison of Water Absorption Analysis between Counter rotating and Corotating Twin-Screw Extruders with Different Antioxidants Content in Wood Plastic Composites",(2011), Vol.20, PP. 2. 0 0.5 W a te r A b s o rp ti o n (% ) Type of Composite Absorption Aseel Basim Abdul-Hussein Al-Khwarizmi Engineering Journal, Vol. 12, No. 3, P.P. 72- 79(2016) 78 [14] D. Chandramohan, and J. Bharanichandar " Narural Fibre Reinforced Polymer Composites for Automobile Accessories ", American Journal of Environmental Science , (2013), No.6 ,Vol. 9, PP.494-504, (doi:10.3844/ajessp.2013.494.504). 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