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Materials and Design 56 (2014) 10681077

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Materials and Design


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Optimization of mechanical properties of epoxy-based hybrid nanocomposite: Effect of using nano silica and high-impact polystyrene by mixture design approach
Y. Rostamiyan a,, A. Hamed Mashhadzadeh b, A. SalmanKhani c
a b c

Department of Mechanical Engineering, Sari Branch, Islamic Azad University, Sari, Iran Department of Mechanical Engineering, Semnan Branch, Islamic Azad University, Semnan, Iran Faculty of Mechanical Engineering, K.N.Toosi University of Technology, Tehran, Iran

a r t i c l e

i n f o

a b s t r a c t
Epoxy resins have tight three-dimensional molecular network structures; because of this reason, these materials are brittle in nature and have pore resistance in front of crack propagation. In the present study, to overcome this issue, the optimized mixture proportions of epoxy-based hybrid nanocomposite with different composition of nano silica as nano reinforcement, high-impact polystyrene as thermoplastic phase and hardener were determined by applying the simplex-centroid mixture design method to achieve the ultimate tensile, exural, compression and impact strength. Results revealed that the best mixture occurs in 2.67 wt.% of HIPS, 4.01 wt.% of nano SiO2 and 28 phr of hardener. Experimental results indicate that new ternary nanocomposite improved ultimate tensile, compression and impact strength up to 59.5%, 45% and 414% compared to those of the neat epoxy resin respectively, although they did not show enhanced exural strength. The tensile and exural elongations at break were improved up to 71% and 83% larger than those of neat epoxy, respectively, but compression strain did not change considerably. Correlation between the morphology of the nanocomposite and its mechanical properties was noted when using the SEM technique. EDX analysis used to indicate homogeneous combination of Silica nano particles in matrix and show solvent evaporated completely under vacuum situation. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 9 September 2013 Accepted 23 November 2013 Available online 1 December 2013

1. Introduction Epoxy resins are considered as one of the most important classes of polymer matrix composite materials, due to their superior mechanical properties, low price, chemical stability and good adhesion. Most of the researches done in the eld of polymer nanotechnology have focused on improvement of the thermal, electrical, optical, and mechanical properties of these materials. Many researchers had improved epoxy resin performance by incorporating thermoplastic llers, rubber agents, diluents, and nanoparticles into the epoxy. Inorganic nanoparticles have the potential to be used as a reinforcing material due to their low cost, ease of fabrication, and environmentally friendly nature [1]. Zhang et al. [2] used silica as reinforcement in epoxy resin and 3040% improvement was obtained in tensile and exural modulus. Zheng et al. [3] showed that addition of 3% silica nanoparticle in epoxy matrix increases tensile strength of 115%, while the impact strength increases by 56%. Ragosta et al. [4] founded that adding 10 wt.% of

Corresponding author. Tel.: +98 151 2133756.


E-mail address: yasser.rostamiyan@iausari.ac.ir (Y. Rostamiyan). 0261-3069/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.matdes.2013.11.060

silica in epoxy matrix improves mechanical properties. Rosso et al. [5] lled epoxy resin with 11 wt.% of silica nanoparticle and improvement in tensile modulus and fracture toughness were observed. However, epoxy has low strength in terms of crack growth and displays brittle fracture behavior because of its tight threedimensional molecular network structure, which resulted in limited usage of this type of polymers under loading conditions [6]. In the last decade, many researches are done in an attempt to increase the toughness of epoxy [7]. Incorporating micro phase dispersed rubber [8] or different types of thermoplastic polymers [9] are well-known, long-established ways of increasing the impact strengths of epoxy thermosetting polymers, although these modications degrade their mechanical properties too, such as their strengths, module, and glass transition temperatures (Tg) [7]. Sultan et al. [10] used rubber in epoxy matrix to improve toughness. They used carboxyl terminated acrylonitrile (CTBN) rubber to toughen diglycidyl ether of bisphenol A (DGEBA) epoxy resin and increasing in the value of fracture energy was observed. Pearson et al. [11] showed that the use of rubber particle in DGEBA epoxy resin as a matrix increases fracture toughness by a particle-bridging/crack deection mechanism. Frounchi et al. [12] added a rubber particle in DGEBA resin as a matrix and 40% increase in

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impact resistance was observed. Although rubber and thermoplastic phases can be used to enhance impact strength, because of their effects on other desired mechanical properties, toughening with engineering thermoplastics such as polysulfone [13], polyether amide [14], ABS [15], or polyethersulfone [16] leads to more usable materials. Generally, although the presence of a rubber or thermoplastic phase in an epoxy resin can signicantly improve its fracture toughness, such a phase also enhances the viscosity of the resin and dramatically decreases its strength, modulus, and stiffness [17,18]. This reason persuaded researchers to use hybrid nanocomposits to improve mechanical properties and impact strength. If used two or more kind of nano or micro particle in matrix, the composite is named hybrid nanocomposite [19]. Rostamiyan et al. [20] lled epoxy resin with nanoclay as a nano reinforcement and HIPS as a thermoplastic phase and synergistic effects were observed on mechanical properties. Their results showed that new ternary nanocomposite possesses tensile, compressive, and impact strengths were improved up to 60%, 64%, and 402%, respectively higher than those of the neat resin. Kinloch et al. [21] added nano-silica and micro-rubber particles to epoxy resin. They showed a signicant increasing in toughness. Their results indicated that the toughness increased slightly when nanosilica particles were added to epoxy. Geisler et al. [22] used a combination of alumina (Al2O3) and rubber particles in epoxy matrix. This composition had fracture toughness values 25% higher than those of epoxy systems having only alumina (Al2O3) or rubber particles. They also showed toughness improvement without signicantly diminishing the other properties such as elastic modulus and glass transition temperature. Mirmohseni et al. [6,15] lled epoxy resin with nano-clay and thermoplastic particles and synergistic effects were observed on tensile and impact strength. To study mechanical properties of hybrid mechanism of epoxy-based nanocomposites the effective quantities factors must be introduced. Conventionally from many previous studies it can be found that, the weight percentage of reinforcement such as toughening agent and nano ller are the most considered parameters affect the mechanical behavior of epoxy-based nanocomposites [6]. Weight percentage of hardener is another important factor in epoxy/thermoplastic/nanoparticle samples preparation. Although determination of appropriate amount of this factor is based on stochiometric ratio, but this expect is not far that specially with the presence of thermoplastic phase as toughening agent and also nano ller in epoxy resin, probability of complete mixture of epoxy monomers and hardener would be dramatically decrease and hence prevent from complete polymerization. Mirmohseni et al. [15] determined the optimum amount of hardener based on the maximum tensile and impact strengths of prepared epoxy samples. Response surface design has been introduced for analysis and optimization of multiple factors, mixture experiments are a special class of response surface experiments in which the product under study is made up of several components [23]. The independent factors of a mixture are proportions of the components and the sum of these proportions must be one. Measured responses depend only on relative proportions and not on the amount of mixture [24]. The main target in mixture studies is developing better or innovative formulations with optimum characteristics able to satisfy determined requirements. The main purpose of this study is to evaluate the effects of SiO2 as nano reinforcement, HIPS as thermoplastic phase and hardener content on mechanical properties of hybrid nanocomposite based epoxy, and achievement to optimal zone where the estimation of the responses (tensile, exural, Compression and impact) can be calculated with the probability of a < 0.05. Mixture design was applied to model the relationship between input variables and determined responses.

2. Experimental details 2.1. Details of materials Epoxy resin utilized in this study was an undiluted clear difunctional bisphenol A, Epon 828 provided by Shell Chemicals Co. with epoxide equivalent weight 185192 g/eqiv. Epon 828 is basically DGEBA (Diglycidyl ether of bisphenol-A). The curing agent was a nominally cycloaliphatic polyamine, Aradur 42 supplied by Huntsman Co. The spherical silica nanopaticles with average particle size 1015 nm and SSA (specic surface area) 180270 m2/g were supplied from TECNAN Ltd. The high impact polystyrene used in this survey was purchased from Tabriz petrochemical Company in Iran. The solvent used was Tetrahydrofuran (THF) with purity (GC) more than 99% provided from Merck Co (Germany).

2.2. Sample preparation In order to prepare homogenous mixture, all of reinforcement adding procedures into resin have been done in proper solvent. To prevent from various solvent effects and also achieving comparably results the authors employed Tetrahydrofuran (THF) as an appropriate solvent for dissolving all of mixture components such as epoxy resin, silica and especially high impact polystyrene. For preparing neat epoxy samples, in order to make an equal situations in compare with other samples, liquid epoxy resin has poured in adequate amount of THF solvent and after 30 min mixing on magnetic stirrer, the mixture has poured into a vacuumed erlen and the solvent evaporated completely under vacuum situation created by a vacuuming pump, as shown in Fig. 1. In this step, stoichiometry ratio of cyclo aliphatic polyamine as hardener, i.e. 23 phr was added and mixed uniformly for 15 min and degassed by a vacuum pump to remove the air bubbles. The mixture was poured into silicon mould and cured for 24 h at room temperature and followed by post-curing from 50 C to 90 C each 2 h with 20 C temperature enhancement interval and at 120 C for 2 h to ensure complete curing. In order to prepare epoxy/HIPS/SiO2 samples, desired amount of the reinforcements dissolved in adequate amount of mentioned solvent and mixed via magnetic stirrer for 30 min. In the current study, the mixture was homogenized by ultrasonicating (Ultrasonic SONOPULS-HD3200, 50% amplitude, 20 kHz, and pulsation; on for 10 s and off for 3 s) for 30 min. The required amount of epoxy resin with same procedure as mentioned before was added to this mixture and mixed mechanically at high speed for 2.5 h and subsequently the mixture sonicated with same previous procedure for 30 min. The previous protocol must be followed respectively as same as neat epoxy and considering this point that stoichiometric ratio of hardener content is varied for each hybrid samples.

Fig. 1. Mixing and solvent evaporation procedure under vacuum situation.

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Y. Rostamiyan et al. / Materials and Design 56 (2014) 10681077 Table 1 Mixtures composition in the hybrid nanocomposite formulated with HIPS, SiO2, and Hardener in a three-component simplex centroid mixture design. Formulation Ingredient proportion X1(HIPS) 1 2 3 4 5 6 7 8 9 10 1.000 0.000 0.000 0.500 0.500 0.000 0.333 0.667 0.167 0.167 X2(SiO2) 0.000 1.000 0.000 0.500 0.000 0.5000 0.333 0.167 0.667 0.167 X3(Hardener) 0.000 0.000 1.000 0.000 0.500 0.500 0.333 0.167 0.167 0.667

2.3. Characterization Tensile tests were arranged as specied in ASTM: D638 at room temperature. This test method covers the determination of the tensile properties of reinforced plastics in the form of standard dumbbell-shaped test specimens. The dimensions of the specimens were chosen in according to the type I of this standard test method. The motion rate of the driven grip when the testing machine was running was 5 mm/min. ve specimens were tested for each sample. Flexural tests were conducted based on 3-point bending according to ASTM: D790. This test method covers the determination of the exural properties of reinforced plastics, including high-modulus composites. The dimensions of the specimens were 127 by 12.7 by 3.2 mm with a support span-to-depth ratio of 16. The compression tests were performed according to ASTM: D695. The specimen sizes were 12.7 by 12.7 by 25.4 mm. All three of these mechanical tests were conducted using an STM-150 universal testing machine from Santam Company (Tehran, Iran) with a load capacity of 150 kN. The impact resistance was assessed with un-notched specimens of size 63.5 12.7 7.2 mm, as indicated in ASTM: D256, using a SIT-50 Izod impact machine from Santam Company. At least 5 replicates were tested for each sample. A scanning electron microscope (SEM1530) and energy-dispersive X-ray (EDX) system from TECNAN (Navarra, Spain) were utilized to observe the dispersion of the fracture surfaces of the cured composites. Each fracture surface was coated with gold prior to the SEM studies to avoid charging of the specimen, and 15 kV of accelerating voltage were applied.

ments, three two-ingredient mixtures and four three-ingredient mixtures as seen in Fig. 2. Total of 10 samples with different compositions were prepared according to simplexcentroid mixture conguration for three-factor system with no replicate (Table 1). 3.1. Statistical analysis and modeling of experimental data In order to choose the best model tting the experimental data the following linear, special cubic and quadratic models were chosen.

Y b1 X 1 b2 X 2 b3 X 3 Y b1 X 1 b2 X 2 b3 X 3 b1 b2 X 1 X 2 b1 b3 X 1 X 3 b2 b3 X 2 X 3

1 2

3. Experimental design In this study, Minitab software version 16.2.4 was used to analyze the effects of mixture components on mechanical properties. A three component, simplex-centroid mixture design was chosen in order to design the experiments. X1, X2 and X3 were the components of the mixture and the experiments were designed in random order. All components had the same range between 0 and 1 and there were not any constraints on the design space. Component proportions were expressed as fractions of the mixture with a sum of one (X1 + X2 + X3 = 1). Table 1 shows the experimental design and levels for these three components as 10 combinations. These 10 design points consist of three single-ingredient treat-

Y b1 X 1 b2 X 2 b3 X 3 b1 b2 X 1 X 2 b1 b3 X 1 X 3 b2 b3 X 2 X 3 b1 b2 b3 X 1 X 2 X 3 3

Both dependent and independent variables were tted to these models and residual plots were generated to check the goodness of the model t. The best model should have high predicted Rsquared, low standard deviation and low predicted sum of squares. Following these guides, the quadratic model was found the best tted model to represent the tted response values. The statistical signicance of the model was determined by analysis of variance (ANOVA) at 5%. The quadratic model for three components takes the form:

g b1 x1 b2 x2 b3 x3 b12 x1 x2 b13 x1 x3 b23 x2 x3 b123 x1 x2 x3


4
where g is the predictive dependent variable (Tensile, Flexural, Compression, Impact), xis are the proportions of mixture components and bis are the equation coefcients which must be determined according to cornell 2002 [25]. Coded and actual levels of the variables used to design the ternary nanocomposite for this study are shown in Table 2. This table indicates the weight percentage of HIPS and SiO2 and although the

Table 2 Actual and coded levels of the design parameters. A. HIPS content (wt.%) 2 3.6 5.3 7 8.6 12 B. SiO2 content (wt.%) 1 2.44 3.97 5.5 6.94 10 C. Hardener content (phr) 21 22.6 24.3 26 27.6 31 Level code 0.000 0.167 0.333 0.500 0.667 1.000

Fig. 2. An overview of the simplex-shaped mixture region for a three-component mixture.

Y. Rostamiyan et al. / Materials and Design 56 (2014) 10681077 Table 3 Experimental design and corresponding responses. Std. Experimental factors (coded value) HIPS content 2 1 3 9 5 6 7 10 4 8 0.000 1.000 0.000 0.167 0.500 0.000 0.333 0.167 0.500 0.667 SiO2 content 1.000 0.000 0.000 0.667 0.000 0.500 0.333 0.167 0.500 0.167 Hardener content 0.000 0.000 1.000 0.167 0.500 0.500 0.333 0.667 0.000 0.167 Responses of mechanical tests Tensile strength 45.6 4 24.0 2 62.1 4 55.2 6 62.3 2 65.4 4 59.6 2 65.2 5 48.8 4 55.2 5 Flexural strength (MPa) 1.09 0.42 0.93 0.23 3.56 0.65 4.25 0.74 3.31 0.36 5.32 0.54 4.62 0.34 5.05 0.63 3.20 0.18 2.27 0.25 Compression strength (MPa) 104.8 08 052.8 03 192.1 11 174.1 14 170.2 15 213.1 17 192.2 16 219.2 11 111.8 14 104.7 10

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Impact Strength (kJ/m2) 28.6 4 13.8 3 42.2 4 43.6 2 33.2 3 49.1 5 42.5 1 47.5 2 38.4 4 36.8 3

hardener content as variables according to levels designed by model.

4.1. Analysis of variance for all responses Table 4 indicates analysis of variance for all responses. According to ANOVAs table, tensile response was well tted to the quadratic model with probability of P = 99%. Two-component interactions: X1X2, X1X3 and X2X3 were signicant with probability of P = 98%, P > 99% and P = 94% respectively and the X1X3 interaction had the highest effect on tensile with P > 99%. Analysis of variance for exural shows that quadratic model is a suitable model for exural with probability of P > 99%. As seen two-component interactions X1X2 and X2X3 inuenced the response with a probability of P = 99% and P > 99% respectively and so X2X3 had the highest effect on exural response, whereas the X1X3 had no effect on exural due to its probability of P = 90%. ANOVAs table indicates that Two-component interaction X1X2 was insignicant on compression with probability of 91% (P P 95%) whereas X1X3 and X2X3 were signicant interactions with probability of 97% and 99% respectively, so X2X3 had the highest effect on compression property. Quadratic model was a good tted model for

4. Result and discussion In this study, the effects of incorporating nano silica as nano reinforcement and HIPS as thermoplastic phase into a DGEBA type epoxy resin on its mechanical properties were evaluated. The results obtained for ultimate tensile strength (UTS), ultimate bending strength (UBS), ultimate compression strength (UCS) and impact strength are shown in Table 3. ANOVA results determined based on condence level at 95% (a = 0.05) and signicance of each term was evaluated according to its probability value (P-value). If the terms have signicant effect on response, probability will be more than 95% (a 6 0.05) and the null hypothesis (H0) will be rejected (Table 4) and if do not have signicant effect, probability will be less than 95% (a P 0.05) and the terms should be eliminated from nal analysis and equations.
Table 4 Analysis of variance for all the responses (component proportions). Source Ultimate tensile strength Regression Linear Quadratic X1X2 X1X3 X2X3 Residual error Total Regression Linear Quadratic X1X2 X1X3 X2X3 Residual Error Total Regression Linear Quadratic X1X2 X1X3 X2X3 Residual Error Total Regression Linear Quadratic X1X2 X1X3 X2X3 Residual Error Total DF 5 2 3 1 1 1 4 9 5 2 3 1 1 1 4 9 5 2 3 1 1 1 4 9 5 2 3 1 1 1 4 9 Seq SS

Adj SS 1371.407 708.546 487.864 141.562 276.305 75.392 49.177 20.5446 5.4931 11.8825 3.5843 0.7699 7.6411 0.8287 27448.0 1225.7 6921.0 948.6 1950.3 4096.7 794.6 957.442 423.951 428.479 251.418 26.961 154.261 22.059

Adj MS 274.281 354.273 162.621 141.562 276.305 75.392 12.294 4.10892 2.74654 3.96083 3.58433 0.76985 7.64109 0.20717 5489.59 6125.36 2306.99 948.57 1950.31 4096.67 198.64 191.448 211.979 142.826 251.418 26.961 154.261 5.515

F 22.31 28.82 13.23 11.51 22.47 6.13 19.83 13.26 19.12 17.30 3.72 36.88 27.64 30.84 11.61 4.78 9.82 20.62 34.72 38.34 25.90 45.59 4.89 27.97

P 0.005 0.004 0.015 0.027 0.009 0.068 0.006 0.017 0.008 0.014 0.126 0.004 0.003 0.004 0.019 0.094 0.035 0.01 0.002 0.002 0.004 0.003 0.092 0.006

Ultimate exural strength

Ultimate compression strength

Ultimate impact strength

1371.41 883.54 487.86 137.92 274.55 75.39 39.18 1420.58 20.5446 8.6621 11.8825 3.5010 0.7404 7.6411 0.8287 21.3733 27488.0 20527.0 6921.0 908.4 1915.9 4096.7 794.6 28242.5 957.442 528.963 428.479 248.042 26.176 154.261 22.059 979.501

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compression with probability of 99%. From ANOVAs table for impact it can be obtained that two-component interactions X1X2 and X2X3 were signicant with probability of P > 99% but X1X3 was not signicant due to its probability of 91%. In addition the probability of quadratic model is more than 99% and so it is a suitable model for tting impact response. 4.2. Regression coefcients and quadratic model for all tests Regression coefcients for all responses determined by Minitab software are shown in Table 5. The coefcients with probability of P > 95% are marked with one star and those with probability of P > 99% are marked with two stars. Eqs. (5)(8) show the tted regression quadratic model for all responses according to regression coefcients. The terms have not signicant effect, are eliminated from the nal equations. Moreover this table shows the coefcient of determination (R2) which is another criterion for evaluating ability of reduced model in predicting results. However, the more this value is close to 100%, to more accurate estimate from the results can be provided. From R2 values in Table 5 it can be concluded the quadratic model provides the most accurate estimation for the Impact response.

4.3. Normal probability plot of residuals for all responses Normal probability plot of residuals determines whether a particular distribution ts collected data and allows, comparing different sample distributions. If the distribution ts the data the plotted points will fall close to the tted distribution line. Normal probability plot of residuals for all mechanical properties are seen in Fig. 3. Some of the plotted points for three mechanical properties (tensile, compression and impact) that can be seen in Fig. 3(-a, -b and -d) are not close to the distribution tted line and some of these points are far from the others. However the normal probability plot for exural (Fig. 3-c) shows that tted points are closer to the tted distribution line compare with the others. Generally it is concluded that distribution of all these mechanical properties is close to the normal distribution but it is closer for the exural property compared with three other properties. 4.4. Response trace plot for all responses Response trace plot (also called a component effect plot) shows the effect of each component of mixture on interesting response. Trace curves show the effect of changing the corresponding component along an imaginary line connecting the reference blend on the vertex. Often the centroid (center point) of the experimental region is chosen as reference blend. Response trace plot for studied mechanical properties is shown in Fig. 4. As shown in Fig. 4(-a), tensile generally decreased with increasing in proportion of HIPS and SiO2, and also increased with increasing in proportion of hardener content to the magnitude of about 70 Mpa and then decreased slightly. Trace plot for exural in Fig. 4(-b) shows that exural decreased continuously with increasing in proportion of HIPS.
99 95 90 80 70 60 50 40 30 20 10 5 1

g 25:84x1 45:19x2 61:69x3 52:89x1 x2 73:89x1 x3


38:59x2 x3 5 6 7 8

g 0:07x1 1:21x2 3:66x3 8:41x1 x2 12:28x2 x3 g 45:9x1 107:69x2 193:99x3 196:3x1 x3 284:5x2 x3 g 14:6x1 28:47x2 42:37x3 70:48x1 x2 55:21x2 x3
99 95 90 80 70 60 50 40 30 20 10 5 1 -5.0 -2.5 0.0 2.5 5.0

Percent

Percent

-0.8

-0.6

-0.4

-0.2

0.0

0.2

0.4

0.6

0.8

Residual

Residual

(a)
99 95 90 80 70 60 50 40 30 20 10 5 1 -20 -10 0 10 20
99 95 90 80 70 60 50 40 30 20 10 5 1 -20 -10

(b)

Percent

Percent

10

20

Residual

Residual

(c)

(d)

Fig. 3. Normal probability plots of residuals for a = tensile, b = exural, c = compression, d = impact.

Y. Rostamiyan et al. / Materials and Design 56 (2014) 10681077


70

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Comp:RefBlend HIPS 0.3333 Sio2 0.3333 hardener 0.3333

60

Comp:RefBlend HIPS 0.3333 Sio2 0.3333 hardener 0.3333

Fitted Tensile

Fitted flexural

50

40

2 30 1 -0.50 -0.25 0.00 0.25 0.50 0.75 -0.50 -0.25 0.00 0.25 0.50 0.75

deviation from reference blend in proportion

deviation from reference blend in proportion

(a)
225 200
Comp:RefBlend HIPS 0.3333 Sio2 0.3333 hardener 0.3333

(b)
50 45 40
Comp:RefBlend HIPS 0.3333 Sio2 0.3333 hardener 0.3333

Fitted Compression

175 150 125 100 75 50 -0.50 -0.25 0.00 0.25 0.50 0.75

Fitted Impact

35 30 25 20 15 -0.50 -0.25 0.00 0.25 0.50 0.75

deviation from reference blend in proportion

deviation from reference blend in proportion

(c)
Moreover increasing in proportion of SiO2 rst increased exural and then decreased it quickly. Finally hardener content had similar effect on exural response with a slower rate compared with SiO2. Fig. 4(-c) indicates trace plot for compression. It is obtained from this gure that compression generally decreased with increasing in proportion of SiO2 and HIPS continuously whereas it increased with increasing in proportion of hardener content to the magnitude of about 220 Mpa and had a little decreasing at last. As seen in Fig. 4(-d), with increasing in proportion of SiO2, impact rst increased to the magnitude about 45 kJ/m2 and then decreased quickly. Increasing in proportion of hardener content had the same effect but with a slower rate compared with SiO2 whereas increasing in proportion of HIPS decreased the impact response. Generally it can be concluded that HIPS had linear antagonistic effect on all of the studied mechanical properties whereas two other components had synergistic effect on all responses with various rate of changes. 4.5. Contour plot for all responses Contour plot is a 2-D dimensional plot which shows the effect of changing in combination of mixture components, on the magnitude of interesting response. This contour involves different regions and changing in the color of regions shows trend of response. So the regions with darker highlight have higher magnitude of response compared with the regions with lighter highlight. Walking on different regions in contour plot indicates various magnitude of response and coordinate of corresponding point and so proportion of components can be calculated according to this point. Fig. 5 shows the contour plot for all responses. As seen in the contour plot of tensile (Fig. 5-a), the highest values for tensile

(d)
Fig. 4. Response trace plot for a = tensile, b = exural, c = compression, d = impact.

response (higher than 60 Mpa) occurred in the dark green region and the edges of SiO2-hardener and HIPS-hardener. These values were obtained for formulations 3, 5, 6 and 10 and the highest value was 65.4 Mpa for formulation 6 with 0 HIPS, 0.5 SiO2 and 0.5 hardener on SiO2-hardener edge (Table 1). The lowest value for tensile was 24 Mpa for formulation 1, with 1HIPS, 0 SiO2 and 0 hardener (Table 1). Walking along contour plot of tensile showed that maximum value for this property was about 66.94 Mpa and occurred on point (x1 = 0.176, x2 = 0.174, x3 = 0.64) and the corresponding values for component proportions were HIPS = 3.76 wt.%, SiO2 = 2.56 wt.%, Hardener = 27.4 phr respectively. The region of high values for Flexural can be seen in Fig. 5(-b). As seen, this region was given in the edge of SiO2-hardener, similar to tensile response. High values for exural response (more than 5 Mpa) belong to formulations 6 and 10 and the highest value was 5.32 Mpa for formulation 6 with 0 HIPS, 0.5 SiO2 and 0.5 hardener whereas the lowest value of exural was 0.93 Mpa for formulation 1 with 1 HIPS, 0 SiO2 and 0 hardener content (Table 1). Walking along contour plot of Flexural showed that the maximum value obtained for this mechanical property was about 5.75 Mpa for point (x1 = 0.01, x2 = 0.32, x3 = 0.668) and so corresponding component proportions would be HIPS = 2.1 wt.%, SiO2 = 3.88 wt.% and hardener = 27.7 phr respectively. Contour plot of compression is shown in Fig. 5(-c). This gure indicates that trend of compression magnitude was almost similar to tensile and exural. High values for compression (more than 200 Mpa) response were given in the edge of SiO2-hardener similar to what occurred for previous sections. These values were 213.1 Mpa and 219.2 Mpa for formulations 6 and 10 respectively and so the highest value for compression belonged to formulation 10 with 0.167 HIPS, 0.167 SiO2 and 0.667

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Fig. 5. Contour plot for a = tensile, b = exural, c = compression, d = impact.

Table 5 Regression coefcients and correlation for the adjusted model to experimental data in mixtures design. Variables Coefcients b1 Tensile Flexural Compression Impact
* **

R2 b2 b3
**

b12
**

b13
*

b23
**

25.83 0.7042* 45.39** 14.60**

**

45.19 1.2137* 107.69** 28.47**

61.69 3.6601* 193.99** 42.37**

52.89 8.4153* 136.9 70.48**

73.89 3.9001 196.3* 23.08

38.59* 12.287** 284.5* 55.21**

0.9654 0.9612 0.9719 0.9775

Signicant at 0.05 level. Signicant at 0.001 level.

hardener (Table 1). The lowest value was 52.8 Mpa which occurred in formulation 1 with 1 HIPS, 0 SiO2 and 0 hardener (Table 1). Maximum value for compression which evaluated by walking along dark green region in contour plot of this response, was about 225.970Mpa for the point (x1 = 0.033, x2 = 0.327, x3 = 0.638) and so proportions of mixture components for this point would be HIPS = 2.33 wt.%, SiO2 = 3.94 wt.% and hardener = 27.4 phr. According to contour plot of impact response in Fig. 5(-d), highest values for Impact were given in the edges of SiO2-hardener and HIPShardener similar to tensile response. The highest value for impact occurred in formulation 6 with 0 HIPS, 0.5 SiO2, 0.5 hardener and magnitude of 49.1 KJ/m2. The lowest value for impact was 13.8 KJ/m2 which occurred in formulation 1 with 1 HIPS, 0 SiO2, 0 hardener (table 1). Maximum value for Impact response was about 50 KJ/m2 for the point (x1 = 0.007, x2 = 0.327, x3 = 0.638) and proportion of mixture components for this point would be HIPS = 2.07 wt.%, SiO2 = 3.94 wt.% and hardener = 27.38 phr.

Fig. 6. Overlaid contour plot of tensile, exural, compression and impact strength of hybrid nano composite samples.

Y. Rostamiyan et al. / Materials and Design 56 (2014) 10681077 Table 6 Optimum mixture proportions. Components HIPS SiO2 Hardener Proportions 2.67 wt.% 4.01 wt.% 28 phr

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Generally it can be concluded that maximum value of response for three of these four mechanical properties occurred in formulation 6 with 0 HIPS, 0.5 SiO2 and 0.5 hardener and so interaction X2X3 had the highest effect on maximizing nal responses unlike minimum value of response for all of studied properties occurred in formulation 1 with 1 HIPS, 0 SiO2 and 0 hardener and so HIPS had the lowest and antagonistic effect on maximizing responses.

combination of SiO2 as nano reinforcement, HIPS as thermoplastic phase and hardener was found but the best solution is presented in Table 6. Therefore, if the main goal is to produce hybrid samples which has the best tensile, exural, compression and impact strength in same time, formulation with HIPS content of 2.67 wt.%, SiO2 content of 4.01 wt.% and hardener content of 28 phr should be used. This optimum solution is shown by a clear ag on the overlay plot (Fig. 6). As illustrated in Fig. 6, the zone indicated by Label D, at the bottom of the plot, represents all appropriate solutions given by the software.

4.7. StressStrain plots Samples with the contents listed in previous step (Table 6) were then synthesized and tested to check and verify the predicted results. The following mean values were obtained (based on 5 replications in each case): 63.8 MPa for UTS, 5.36 MPa for UBS, 219.2 MPa for UCS, and 47.3 kJ/m2 for impact. These results indicate that the real values were in good or acceptable agreement with those predicted by the model. Fig. 7 indicates stressstrain plots for tensile, exural and compression tests. As it is obvious

4.6. Mixture proportion optimization optimal mechanical properties of epoxy-based hybrid nano composite was obtained by solving the previous equations (Table 5) to yield the average of each independent variable measured for mechanical properties as a response. Using this approach, a set of

Fig. 7. StressStrain plots for (a) tensile, (b) exural, (c) compression.

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Fig. 8. Impact strengths of different epoxy-based systems.

from this gure adding HIPS alone will considerably decrease the tensile and exural strengths and also has negligible positive effect on compression of epoxy matrix in low concentration. From Fig. 7(-a) it is clear that incorporating the nanosilica and thermoplastic phase into the epoxy matrix increased the ultimate tensile strength and elongation at break are up to 59.5% and 71% compared to neat resin, by 82% and 200% compared to epoxy/

2.67 wt.% HIPS and by 16% and 71% compared to epoxy/4.01 wt.% SiO2 respectively. Also this gure shows that combination of nano silica and thermoplastic phase decreased elastic modulus compare to neat epoxy. With compare to other works it can be observed that adding HIPS decreased tensile strength of epoxy/Sio2 binary nano composite [3]. As presented in Fig. 7(-b) the exural strength of hybrid nanocomposite in comparison with neat epoxy sample is decreased down 11%. Decrease in exural strength was observed in previous studies when HIPS added as thermoplastic phase in hybrid mechanism [20,26]. Based on Fig. 7(-b) and the elongation at break is increased compared to neat resin up to 83%. Also it can be found that with adding thermoplastic or nanoparticle phases, the exural modulus takes a general decreasing trend. Fig. 7(-c) indicates that new ternary nanocomposite improved ultimate compression stress up to 45% compared to neat epoxy, but compression strain does not change considerably. Also this gure shows that new ternary nano composite improved ultimate compression strength up to 19% compare to epoxy/2.67 wt.% HIPS and 28% compare to epoxy/4.01 wt.% nano silica. Also Fig. 8 indicates ultimate impact strength of different epoxy-based system. From this gure it can be concluded that incorporating nano sio2 as nano reinforcement and HIPS as a thermoplastic phase improved ultimate impact strength up to 414% compared to neat resin, bye 11.5% compared to combination of HIPS and epoxy resin and by 272% compared to epoxy/SiO2 binary

(a)
50000
C K

(b)

40000

30000

20000

10000
O K AuM AuM SiK

0 0 5

AuLl

AuL

AuL

keV

10

(c)
Fig. 9. Scanning electron micrographs of fracture surface for samples (a) neat epoxy, (b) incorporating 2.67 wt.% HIPS and 4.01 wt.% nano silica, (c) EDX analyze.

Y. Rostamiyan et al. / Materials and Design 56 (2014) 10681077

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nanocomposite. The results of impact test shows that adding HIPS in epoxy resin increase impact strength more compare to another thermoplastic materials such as rubber particle [10,11]. In previous studies, different results were achieved by adding thermoplastic and nanophases simultaneously to epoxy resin. Rostamiyan et al. [20] lled epoxy resin with nanoclay as a nano reinforcement and HIPS as a thermoplastic phase and improvement in tensile, compression and impact strength were observed about 60%, 64%, and 402%, respectively higher than those of the neat resin. Asif et al. [27] reported that incorporating clay and ether ketone led to a dramatic decrease in impact strength. Bakar et al. [28] showed that adding 2% clay and 20% polyamide enhances the impact strength by up to 115%. Mirmohseni et al. [29] demonstrated that the incorporation of 2.5% nanolayered clay and 4 phr ABS into an epoxy matrix resulted in a 133% increase in impact strength. Fereidoon at el. [26] showed that using multi-walled carbon nanotube in present of high impact polystyrene improved mechanical properties such as tensile, compression and impact up to 52%, 43% and 334%, respectively higher than those of the neat resin. 4.8. SEM and EDX analyze The micrograph shows cut surface of tensile specimen at optimum amount of HIPS, SiO2 and hardener in Fig. 9. In epoxy materials, crosslink density plays a vital role to achieve good mechanical properties. Obviously in Fig. 9(-b), good dispersion of Silica nanoparticles and high impact polystyrene as thermoplastic phase with little agglomeration is occurred. Also it can be obtain that phase separation of nano and micro particles in epoxy rich matrix was observed. This modier with homogenous dispersion can play important role as crack stoppers and also reinforcements in enhance mechanical strengths [30,31]. In agreement with SEM investigation, as shown in Fig. 9(-c), EDX analysis of the epoxy/HIPS/SiO2 samples showed a homogeneous combination of Silica nano particles in matrix. Also from this gure it can be concluded that the solvent evaporated completely under vacuum situation. 5. Conclusions In this paper, the mechanical properties (Tensile, Flexural, Compression and impact) of new ternary epoxy-based hybrid nanocomposite incorporating nano silica as nano reinforcement and high-impact polystyrene (HIPS) as thermoplastic phase were tested. From the results of the present work, it can be concluded that mixture design approach is a tting method to optimization of mentioned mechanical properties. According to experimental results, contours and stressstrain plots of hybrid samples with an HIPS content of 2.67 wt.%, a nano SiO2 content of 4.01 wt.% and hardener content of 28 phr has best tensile, exural, compression and impact strength. Also stressstrain plots indicates that new hybrid of nano reinforcement and thermoplastic phase significantly increased ultimate tensile, compression and impact strength compared to those of the neat epoxy resin by up to 59.5%, 45% and 414% respectively, but the exural strength was not enhanced by adding both nanosilica and HIPS. The tensile and exural elongations at break were up to 71% and 83% larger than those of neat epoxy, respectively, but compression strain was not change considerably. Correlation between the morphology of the nanocomposite and its mechanical properties was noted when using the SEM technique. References
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