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Toughened FRP Composites Reinforced with Glass and Carbon Fiber Debdatta Ratna PII: DOI: Reference: To appear in: Received Date: Revised Date: Accepted Date: 10.1016/j.compositesa.2007.12.005 JCOMA 2156 Composites: Part A 7 May 2007 9 December 2007 16 December 2007
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Please cite this article as: Ratna, D., Toughened FRP Composites Reinforced with Glass and Carbon Fiber, Composites: Part A (2007), doi: 10.1016/j.compositesa.2007.12.005

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Toughened FRP Composites Reinforced with Glass and Carbon Fiber
Debdatta Ratna* Institut fur Verbundwerkstoffe GmbH (Institute for Composite Technology) Technical University, Kaiserslautern Erwin-Schrodinger-Str. 58 D-67663, Kaiserslautern GERMANY ABSTRACT Glass fiber reinforced plastic (GFRP) and carbon fiber reinforced plastic (CFRP) composites were made using epoxy/hyperbranched polymer (HBP) blends as matrices. The morphology of the blends was investigated both in the castings and composite form. Unlike the castings, where no reduction in epoxy Tg was observed up to 15 wt% of HBP, the Tg of the blend matrix was found to decrease as a result of addition of HBP (0 to 20 wt%) in case of GFRP and CFRP composites. Incorporation of HBP resulted in a significant increase in impact strength in GFRP composites whereas no significant improvement was observed in case of CFRP composites. Fracture surfaces of the composites were analyzed by scanning electron microscope (SEM), which indicates a two-phase microstructure. The microstructure was found to be different in castings and composites.

Key Words: FRP composites, mechanical properties, glass fibre, epoxy resin -----------------------------------------------------------------------------------------------------------* Tel. 0049-631-2017242, Fax : 0049-631-2017198,e.mail : ratnad29@hotmail.com , Permanent Address: NMRL, Shil-Badlapur Road, Anand nagar P.O., District Thane Maharashtra - 421 506, India.

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1. Introduction Over the last two decades, the use of epoxy based fiber reinforced plastic (FRP) composites, in structural applications, has increased tremendously and this dramatic growth is expected to continue in the future. The composites possess many useful properties like high specific stiffness and strength, dimensional stability, adequate electrical properties and excellent corrosion resistance which make them attractive to the automobile and aerospace industries [1-3]. However, the thermoset based FRP composites are known to be highly susceptible to internal damage caused by a low velocity impact, which may lead to severe safety and reliability problems. Hence, the improvement of damage tolerance of FRP composites by enhancing their impact strength has been of considerable research interest [4, 5]. There are several methods to enhance the toughness of FRP composite ; examples of these are matrix toughening [6,7], insertion of interlaminer interleaf layers [8,9], utilization of high strain fibers and fiber hybridization[10,11]. The last two approaches are particularly effective in improving the impact penetration resistance of composites under high-incident-energy condition which is the main concern for composite amour. Using a particular fiber the low-velocity- impact resistance of a composite which is desirable for structural application, can be controlled to a great extent by increasing resin toughness [12-15]. Toughening of a thermoset, can be achieved by reduction of crosslink density or use of plasticizers, which lead to increased plastic deformation. However, this approach may seriously affect modulus and thermal properties of the material for only a modest increase in toughness. The most effective approach is the introduction of a second component, which is capable of phase separation such as reactive liquid rubber [16, 17], engineering thermoplastic [18, 19] or core-shell particles [20, 21]. An attraction of liquid rubber like carboxyl-terminated copolymer of butadiene and acrylonitrile (CTBN) as a modifier, is their solubility in base epoxy with the formation of initially a homogeneous solution. As the curing reaction proceeds, the molecular weight increases and the phase

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separation occurs at some stage, leading to the formation of a two-phase morphology [22, 23]. Such a two phase system having a small amount of rubber ( 5-10 wt % ) often shows outstanding fracture properties as the rubber particles dispersed and bonded to the epoxy matrix act as centers for dissipation of mechanical energy by cavitations and shear yielding[17,23]. The improvement in fracture toughness is generally achieved without a significant reduction of thermal and mechanical properties of the crosslinked epoxy resin. However, the main deficiency of CTBN is the high level of unsaturation in their structure, which provides sites for degradation reaction in oxidative and high temperature environment [24]. The presence of double bonds in the chain can cause oxidation reaction and/ or further cross-linking with the loss of elastomeric properties and ductility of the precipitated particles [25]. Secondly, there remains a possibility that traces of free acrylonitrile, which is carcinogenic, might exist and limits the use of these materials [26]. The saturated liquid rubbers such as siloxane [27], polyurethane [28], acrylates [29, 30] etc., have been reported as alternatives to CTBN. The modification of epoxy with a linear liquid rubber results in a significant increase in prepolymer viscosity. The increase in viscosity of the resin hinders resin impregnation into the fibers resulting in poor mechanical performance of the FRP composites. Very recently, new classes of reactive liquid rubber, which are dendritic hyperbranched polymers (HBPs), have been investigated as modifiers for epoxy resin [31-35]. The advantages of HBPs over conventional toughening agents are that HBPs offer much lower prepolymer viscosity because of their spherical structure and lack of chain entanglement and stronger adhesion with the matrix due to the presence of high density of surface functional groups. Recent studies on the behavior of polymer blend in presence of inorganic fillers indicate that inorganic filler increases the compatibilization [36, 37]. It is in the light of this finding that the present study was carried out with the aim of examining the morphology of epoxy/HBP blends in the composite form and evaluating their relative performance for composite applications. Effect of incorporation of HBP on the

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mechanical, dynamic mechanical properties and morphology of glass and carbon fiber reinforced composites were investigated. 2. Experimental 2.1 Materials The epoxy resin used was a liquid diglycidyl ether of bisphenol A (DGEBA) (DER 331 Dow epoxy resin) containing 5.27 mmol epoxide per gram of resin. The curing agent, Ethacure 100, of Albemarle Corp., USA, is a mixture of the two diethyltoluene diamine (DETDA) isomers (74-80% 2, 4 isomer and 18-24% 2, 6 isomer). The chemical structures of the epoxy resin and hardener are shown in Fig. 1. The epoxy functional dendritic hyperbranched polymer (Boltorn E1) with an epoxy equivalent weight of ~ 875 g/eq and a molecular weight of ~ 10500 g/mol, was supplied by Perstorp Speciality Chemicals, Sweden. Boltorn E1 consists of a highly branched aliphatic polyester backbone with in average 11 reactive epoxy groups per molecule. A schematic representation of E1 is shown in Fig.1. E glass cloth (150 m thick) was obtained from FGP Ltd., India. The carbon cloth (450 m thick) was supplied by Nikunj India Pvt. Ltd. The composition and properties of the glass fiber and carbon fiber are shown in Table 1. 2.2 Fabrication of composites The fiber cloth was cut to size and heated in the oven at 150 C to make it moisture free before processing. The epoxy/HBP blend and hardener mixture was applied onto the glass surface by a hand-lay-up technique. 15 layers of glass or 8 layers of carbon layers were added successively in order to get about 3 mm thick GFRP and CFRP composites respectively. The laminate was compressed thereafter, in a mold (30 cm x 30 cm)) at a pressure of 50 kg/cm2 and allowed to cure 130 C for 2h, 160 C for 3h. The FRP sheet was then taken out from the mold and post cured at 210 C for 2h. 2.3 Determination of glass content

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The glass content for the composite samples were determined by a resin burn-off test according to ASTM D3171-99. The wt. % glass (x) was determined from the following formula:
x= w 100 wo

(1)

wo and w are the initial weight and weight after the matrix burn-off respectively. The vol % glass (y) was determined from the formula given below :

y=

x x + (100 x) dg de

(2)

dg & de are the densities of glass and epoxy respectively. 2.4 Evaluation by DMA DMA analysis was carried out in a VA 4000 viscoanalyser (Metravib RDS, France). In practice, the viscoanalyser is used to apply a displacement d(w) at the upper end of a sample and measure the force F(w) transmitted to the fixed lower end . F(w), and f are the values which can be obtained using sensors. F(w) is measured by a dynamic force sensor and d(w) is measured by displacement or acceleration sensor. By measuring the upstream displacement and downstream force, the measurement method has the advantage of being capable of obtaining the stiffness, irrespective of the weight of the sample. The phase angle (w) i.e. the phase shift between the dynamic force and dynamic displacement was calculated using the processing of the signals F(w), d(w) according to first Fourier transform (FFT). Samples of size 45 x12 x 3 mm3 were exited in flexural (three point bending) mode under a temperature ramp of 3 Kmin-1 at a fixed frequency of 5 Hz. The temperature range was 30 C to 180 C to observe the full loss curve response for all the samples.

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2.5 Flexural test The flexural properties were measured with rectangular samples according to ASTM D790, using the same UTM at crosshead speed of 4 mm/min. The fracture strength (F.S) was determined from the peak load (kg) using the following formula:

3 peakload span 9.8 F .S = 2 width (thickness ) 2

(3)

The results are expressed in MPa, which is the average of the results from three samples. The flexural deformation was determined by an LVDT system. 2.6 Impact Properties The Izod impact test was carried out according to ASTM D-256 using an impact tester (Tinius Olsen, Model 892 T). The impact test was carried out at room temperature and impact energy was reported in J/m. The quoted result is the average of the determinations on five samples. 2.7 Optical microscopic analysis The hot stage optical microscopy was performed on a Reico optical microscope in which two polarizers are aligned. The epoxy/HBP blend (epoxy + HBP + DETDA) was applied on a slide and the optical photographs were taken in magnification of 400 at various interval. 2.8 SEM Analysis A low voltage scanning electron microscope (SEM), (Cameca, SU-30) was used to examine the fracture surfaces of the toughened epoxy castings and composite samples. A thin section of the fracture surface was cut and mounted on an aluminum stub using a conductive (silver) paint and was sputter coated with gold prior to fractographic

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examination. SEM photo micrographs were obtained under conventional secondary electron imaging conditions and with an accelerating voltage of 20 kV. 3. Results and Discussion 3.1 Dynamic mechanical analysis The composite samples were subjected to dynamic mechanical analysis from room temperature to 260 C. The tan vs. temperature plots of GFRP and CFRP composites based on the unmodified epoxy and 15 wt% HBP modified epoxy matrices are shown in Fig. 2. As temperature is increased, it is observed that the tan goes through a maximum in the transition region and then decreases in the rubbery region. The damping is low below Tg as the chain segment in that region is frozen. Below Tg, the deformations are thus primarily elastic and the molecular slips resulting in viscous flow is low. Also above Tg, in the rubbery region, the damping is low because the molecular segments are free to move, and consequently there is little resistance to flow. The maximum damping occurs in a region where most of the chain segments take part in this co-operative microBrownian motion under harmonic stress. The position and height of the loss tangent peak in the relaxation spectra of a polymer are indicative of the structure and extent to which the polymer is crosslinked. The dynamic modulus (E` ) rapidly decreases in the relaxation temperature zone due to the decreasing stiffness of the samples as the segmental motion sets in. It is evident from the loss tangent plots (Fig. 2) that both the GFRP and CFRP composite samples show a relaxation peak at temperatures lower than that obtained in the case of bulk cured resin. The Tg for GFRP composite based on the unmodified epoxy is 190 C whereas for unreinforced cured epoxy it is 217C. Theocaris and Papanicolaou [38] reported that the temperature of tan peak of an epoxy resin was significantly higher (25 C) in the bulk resin than that in the glass fiber composite containing the same resin. Ghosh et al. [39] reported similar effects in the case of jute fiber reinforced composites. This can be explained by considering the effect of organosilane coating, which is used for commercial fibers in order to increase adhesion with the matrix. The organosilane group with unreactive organic groups leads to an interface with many
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unrestrained or free end groups which result in reduction in the crosslink density of the polymer network in the interface region [40]. The plasticized region then yields decreased internal friction and thereby causes a reduction in relaxation temperature. It is interesting to note that in case of castings, there is no change in epoxy Tg up to 15 wt% of HBP whereas in case composites reduction in epoxy Tg was observed as a result of incorporation of HBP. The decrease in Tg for cured rubber modified epoxy systems arises from the incomplete phase separation and plasticization phenomenon caused by the dissolved rubber that has been noted in varied rubber modified epoxy formulations [41, 42]. This indicates that the presence of fibers initiates partial miscibility of the HBP with the epoxy matrix due to chemical interaction of epoxy/HBP blend with fiber in the interface. 3.2 Morphology Epoxy/HBP blend (castings) is initially homogeneous at curing temperature (130C) and undergoes reaction-induced phase separation with the advancement of curing reaction as shown by optical microscopic analysis (Fig.3). Combining the Flory- Huggins equation and the Hildebrand equation [43], the free energy of mixing can be expressed as: Gm /V = e r (e - r )2 + RT(e/Ve . ln e + r / Vr . ln r ) where (4)

e , r are the volume fractions and e , r are the solubility parameters and Ve

and Vr are the molar volume of epoxy and rubber respectively. Since e , r are fractions (<1), the second term (change in entropy) is always negative. Thus increases in temperature favor the mixing, by increasing the second term, resulting in HBP solubility with epoxy above 100C. As the epoxy resin cures, the value of Ve and Vr increases, resulting in a decrease in the second term. At a critical conversion Gm becomes positive and phase separation occurs. However, if (e -r) i.e. the difference between the solubility parameters of the epoxy and the liquid rubber is very low, then the change in entropy due to the curing reaction will not result in a positive free energy change of

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mixing (Gm) prior to gelation [44]. Thus a moderately slow curing rate is necessary to ensure complete phase separation. In case of composite, the free energy change of the system including three components, epoxy, HBP and fiber, can be described as Gm = GEF + GHF - GEH (5) are where GEH is the free energy of mixing between epoxy and HBP, GEF & GHF

the free energy of interaction of the two components with the fiber surface. Since both the components strongly adsorbed to fiber surface, Gm will always be negative and hence equilibrium phase diagram is shifted to higher compatibility. This explains why epoxy/HBP blend shows more compatibility in composites compared to that in casting. The fracture surfaces of epoxy/HBP blend (15 wt%) and corresponding GFRP and CFRP composites were analyzed by SEM. The SEM microphotographs are shown in Fig.5. Both the unreinforced matrix and the composite matrices show a two-phase microstructure. It is clear from the figure that the volume fraction of HBP is less in the composites compared to that in the unreinforced matrix. This substantiates the DMTA results, which indicates the presence of dissolved rubber in the composite matrix unlike the unreinforced matrix. In the case of castings, the HBP particles are uniformly distributed throughout the matrix. The particles have dimension in the range of 1-2 m and their distribution is bimodal in nature. It is interesting to note that in composites the particles are comparatively bigger and the uniformity in particle size distribution is lost to some extent. It appears that there is not much effect of the nature of the fiber as the morphologies are similar for both GFRP and CFRP composites. This indicates that fibers act only as a nucleating site. Similar results were reported in the literature for thermoplastic modified epoxy system [45]. The rubber particles bonded and dispersed in the matrix of a composite enhances the toughness of the composite by rubber cavitations and shear yielding [46, 47], as will be discussed next. 3.3 Flexural properties

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The representative flexural stress-strain diagram for GFRP and CFRP composites are shown in Fig. 6 and Fig. 7 respectively and the flexural properties of GFRP composites are presented in Fig. 8. It was found that there is little change in the flexural modulus due to incorporation of HBP. The reason is that modulus is predominantly dictated by the high modulus fibers and all the composites contain almost same glass/carbon content. However, the fracture behavior changes in case of GFRP; the flexural strength decreases and yielding during break increases as a result of incorporation of HBP. This indicates that the GFRP composite based on epoxy/HBP blend would show higher toughness compared to the unmodified epoxy based composite. On the other hand no significant change in fracture behavior was observed in case of the CFRP composites. 3.4 Impact property The effect of HBP content on the impact strength of GFRP and CFRP composites were also investigated and the results are shown in Fig.9. It was observed that there is a significant increase in impact strength in case of GFRP composites due to the incorporation of HBP. The GFRP composite based on 15 wt% HBP modified epoxy shows impact strength 1300 J/m compared to 900 J/m for the unmodified epoxy based GFRP composite. The increase in the impact strength of GFRP composites can be attributed to the increase in the toughness of the epoxy matrix due to the addition of rubbery HBP. According to recent theories, the most accepted mechanism for rubber toughening is rubber cavitations followed by shear yielding [13]. In rubber modified plastics, under triaxial tensile stresses, voids can be initiated inside the rubber particles. Once the rubber particles are cavitated, the hydrostatic tension in the material is relieved, with the stress state in the thin ligaments of the matrix between the voids being converted from a triaxial to a more uniaxial tensile stress state. This new stress state is favorable for the initiation of shear bands. In other words, the role of rubber particles is to cavitate internally, thereby relieve the hydrostatic tension and initiate the ductile shear yielding mechanism [13, 46, 47].

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However, the improvement in impact strength in GFRP composite, is less compared to that observed in the matrix reported earlier [33]. Similar observation was reported by others using various polymer matrix [48]. This is due to fiber constraint suppressing inelastic resin deformation at the crack tip [48, 49]. In case of CFRP composites, prepared using the same compositions/conditions, no significant improvement in impact strength (Fig.9) was observed as a result of incorporation of HBP. The fracture property of CFRP composites is reported [50, 51] to be governed by the interfacial adhesion and internal stress development during cure, which can be manipulated by material and process tailoring. Thus these aspects need to be analyzed critically. However, the apparent difference in behavior of HBP-modified epoxy-based GFRP and CFRP composites prepared under the same conditions, can be explained in the light of the inherent properties of the fibers (Table1). Carbon fibers are much more brittle (tensile strain = 1%) compared to glass fiber (tensile elongation = 2.5%) [52]. This is also reflected in the impact behavior of GFRP and CFRP composites. The impact strength of unmodified epoxy based CFRP composite is 500 J/m compared to 950 J/m for corresponding GFRP composite. It is well established that dispersed rubber particle enhances the toughness of the epoxy system by cavitations of rubber particle followed by shear yielding and their effectiveness decreases with increase in the rigidity of the system [53, 54]. Highly brittle carbon fiber imposes restriction on the induction of plastic deformation by the rubber particle. In fact failure of the CFRP composites occurs due to fiber breaking. 4. Conclusion Epoxy/HBP blends were evaluated both as castings and as FRP composites. The epoxy resin matrices of FRP composites exhibit lower Tg compared to the corresponding castings. The epoxy/HBP blends show a two-phase morphology both in castings and in FRP composites. The microstructure was found to be different in FRP composites compared to that observed in castings. In FRP composites, the morphological features are similar in the FRP composites, irrespective of the nature of fibers. The epoxy Tg

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decreases with the incorporation of HBP in FRP composites, on the other hand no significant decrease in epoxy Tg was observed in castings, up to 15 wt% of HBP. This indicates that the presence of fiber increases the compatibilization of epoxy/HBP blend and thereby increases the amount of dissolved rubber. Incorporation of HBP resulted in significant increase in toughness in GFRP composites with slight decrease in Tg and flexural strength. Whereas no such effect was observed in CFRP composite. Acknowledgement The author is thankful to the Alexander von Humboldt (AVH) foundation for the grant of a post doctoral research fellowship.

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Table 1 Properties of glass and carbon fibres Properties Glass fibre Carbon fibre

Density, g/cc

2.54

1.8

Tensile strength, GPa

1.5

2.5

Tensile strain, %

2.5

Tensile Modulus, GPa

75

246

Sp. Tensile strength

0.6

1.4

Sp. Tensile Modulus

29.5

137

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Legends to the figures

Figure 1 Chemical structures of epoxy, curing agent and HBP Figure 2 Loss tangent vs. temperature plots of GFRP and CFRP composites Figure 3 Loss tangent peak temperatures (Tg) of castings and GFRP composites plotted against HBP content Figure 4 Optical microphotographs for epoxy/HBP blend (a) before curing and (b) after curing Figure 5a SEM microphotographs for the fracture surface of epoxy/HBP blend (15wt%) as casting Figure 5b SEM microphotographs for the fracture surface of epoxy/HBP blend (15wt%) as GFRP composite Figure 5c SEM microphotographs for the fracture surface of epoxy/HBP blend (15wt%) as CFRP composites Figure 6 Representative stress-strain diagrams for GFRP composites based on epoxy/HBP blends with 0 wt% and 15 wt% HBP Figure 7 Representative stress-strain diagrams for CFRP composites based on epoxy/HBP blends with 0 wt% and 15 wt% HBP Figure 8 Flexural strength and modulus of GFRP composites plotted against HBP content. Figure 9 Impact strength of GFRP and CFRP composites as a function of HBP content

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Figure 1

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Figure 2

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Figure 3

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Figure 4

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Figure 5a

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Figure 5b

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Figure 5c

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Figure 6

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Figure 7

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Figure 8

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Figure 9