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Studies on the thermal and morphological characteristics of laminates based on vinyl ester resin and glass fabric

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Abstract The effect of variation of styrene content on the thermal, mechanical and morphological behaviour of epoxy novolac vinyl ester resin (VER) /glass fabric laminate composites have been investigated. The vinyl ester resin matrix was synthesized indigenously using epoxy novolac resin and acrylic acid catalyzed by triphenylphosphine at a temperature of 900C in nitrogen atmosphere. Differential scanning calorimetric (DSC) technique was used to investigate the curing behaviour of the VER matrix. Thermal stability of the prepared samples was analyzed by dynamic thermogravimetric runs. Dynamic mechanical analyses of the samples were done to determine the viscoelastic properties. Cross-sections of the cured samples which failed during impact testing have been critically studied through scanning electron microscopic (SEM) analysis to gain insight into the phase morphology. Key words: vinyl ester resin, glass-fabric, composites, DMA, SEM. 1. Introduction Glass fabric reinforced polymer composite have found wide use for a range of structural and functional applications because of their superior performance combined with a high strength, stiffness and weight reduction. The low cost, high level of ultimate strain achievable, impact resistance, damage tolerance and general ease of processing, high specific strength and stiffness, good formability, corrosion and fatigue resistance makes the use of glass-fabric reinforcement very attractive to the aerospace and automotive industries. Vinyl ester resins are widely used as thermoset matrix to fabricate a variety of reinforced structures [1-3] including pipes, tanks, scrubber and ducts. They are the prime candidates for use in composite for transportation and/or infrastructure. Vinyl ester resins are based on the reaction product of an epoxy resin and an ethylenically unsaturated carboxylic acid, which results in a polymer with chain end unsaturation. Various epoxy resins are used, including the diglycidyl ether of bisphenol A, or higher homologues thereof, the diglycidyl ether of tetrabromo bisphenol A, epoxylated phenol-formaldehyde

novolac and polypropylene oxide diepoxide. The most commonly used acids are acrylic and methacrylic acids. In the present article, an attempt was made to develop composites based on epoxy vinyl ester resin and glass fabric and to study the thermal, mechanical and morphological characteristics of laminates based on vinyl ester resin and glass fabric by varying the styrene concentration. 2. Experimental 2.1 Material The novolac based epoxy resin used was EPN 1138 with an epoxide equivalent weight of 250 g/equiv., as determined by acid titration and the cure agent HY 951 (triethyl tetramine) were procured from M/s Ciba Specialty Chemicals Pvt. Ltd., Mumbai, India. Methacrylic acid and triphenylphosphine procured from M/s CDH Pvt. Ltd , New Delhi were used for the synthesis of vinyl ester resin. Styrene, benzoyl peroxide and hydroquinone were obtained from E.Merck, Germany, which were used for the curing of vinyl ester resin. Glass-fabric (aerial density 351 g/m 2) obtained from M/s Unnati Corporation, Ahmedabad, India was used for the preparation of the composites. 2.2 Synthesis and curing of vinyl ester resin Epoxy vinyl ester resin was prepared by using 1:0.9 mole ratio of epoxy resin and methacrylic acid. The reaction was carried out in the presence of triphenylphosphine (TPP) catalyst (1% by weight of the epoxy resin) and hydroquinone (200 ppm as inhibitor) at 850C in nitrogen atmosphere for about five hours to obtain a product with desired acid value [4]. The acid formed during the synthesis, in the form of an acid salt, was extracted by water and benzene was evaporated using a Rotovap TM evaporator under vacuum [5]. The curing of vinyl ester resin was done by using varying concentrations of styrene (as per the formulations given in Table 1) viz., 35, 40, 45 and 50% (w/w) and free radical initiator benzoyl peroxide (2% by weight) into hot air over at 1200C for 1 hour and then post cured for 2 hours at 1500C.. 2.3 Composite Preparation The prepregs for the glass-fiber/vinyl ester composite were prepared by using vinyl ester resin, styrene and benzoyl peroxide in the ratios as discussed in art 2.3 above. Each layer of fabric was well impregnated with a solution of this mixture by using the hand lay up method. Glass fabric (20 pieces each of size 25cm x 30cm) and stacked between two plain teflon sheets. This system was placed in between the two mild steel plates between the two pre-heated platens of a hydraulic press. The laminates were moulded at 120C under a pressure of 50 kg/cm 2. Postcuring was done at 150C for 2 hr to release the residual strains in the laminates. 2.4 Characterization of the samples Cure temperature of the prepared samples were observed by taking very little quantity of samples into shallow aluminium pan sealed by an aluminium cover of differential scanning calorimetric (DSC)

(TA Instrument, USA; Modulated DSC 2920). The percent weight loss and thermal degradation characteristics of prepared samples were evaluated by thermogravimetric analyzer (TGA) recorded on TA Instrument (Model Hi. Res. 2950) TGA unit interfaced with TA instruments Inc. Thermal Analyst 2100 (Du Pont) control unit. The glass transition temperature of cured samples were determined by dynamic mechanical analyzer (DMA) with TA Instruments DMA 2980 by applying a controlled sinusoidal strain to a sample and measuring the resulting stress. DMA gives both storage modulus and loss-modulus characteristics as a function of temperature. The fractured samples under mechanical analysis were sputter coated with gold prior to scanning electron microscopy (SEM) examination. Joel JSM 5800 model was used to view the specimens; several micrographs were taken for each sample. 3. Results and Discussion 3.1. Differential Scanning Calorimetry The dynamic DSC scan of vinyl ester sample V-3 has been shown in Fig.1. The onset temperature of curing (Tonset), the exothermic peak temperature or the temperature of maximum cure (Tp) and the final temperature or the temperature at the end of the cure (Tstop) for the samples were determined from DSC scans and the results have been tabulated in Table 1. It is evident from the data (refer Table 2), the onset temperature decreased as the styrene concentration increased probably due to the reduction in resin viscosity and thus increased oxygen diffusion out of the resin during sample preparation in nitrogen atmosphere. The peak exothermic temperatures were 110, 114, 117 and 127oC respectively for samples V-1 to V-4. 3.2. Thermogravimetric analysis The TGA curves of crosslinked vinyl ester resin (e.g. sample V-3) have been shown in Fig. 2. A clear-cut single step decomposition behavior was observed in all the thermograms of vinyl ester resins. The results of the thermograms (Table 2) indicated that the presence of different concentrations of styrene did not affect the nature of crosslinks formed during curing. In all the samples, initial weight loss of ~13% was observed between 100-300oC, which was probably due to the volatilization of the residual solvents or diluents, byproducts of curing reactions as well as the entrapped moisture present in the sample[6, 7]. However rapid decomposition was observed in the temperature range of 350 to 600C and ~ 76-80% of the sample was lost during the major decomposition step. 3.3. Dynamic Mechanical Analysis DMA provides a direct method for determining the crosslink density () of crosslinked materials by measuring the modulus at a temperature well above the Tg. The values of E in the rubbery region at T > Tg were taken to calculate by using Eq. (1) [8, 9]:

E' 3RT

(1)

Where Eis the storage modulus at Tg + 50oC, R be the gas constant and T be the absolute temperature at Tg + 50 oC. Fig. 3 showed the DMA trace of sample V-3. Increasing the amount of styrene in the system not only reduced the temperature of the glass-rubber transition, but also reduced the width of the peaks and increased its height [10]. For vinyl ester system, it has been suggested [11] that phase separation occurs during cure producing highly crosslinked, methacrylate rich region possessing a high Tg, surrounded by lightly crosslinked, styrene-rich region, presumably possessing a low Tg. 3.4. Scanning electron microscopy Fig 4 showed the morphology of fractured surfaces of the matrix and laminate of vinyl ester resin having 45% styrene. There appeared fine cracks in the fractured sample and it exhibited a single-phase morphology. In the case of composite laminates, the shear fracture occurred in the matrix-dominated interface area between the piles [12]. For typical glass fabric/vinyl ester laminates, the fracture micromechanism primarily occurred as interfacial de-bonding of the matrix from the fibers. Conclusion The following conclusions are based on the findings reported in this paper: 1. 2. 3. FTIR spectra showed that the chemical reaction occurred in between the epoxy novolac resin and methacrylic acid in the presence of basic catalyst to produce vinyl ester resin. Thermal stability was almost the same for the vinyl ester resin samples cured using varying concentrations of styrene. SEM photomicrographs of glass fabric/vinyl ester laminates displayed direct matrix debonding from the fabric surface. Moreover, interlaminar shear failure involved several fracture mechanism which occurred during delamination, such as matrix deformation and fracture, fabric pull-out and fabric bridging and fabric/matrix interface debonding.

4. DMA results showed that an increase in styrene content produced a decrease in Tg.
Acknowledgement Authors are thankful to the Director, Defence Materials Stores Research and Development Establishment (DMSRDE, a unit of Defence Ministry, Government of India) Kanpur, India, who had permitted to do the work in the organization. Thanks are due to Shri S.B. Yadaw, Head Composite material Division. Special thanks to Mrs. Poonam Awasthi for helping us in DSC analysis. References 1. Kelly, M. E. (1976). In Bruins, P.E. (ed.), Unsaturated Polyester Technology, pp. 343349, Gordon and Breach, New York. 2. Yeh, H. Y. and Yang, S. C. J. Reinf. Plast. Compos. 1997, 16, 414.

3. Sonti, S.S.; Barbero, E. J. J. Reinf. Plast. Compos. 1996, 15, 701. 4. Ogg C. L.; Porter W. L.; Willitis C.O. Ind Eng Chem Anal Edn 1945, 17, 394 5. Malucelli G.; Gozzelino G.; Ferrero F.; Bongiovanni, R.; Priola, A.. J. Appl Polym Sci 1997, 65,
491.

6. Rodriguez E. L. Polym Eng Sci 1991,31, 1022.


7. Agrawal, S. ; Singhal, R.; Rai, J. S. P.; J. Macromol. Sci. Pure Appl. Chem. 1999, A36, 741

8. Agrawal, S.; Mishra, A.; Rai, J. S. P. J Appl. Polym. Sci., 2003, 87, 1952.
9. Prime, R.B. In Thermal Characterisation of Polymeric Materials; Turi, E.A., Ed.; Academic Brooklyn, 1981, p-1380. 10. Rey, L.; Duchet, J.; Galy J.; Sautereuu, H.; Vougner, D. ; Carrioon, L. Polymer 2002, 43, 4375. 11. Nielson, L. J Macromol Sci.- Rev Macromol Chem 1969, C3(1), 69. 12. Roy, R.; Sarkar, B. K.; Bose, N R Bull. Mater. Sci., 2001, 137.

Table 1 : Data obtained from dynamic DSC scans

S. No.

Samples

Ti (oC) 88.2 67.1 60.9 51.8

Tonset (oC) 97.4 89.9 82.9 62.5

Tp (oC) 110.1 114.4 117.3 127.7

Tstop (oC) 132.3 142.1 147.1 153.6

H (Jg-1) 80.1 75.9 73.1 70.8

tc(min)

Tg

1 2 3 4

V-1 V-2 V-3 V-4

60.5 59.5 58.2 57.5

86.0 75.0 74.8 74.3

Table 2: Data obtained from TG/DTG traces of prepared samples


S.No. Sample s EVER-1 EVER -2 Ti (0C) Tmax (0C) 490.8 490.0 Tf (0C) 600 700 ML (%) 77.4 79.5

1 2

250 252

3 4

EVER -3 EVER -4

351 260

488.0 488.1

700 750

76 79.6

Tq : Initial degradation temperature: Tmax : Peak degradation temperature: Tf: stop degradation temperature: ML: Mass Loss

Fig. 1: DSC scan of vinyl ester resin, sample V-3

Fig. 2: TGA scan of vinyl ester resin, sample V-3

Fig. 3: DMA trace of vinyl ester resin, sample V-3

Fig. 4: SEM of vinyl ester resin, sample V-3