Malaysia Polymer International Conference (MPIC 2009)

EFFECT OF ANTIOXIDANT AND FLAME RETARDANT ADDITIVE ON THERMAL DEGRADATION AND FLAMMBILITY OF SBR FILLED EPS/UPR COMPOSITE

Rashidan Khosim, Rahmah Mohamed, Nor Zaini Ikrom Zakaria, Mohd Hafiz Makul Polymer Technology Programme, Faculty of Applied Sciences, Universiti Teknologi MARA Malaysia, 40450 Shah Alam, Selangor, Malaysia Email: sidan_frank@yahoo.com

Abstract Thermal Degradation and Flammability of composite especially for building and construction industry application are important to pass specification set for flammability of plastics composite. Additives such as antioxidant (AO) and flame retardant (FR) are incorporated to UPR /EPS resin in this work to impart flammability resistance and increase thermal decomposition of said composite. Thermal

decomposition of composite were characterized via Thermal Gravimetric Analyser of 20% SBR with and without AO and FR additives. Thermal decomposition was also followed for combination of AO and FR. Flammability test were also performed and linear burning rate were evaluated. It was found that increase in thermal stability was found for combined AO and FR additive system. There were synergistic mechanism towards degradation resistance with combined AO and FR additives at high temperature range; Tmax deg rate of 530C were found for filled composite system. It was also found that high % Residue or char yield for system SBR AO and SBR AO FR showed that AO prevent oxidative process and increase the char yield of the product. Linear burning rate for SBR-FR were reduced by more than half if flame retardant is incorporated. Hence, it was shown that addition of antioxidant and flame retardant additives had enhanced thermal stability of SBR/EPS/UPR composite system Keywords: Flammability, Thermal degradation, UPR composite, Antioxidant, Flame Retardant

1.

Introduction

Flame retardants are incorporated in FRP composites to achieve a desired fire resistance. Flame retardants suppress combustion by acting either through the vapor phase or the condensed phase by chemical and/or physical mechanisms. Lu and Hammerton provide had summarized common types of flame retardants and mechanism of action. (.Lu., 2002) Phosphorus (PN) compounds based on phosphoramidate were used and flame-retarding efficiencies had been evaluated by the limiting oxygen index (LOI) and UL-94 vertical test methods. Nyugen and Kim found that bisphosphoramidates are more thermally stable and produce more
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charred residues when compared to the corresponding bisphosphate compounds upon addition of 3 5 wt%. With bisphosphoramidate FRs, remarkably high residues at 600 C remained.

Thermogravimetric analysis (TGA) results indicated compounds work in condensed phase rather than in gas phase. (Nyuyen & Kim, 2006). Environmentally friendly fire retardant vinyl ester resin composites by blending fatty acid vinyl ester (FAVE) resins with environmentally friendly fire retardants: polyhedral oligomeric silesquioxanes (POSS) was investigated recently. POSS additive maintained resin viscosity, improved Tg, increased cross-link density, and flame retardance. However, the flame retardance of even this relatively high performing POSS-filled composite was very poor compared to that of brominated resins.(Glodek et al, 2008). Intumescent flame retardantmontmorillonite synergism in nanocomposites had also been investigated ( Haiyun et al.2008) Preparation And Properties Of New Flame Retardant Unsaturated Polyester Nanocomposites Based On Layered Double Hydroxides had been investigated too ( Pereira et al 2009). Flame retardants can be incorporated into polymeric materials either as additives or as reactive materials. (Burchill, 1996) Unsaturated polyester matrix composites have been used for many years in a broad technology fields such as naval construction, offshore applications, waterlines, building construction. Unsaturated polyester is an economical thermoset material that is widely used due to its excellent process ability and good crosslinking tendency as well as mechanical properties when cured. Expanded polystryrene (EPS) sheet has been used as core material for sandwich core composite door shutter to replace wooden door shutters in building. (Vaidya et al., 2000). Studies had been done on use of EPS incorporated into Unsaturated Polyester resin (UPE) with relevant diluent.2. Toughening of the unsaturated polyester resin is very important to increase impact performance especially for building structures. Contrary to epoxy resins, for toughening of vinyl ester, nitrile rubbers modifer were mostly incorporated in VE resin (G ryshchuk et al., 2002). Different plastic pocess decomposition temperature profile limit. Decomposition of polymer can be evaluated through thermal thermal gravimetric analysis(TGA) and its derivative (DTG) thermogram. In most cases, decomposition occurs via free radical chain reactions, initiated by traces of oxygen or other oxidizing impurities, which are trapped in all plastics during manufacture. The oxidative degradation of polymers usually proceeds via the formation of hydroperoxide groups. ( Regnier et al, 1995). Ignition depends on numerous variables such as oxygen availability, temperature, physical and chemical properties of polymer. Reaction with oxygen is exothermic and if sufficient energy is available, overrides the endothermic pyrolytic reaction and initiates flame spread. Flame spread, or the rate of travel of a flame front under given conditions of burning, is a measure of fire hazard. The spreads of flame along the surface of a material can transmit fire. As for Ignition, flammable gases formed by pyrolysis, mix with atmospheric oxygen, and reach the lower ignition limit and are either ignited by an external flame or, if the temperature is sufficiently high, it will selfignite.
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This paper emphasized on degradation behavior of SBR modified EPS/UPR composite system with AO and FR content and SBR and flame retardancy is evaluated as well. Thermal analysis(TA) has assumed an important role in the study to give information and the development of the new composites materials.[ Mortaigne, 1999]. Thermal stability of composite were investigated by Thermal Gravimetric Analysis (TGA) via the profile of their thermal decomposition. The aim of this work was to evaluate the thermal degradation, fire resistance and hardness of different percentage of SBR in UPE-EPS composites and FR with and without Antioxidant.

2.

Material and Methods

The selected thermoset matrix materials used for fabricating composite system is UPR resin system, Reversol consisting of vinyl ester oligomers having density of 1.12 g/cc, viscosity of 450-600cps with 41-44% styrene content. Pack of methyl Ethyl Ketone Peroxide (MEKP) as initiator and Cobalt solution as promoter are supplied together with UPE resin by Revertex Sdn Bhd. EPS (expanded polystyrene) or styrofoam from waste material and General Purpose SBR, SBR 1502 were used. The SBR 1502 is a cold polymerized styrene-butadiene copolymer with styrene content of 23.5% supplied by Lembaga Getah Malaysia (LGM). Irganox 186, antioxidant was supplied by Ciba Geigy and Phosphate Ester as flame retardant additive was supplied by Asachem Sdn Bhd.

2.1

Composite Fabrication and Testing

Recycled Expanded Polystyrene (EPS) was blended with UPE resin with high speed agitation mixer and complete dissolution were attained to ensure gaseous present are eliminated from the mixture with vacuum suction. SBR was masticated first via two roll mill to ease dissolution process. EPS and SBR content was fixed at 20% parts by weight (pbw) of Unsaturated Polyester resin. Hand lay up process were done onto aluminium mould. FR and AO additive about 0.5 % were added, followed by MEKP and cobalt to EPS/SBR solution. Upon fabrication ; gelation time was set to be about 20 to 30 minutes. Once gel, low pressure press were applied to retain required shape and complete curing were done for 24 hours at room temperature. Thermogravimetric analysis (TGA) was carried out on the composites by means of a Perkin Elmer Thermal analyser at a heating rate of 50 oC/min under nitrogen atmosphere. Temperature range was from 50-1000 oC. Flammability test follows ASTM D635 with prepared specimen size of 125 mm x 20 mm x 3 mm. Fix distance of 75cm for combustion is used to complete flame propagation and the sample been placed to burn in horizontal position by using candle flame at room temperature (RT). Linear burning rate were assessed from time taken to reach specified distance.

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3.

Results and Discussion

To evaluate Thermal degradation properties of UPR/EPS/SBR composites with additive AO and FR, Thermogravimetric analysis (TGA) tests were conducted and the related data were as shown in Table 1. It can be seen that there more than one decomposition products; two to three T
Max. Dec.(

C)

peak were present for all of the material that differ in composition. From the sample degradation profile, Tmax dec. (C ) ,composition of UPR/EPS/SBR with AO and FR were shown to have highest value about 20% to 60% compared to single AO, single FR or without both AO and FR. Addition of FR shows significant thermal decomposition profile for 1st decomposition product at low temperature range. Temperature at Tmax deg were increased significantly upon synegrgistic combination of AO and FR but FR had introduced lower thermal stability initially where addition of FR only had lowered the 1st decomposition product temperature to160C. Similar synergistic thermal stabilization mechanism were depicted for 2nd decomposition product where its Tmax deg were increased significantly . Upon higher temperature range, 3rd decomposition product also showed higher Tmax deg at 897.85C compared to 761.52C which is without FR.

Table 1: Data of TGA and DTG curve Sample UPR/EPS 1st Curve DTG 2nd Peak Curve DTG 3nd Peak Curve DTG Peak Temp. Dec. at early stages (C) Temp dec. at Residue final stages (C) (Wt. loss) (%) 5% SBR SBR-AO SBRAO/FR SBR-FR 308.18 160.11 529.46 453.89 235.46 333.84 482.26 492.61 3.71 251.17 254.81 451.17 457.08 761.52 897.85 276.23 275.68 10% 354.2 90% 95%

Decomposition Decomposition Decomposition Temp.(C) Temp.(C) Temp.(C)

482.41 494.54 1.21 1.25

353.37 496.92 741.8

318.646 403.05 546.16 836.05 2.28

With AO additive only, thermal stability does not show any improvement except above 450C where near 90% degradation starts to occur. AO proved to significantly increase thermal stability at high temperature range above 700C where temperature degradation at 95% were increased up to 741.8C as compared to only 494.54C when degradation persists without AO. AO could probably the main controlling factor for thermal stabilization at high temperature range. Highest thermal stability was depicted by use of AO and FR addiitives in combination; specifically through the Temperature at 5%, 10%, 90% and 95% decomposition stage. Residue or
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char yield left were greater compared with AO only. This indicated that at near 900C both AO and FR is the agent controlling factor to enhance the stability of the composite system at high end temperature range.FR effect were also shown. But when the FR by itself, thermal stabilisatioon did not work as effective as when combined with AO.Therefore, the AO and FR are required to be use together in formulation to get highest thermal decomposition profile to enhance thermal stability of composite. Figure 1 showed comparison of thermogram of 20% SBR with and without AO and FR additives. Combination of AO and FR additives were found to increase thermal stability of the 20%

SBR composite. There is synergistic mechanism towards degradation resistance with combined AO and FR additives. Tmax system. SBR FR filled additive have similar behavior as SBR unfilled composite. However, SBR AO and SBR AO FR do give better stability at high end temperature range above 500C. This showed that presence of AO cause hindrance to degradation process whereby antioxidant could have quench of the formation of free radicals which initiate pyrolysis reaction upon chain breakdown reaction. However, AO did not affect any thermal degradation for low temperature range as its Tmaxdeg and % wt loss with and without AO is similar. High % Residue or char yield for system SBR AO and SBR AO FR showed that AO prevent oxidative process and increase the char yield of the product. Upon additition of these additives, thermal stability is enhanced.
deg

was

530C; this value is well above other 20% SBR filled composite

Figure 1: TGA thermogram of Comparison for with and without AO and FR additive for 20% SBR filled composite

3.1

Flammability test

Table 1 showed the time required to burning the sample at the fixed distance that called elapsed time(s) and the rate of combustion showed by linear burning formulation, V(mm/s) , Linear Burning, V = 60L/ t
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Where: L = the burn length,in milimeters btween reference mark(100-25=75) t = the time(s)(elapsed time from distance of 25mm to100mm reference mark)

Based on Linear Burning formulation, Rate of combustion will be reducing when the longer elapsed time. From table 2, time taken for complete combustion will be increased when AO is incorporated with SBR and also FR with SBR into UPE/EPS composite. The elapsed time was increase when the additive material of AO and FR together incorporate into the UPE/EPS composite. The burning rate, V of the composite with AO and FR shows the lowest at 10.71mm/s compare to the composite without additive at 23.08mm/s. Addition of either AO or FR also reduce the burning rate at 17.65mm/s and 14.29mm/s respectively. This means, incorporation of AO and FR in composition will improve the ability of sample to retard fire.

Table 2: Comparison elapsed time of combustion in different Additive material Additive in UPE/EPS elapsed Composite SBR SBR-AO SBR-FR SBR-AO-FR time(s) 65 85 105 140 LINEAR BURNING,V=60L/t (mm/s) 23.08 17.65 14.29 10.71

From figure 2, shows in decreased rate of combustion when AO and FR were incorporated with UPE/EPS/SBR composite. The lowest burning rate shows by combination of AO and FR in UPE/EPS/SBR composite than the single of AO or FR in the composite. That means the combination of AO and FR additive was gave the synergistic mechanism effect to retard fire, by slower the ignition of fired to the sample. Generally, FR was used to reduce the likelihood of fire starting by providing increased material resistance to ignition and AO was used to increase the degradation of material. Therefore, synergistic effect of AO and FR is good flame retardants to retard and to delay the spread of flames. This provides extra time in which either the fire can be extinguished or an escape can be made. Its save lives and property and provide safer materials without compromising performance.

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LINEAR BURNING,V=60L/t (mm/s)

30 25 20 15 10 5 0 SBR SBR-AO SBR-FR SBR-AO-FR

ADDITIVE COMPOSITE

Figure 2: Comparison rate of combustion in different composition of AO and FR

4.

Conclusion

In conclusion, by using UPE as the polymer host, the EPS added with SBR and fillers could be prepared by using Hand Lay-Up technique.. In TGA, composition of UPR/EPS/SBR that contained AO-FR give good result in term of thermal stability and also achieve high temperature to decomposition. In terms of flammability, shows the formulation with AO and FR additive gave better burning rate which is just only 10.71mm burning for 1 second that gave 100% or 2 time decrease in burning rate. Although this result showed that UPR/EPS/SBR with filler AO-FR gave best performance for the composite system.. Properties UPR/EPS/SBR composites with added FR or AO can be applied for various specific applications such building and architectural application.

5.

Acknowledgement

I would like to thank the laboratory technician and staffs for their assistance during the fabrication and testing of the composite at Polymer Workshop and Physical testing lab at Faculty of Applied Sciences, UiTM Shah Alam. I am also indebted to my colleagues and lecturers for discussions related to this work

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