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, Rogers D. and Van Erp G.
Centre for Excellence in Engineered Fibre Composites, CEEFC University of Southern Queensland, USQ, Toowoomba, QLD, 4350 - Australia
The influence of styrene content and thickness of the samples on the UV curing of Vinyl ester/Styrene resins (VERs) was investigated by DSC and the combination of TGA and FTIR (TGA-FTIR). The glass transition temperatures of the network polymers after curing were found to be lower for the VERs with higher styrene content. The released heat during UV curing further increased the Tg, with this increase being proportional to the volume of the resins. Within the range of thickness investigated (up to 30 mm) the relative amount of emissions of ST, VE and CO2 were found to be the similar at the top and at the bottom of the samples. Similar results were obtained from the TGA analysis, indicating that the VERs were fully or almost fully cured all along the cross section. A good correlation was found between the analysis of the thermal properties by DSC and the results obtained by the TGA-FTIR system.
Keywords TGA-FTIR, Styrene, Vinylester, UV curing, Tg, Heat released, Crosslink density.
Australia. The initial cure at room temperature is followed by post curing at higher temperature. are more reactive than unsaturated polyester resins. INTRODUCTION Vinylester resins are important thermosetting polymers that are widely used in polymer composite manufacturing processes such as hand lay-up. Ph: 61-7-4631 5516. UV light initiates free-radical polymerization with very low activation energy. Ultraviolet (UV) radiation technology is widely used in many industrial applications including electronics. 2). Typically. methyl ethyl ketone peroxide (MEKP) based free radical initiators are used in conjunction with cobalt octoate or cobalt naphthenate promoters. Vinylester resins are typically manufactured via reaction of bisphenol A epoxy resins with acrylic or methacrylic acids. This allows high polymerization rates at room temperature because the rates are not temperature dependent in the early stages(1. usually styrene.au.Correspondence to: Cardona Francisco. Vinylester resins have terminal carbon–carbon double bonds. E-mail: cardona@usq. Fax: 61-7-4631 2110 .edu. so VERs are diluted by adding a low molecular weight co-monomer. 4350. UV radiation technology includes curing of monomeric or oligomeric materials with the aid of UV light. pultrusion and resin infusion. CEEFC Group. QLD. which contain internal carbon–carbon double bonds. USQ University. The low room temperature viscosities of the vinyl-ester resins (VERs) coupled with rapid cure schedules and low cost make them prime candidates for composites in transportation and infrastructure. Toowoomba. and hence. water and food treatment. UV curing technology can offer a cleaner and more cost 2 . chemicals. VERs can be cured with the use of initiators and promoters to generate free radicals through redox mechanisms. The reaction product of these reagents is highly viscous.
vitrification of the network occurs and all reactive groups are frozen in the matrix(10). while consumption of the smaller. the development in the last 15 years of UV initiators with the ‘photobleaching’ effect allows the incident radiation to penetrate progressively deeper into the sample and thus promote a frontal polymerization process(3. 4). In general published work on characterization of UV curing of Vinylesters is quite reduced. 3 . The most common prejudice in the industry against the extensive use of UV curing is the believe that the curing of the composites is limited to the surface and below it the network remains only partially cure due to oxygen inhibition of the UV initiators and/or difussion limitations. which allows for the conversion of methacrylate and styrene groups to be monitored independently. 11) .8). more mobile styrene groups continues for some time before ceasing(9). Further work is required to promote the adoption of UV curing technology for composite manufacture in the large scale industrial production. giving place to the previously reported effect that VERs don’t achieve 100% conversion (9. post-cure above the glass transition temperature (Tg) is necessary to increase molecular mobility and allow full cure to occur. During the curing of VERs it has been observed that the conversion of methacrylate groups is initially faster than styrene. methacrylate group consumption ceases. Towards the end of the cure reaction. The increased speed of cure available through UV curing technology could address both these issues.effective manufacturing processes to the fibre reinforced composites industry in comparison with the traditional thermal induced curing. The free-radical curing of VERs is diffusion-controlled. costs are reduced through improvements in productivity. However. and the time over which Volatile Organic Compounds (VOCs) such as styrene are emitted is significantly shortened. Once the network is vitrified. The cure of VERs has been investigated previously using infrared (FT-IR) spectroscopy(5 . Eventually.
thermal gravimetric analysis (TGA) and a combination of Fourier transform infrared spectrometer and TGA (TGA-FTIR). respectively.com. This study was undertaken using a differential scanning calorimeter (DSC). The fast photobleaching of the phosphine oxide component of the Solcat Initiator allows the incident radiation to penetrate progressively deeper into the sample and thus promote a frontal polymerization process. The received VE45 resin contained a Cobalt Octoate pre-promoter (0. and the second (Hetron 922) with a styrene monomer content of 45% was denoted VE45.5~150 mW/m2/sec). the TGA/FTIR technique is applied as numerous investigations of the thermal degradation of various polymers have shown the advantage of the combined technique of TGA coupled with infrared spectroscopy(12. To our knowledge not previous study of the effect of styrene content on the UV curing of VERs using the simultaneous TGA/FTIR technique have been presented for publication. 13). Also presented in this study is a correlation between the results of thermal analysis of VERs (residual heat of reaction and Tg values) and the analysis of the samples from the TGA-FTIR system.The focus of the present work is to investigate the effect of UV photocuring on the degree of curing and thermal properties of VERs with different styrene content. In this paper. EXPERIMENTAL In this study two different vinylester resins donated by Huntsman Company (Australia) were used. as 4 .au).0 units (137. A powder photoinitiator Solcat – S2 from Soltek Company in Australia (www.soltekonline. The Two VE resins were thoughtfully mixed with 0.5 w/w% of Solcat-S2 and exposed directly to sunlight for 60 min. was chosen to achieve both surface and deep through cure. The measured UV index during the curing of the samples was 5.6%). The first one (Hetron 914) with Styrene monomer content of 22% is denoted as VE22 in this work.5~6.
0ºC/min for modulated MDSC scans. The glass transition temperature (Tg) was determined using the analysis software provided with the instrument. 15 and 30 mm.5 nm increments.determined in the area of Toowoomba (Australia) using a spectral UV measurement system in an environmentally sealed enclosure for automatic measurements at each five minute period of daylight of the spectral solar UV in 0. Sample weights of approximately 10 mg were used in all cases. Spectral and thermo gravimetric data were acquired every 30s with a twocomputer workstation as the sample was heated in the TGA at 10°C/min under a positive flow of nitrogen. Dynamic Scanning Calorimeter (DSC) analysis was undertaken using a Q800 Instrument from TA Instruments. All scans were made in N2 atmosphere and with a heating rate of 20oC/min for Standard DSC runs and 3. Sample weights of approximately 30 mg were used. which gave an increasing thickness of 5. Thermo gravimetric analysis (TGA) was carried out in nitrogen atmosphere at heating rate of 10°C/min from 30°C to 620°C using a Q500-TGA Instrument from TA Instruments. TGA/FTIR system Experiments were performed using an integrated TA Instruments/Nicolet NEXUS Evolved Gas Analysis system. 5 . This system consists of a TA Instruments Q500 thermo gravimetric analyser system fitted with a TGA Interface Unit interfaced to a Nicolet NEXUS FT-IR spectrometer. Spectral searches were done using the OMNIC Search master software incorporated in the Nicolet system and with its vapour phase library and algorithms. The enthalpy of reaction (J/g) and residual heat of reaction were measured from the area under the DSC peaks. Sample sizes for these studies were ca. 20 mg. Different amounts of the two VE resins (25. 50. 100 and 150 gr.). 10. The IR cell and transfer lines between the TGA and FT-IR units were held at 220°C to avoid condensation of gases. were prepared.
Processing of a reactive polymer must be performed at temperatures above the Tg of the cured material in order to reach the maximum conversion. Figure 1 shows the plots for the VER resins of the obtained values of the glass transition temperatures (Tg) from samples taken at the top (directly exposed to UV radiation) and from the bottom of each VER. The main factor affecting the glass transition temperature is the crosslink density (Mc) of the material(16). at which point Tg equals the cure temperature.DSC The glass transition temperature (Tg). It has been suggested that the glass transition temperature could be used to monitor the degree of curing because Tg is sensitive to the resin conversion in the later stage of curing(14. with the Tg for the bottom samples being a bit lower than the values for the top side. The relationship between Tg and the fractional conversion determines the onset of solidification (vitrification). and an increase in styrene content in VERs results in a decrease in the Tg value for the same curing conditions. Figure 2 shows a MDSC runs of VE45 (30 mm thickness) taken after UV curing (top and bottom samples). The results show that the Tg values at the top and at the bottom for the two VERs are similar. Also it is evident that the Tg of the UV cured resins are similar to the Tg values of the fully cured samples (Tg taken from the 2nd DSC run of VE samples in a Heat/Cold/Heat cycle in standard mode). The proximity of the Tg values between the top and the bottom indicates that the VER samples are cured to a similar degree all along the cross section. This may be due to a decrease at the bottom of the resins in the intensity of the incident light. The dependence of the glass transition temperature 6 . 15). is one of the most important parameters that characterises glassy polymers.
The relationship between Tg and the fractional conversion determines the onset of solidification (vitrification).Top VE22 . With the MEKP curing of VERs we found a clear correlation between the applied postcuring temperature. as a result of its effect on the crosslink density of the cured material. VE45 . with thickness less than 1 mm).Bottom 120 115 110 Tg (oC) 115 Tg (oC) 0 5 10 15 20 25 30 110 105 100 95 90 105 100 95 90 0 5 10 15 20 25 30 Thickness (mm) Thickness (mm) Figure 1.on 1/Mc has been reported as typically linear relationship(16.Bottom 135 130 125 120 VE22 . the degree of curing (%) and the obtained Tg values(19). the glass transition temperature displays a smooth variation with respect to crosslink density for the vinyl ester/styrene system.22) has been suggested that the glass transition temperature could be used to monitor the degree of curing because Tg is sensitive to the resin conversion in the later stage of curing. at which point Tg equals the cure temperature (Tc). with an increase in the initial content in the resin resulting in a reduction on the value of Tg. Our results confirm this trend that the increases in styrene content in the VERs results in lower Tg values. Change in the Tg values with thickness for the UV cured VERs (0 Thickness: the Tg of a cured thin film of the resins. 17). The values of the residual heat of reaction (J/g). The styrene content appears to have a significant plasticizing effect on the network of the VERs. We reported a similar behaviour of the Tg values for the MEKP curing of the VERs in a previous publication(19). as calculated from the DSC results. In previous studies(20 . Although unusual departure from the typical linear dependence of Tg on 1/Mc has been observed in VERs(18).Top VE45 . for the two VER 7 .
15 VE22-Top VE22-Bottom VE45-Top VE45-Bottom 10 Enthalpy J/g 5 0 5 10 15 20 25 30 Thickness (mm) Rev Heat Flow (W/g) Heat Flow (W/g) 8 .04 -0. indicating a better curing in the top than in the bottom.02 -0. Samples taken from the top and bottom of a UV cured sample with 30 mm thickness. the degree of curing of the top samples in comparison with the respective bottom samples.00 -0.samples with increasing thickness are presented in Figure 3.06 -0. This may be due to a decrease at the bottom of the resins in the intensity of the incident light.03 -0.14 20 Exo Up -0.08 40 60 80 100 120 140 160 Universal V3. is slightly higher for all different thickness.05 -0.06 -0.12 -0.02 -0.10 -0. the degree of curing of VE22 and VE45 resins are close to fully cure (~100%) for all VERs samples after UV curing.04 Nonrev Heat Flow (W/g) -0. The Tg was taken from the Rev. However.01 -0. Therefore.04 -0. 0.02 -0. the remaining heat of reaction (J/g) after UV curing is very low in comparison with the total heat of reaction for 100% curing for the VE22 (272 J/g) and VE45 (352 J/g) resins. Clearly.9A TA Instruments Temperature (°C) Figure 2.08 -0.00 0. Heat Flow runs (solid lines). MDSC scans of VE45 resin.
This is due to the higher increase in temperature in VE45 during UV curing. During the UV curing there is a heat release as a result of the exothermic curing reaction of the VERs. The larger the volume of the VERs the higher is the amount of released heat. As a result. This increases in temperature induces further crosslinking of the VE/ST network and accounts for the higher Tg value of the VERs with increasing thickness (see Figure 1). there is a significant increases in the temperature in the bulk of the samples with thickness during the UV curing process. 130 120 110 VE22 -15 mm VE22 .30 mm Temperature (oC) 100 90 80 70 60 50 40 30 0 10 20 30 40 50 60 Time (min) Figure 4.30 mm VE45 . as the plots in Figure 4 indicates. Plot of the residual heat of reaction (J/g) vs thickness for the VERs.15 mm VE45 . Change of temperature in the bulk of VERs with time during UV curing. FTIR/TGA System 9 . This increase in the Tg value with thickness is higher in VE45 than in VE22 and in particular for the top samples the temperature increases goes well above of the value for a 100% curing (108oC). as shown in Figure 4.Figure 3. in comparison with VE22.
The TGA was recorded in N2 atmosphere and with 10 oC/min heating rate. For the VERs in our study.in Styrene) and 945 cm-1 (vinyl group CH2=CH. In order to evaluate the evolution of styrene monomer present in the vinyl ester during the thermal degradation of the two VERs. a TGA-FTIR run of a polystyrene (PS) sample mixed with styrene monomer was undertaken at the same experimental conditions as for the run taken for VERs (TGA furnace in N2 atmosphere and with a heating rate equal to 10oC/min). 3D Waterfall of VE22 (5 mm thickness. the absorption peaks at 910 cm-1 (CH2=CH. 23). The obtained 3D waterfall of IR spectra is presented in Figure 6.10 10 0. top sample).00 3000 Wavenumber (cm-1) 1 2000 1000 Figure 5.05 0. As mentioned above. the UV curing process of the VER system was carried out by exposing the samples to sun light. min 10 . The full curing of the resins is confirmed by the IR spectra. The styrene monomer evolved from the TGA furnace in the first 15 min (up to 160 oC). 60 50 40 30 20 0.in VE) were reduced or almost disappeared with the full curing of the resins(5-8. after that there are not further gas emissions until reaching the decomposition temperature of PS at about 370oC (40 min in the Waterfall diagram in Figure 6). and as previously reported.The 3D diagram of the IR spectra of the evolved gases (generated ‘waterfall’ with the OMNIC software) from the TGA furnace of VE22 sample is illustrated in Figure 5.
The conditions are the same as in Figure 5. see Figure 7). In the spectra the Styrene peak is evolving together with the IR bands associated with the Vinyl ester resin such as the bands at 1740 cm-1 (C=O carbonyl stretching vibration) and 1100 cm-1 (symmetric C-O stretching vibration).05 10 0. Significantly. 11 .10 0.Abs 0. the Styrene units are not evolving in the early stages of the TGA thermograph (up to 15 min or 180oC). The vinyl groups on the ends of the VE monomers copolymerize with styrene to form a cross-linked network via bulk free radical chain growth copolymerization. as we previously observed for the same VERs cured with MEKP and thermal treatment (19).25 40 0. induces changes in the kinetics of curing and development of the network that significantly affects the processing characteristics such as viscosity. This is indicated by the presence in the waterfall diagram in Figure 5 of the characteristic peak of styrene at 696 cm-1 (C-H bending vibration of phenyl ring).20 30 min 0. 3D Waterfall of Polystyrene/Styrene. It is clear from spectral comparison of Figures 5 and 6 that styrene units are evolving together with the Vinyl ester groups at the temperature of degradation of VERs in the TGA furnace (~375oC. The extremely high polymerization rates during UV curing. time to gelation and time to vitrification.30 0. while the styrene monomer provides linear chain extension.00 3000 cm-1 2000 1000 Figure 6. in comparison with thermal curing. the photo-curing of VERs appears to consume all the styrene monomer in a copolymerization reaction with the vinyl ester units.15 20 0. It is expected that all these changes will affect the physical and mechanical properties of the cured polymer. This indicates that as opposed to thermal curing. The VE monomer provides cross-linking capacity and branch points for the network. rate of heat evolution.
This similarity in the TGA runs between the top and the bottom samples was observed for all the VE45 and VE22 resins.9A TA Instruments Temperature (°C) Figure 7. 12 . This indicates that the thermal stability is the same at the top and at the bottom. However. 15 mm thickness). TGA thermographs of UV-cured VE45 resins (15 mm thickness). This is consistent with the higher cross-linked network in VE22 samples than in VE45 resins. The thermographs in Figure 7 of the VERs. show the same onset temperature of the degradation and similar amount of non-volatile residues (~7%) for both samples.69°C 80 Weight (%) 60 40 20 0 0 100 200 300 400 500 600 Universal V3. the non-volatile residue (char yield) is consistently higher in the VE22 samples (12~14 %) in comparison with the VE45 (5~8 %). taken from the top and the bottom of the UV cured resins (VE45.120 ––––––– VE45-15 mm .Top 100 374. For the analysis samples (~30 mg) were taken from the top and bottom of the cured resin. as indicated by the higher Tg values in the former than in the latter.Botton –––– VE45-15mm . indicating a similar degree of UV induced curing all along the cross section of the resins. which points to a less volatile emissions from VE22 samples.
0 3.0 10.0 4.9 2.0 27.0 2.5 2. The results of the areas under the Gram-Schmidt peaks for all VERs are shown in Table 1.6 39.0 Intensity top VE Styrene 3.7 31.5 7.0 28.2 2.0 0.8 7.5 1. the higher content of Styrene in VE45 than in VE22 results in a higher peak for Styrene in the former than in the latter.6 3.4 30.5 5.4 3.7 Table 1.0 0. Results of the areas under the peaks taken from the Gram-Schmidt plots of VERs.5.7 2.3 27.2 2.0 0 10 20 30 Time (minutes) 40 50 60 5.2 10.0 4.0 0 10 20 top Styrene VE 30 Time (minutes) 40 50 (a) (b) Figure 8.2 31.0 31.6 31.6 7.0 Vinylester Top Bottom 26. Gram-Schmidt plots of the Styrene (910 cm-1) and VE (1740 cm-1) IR peaks for VE22 (a) and VE45 (b) resins.2 9.6 11.0 1.5 0. The Gram-Schmidt plots obtained from samples taken from the top (exposed directly to UV light) and the bottom of the cured VERs (15 mm thickness) are presented.5 Intensity 3.3 30. Figure 8 shows the Gram-Schmidt plots of the areas under the IR bands of styrene units (696 cm-1) and VE (1740 cm-1) for the two VERs. Also in Figure 8 is evident that the intensity of the Gram-Schmidt peaks (Styrene and VE) for the top sample are higher than the equivalent peaks for the bottom sample.9 2.0 20.5 4.5 4.0 2. 13 .4 37.9 8. SAMPLE VE22 – 5 mm VE22 – 10 mm VE22 – 15 mm VE22 – 30 mm VE45 – 5 mm VE45 – 10 mm VE45 – 15 mm VE45 – 30 mm Styrene Top Bottom 2.0 33.5 2.2 35.5 1. As expected.0 1.5 3.5 5.4 38.5 0.
5 0. There is not a clear trend in the values of the relative concentrations of emitted VE between the two VER samples and this could be due to the Vinylester being the main component in both resins.0 5. as shown in the Gram-Schmidt plots of Figure 9. However. The results in Table 1 indicates that the relative amount of emitted Styrene is consistently higher for VE45 in comparison with VE22 for all samples. The TGA-FTIR scans were taken from the top of the two VERs with 5 mm thickness. 6. toluene. the measured relative concentration of emitted VE does not give a similar result when comparing the VE values for the two VERs (see Table 1).The thermal degradation of PS proceeds by a random scission process(24). During the thermal degradation of VERs the CO2 is generated from the chain scission and decomposition of the vinyl ester units. styrene and styrene oligomers begins at about 350oC(25). The first at lower temperature (375oC or 40 min) and the second at 14 . Gram-Schmidt plots for the emitted CO2 from the VERs.5 1.5 5.0 VE22 Intensity 3.0 2.0 1. The emissions of CO2 from the UV cured VERs are significantly different from VE22 and VE45. as obtained from the area under the Gram-Schmidt plots) than in VE45 (~30 units).0 10 20 30 40 50 VE45 Time (minutes) Figure 9. The higher content of VE in VE22 results in a proportional higher CO2 emissions (~60 units. Figure 9 also shows two separate peaks. indicating that there are two different types of emitted CO2.0 0. where the production of benzene.5 4.5 3.5 2.0 4.
CONCLUSIONS The TGA/FTIR technique was successfully used to investigate the stability and curing induced by UV photo-initiation on a set of VERs with different thickness. The DSC and TGA results also confirms that the VE/ST network after UV curing is fully or almost fully cured all along of the cross section. ACKNOWLEDGMENT The authors would like to thank Huntsman Chemical Australia for the donation of the vinyl ester resins used in this work. whereas the second is emitted from the CO2 formed from the chain scission of C-O in the main chain. within the thickness of the resins investigated in this work.higher temperature (470oC or 50min). The relative amount of CO2 emitted is similar for the top and bottom of each of the VERs. within the thickness investigated in this work. not separate or early emissions of Styrene were detected indicating that there is not a residual monomer or unattached polystyrene in the VERs after UV curing. and the Styrene evolves simultaneously with the VE groups at the same temperature. 15 . This technique provided a more complete understanding of the curing process by monitoring the emissions of Styrene. In addition. VE groups and CO2 from the top and bottom of a set of samples with different thickness. This indicates that the UV curing induces a full consumption of the initial Styrene in the copolymerization and formation of the cross linked network. This is similar to the results obtained from the TGA analysis and indicates a similar degree of curing along the cross section of the resins. The first one correspond to the CO2 formed from the C=O on the side chain. The results indicate that the emissions of Styrene units is higher for the VER with higher styrene content.
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