Inuence of Ultrane Zinc Borate on the Thermal Degradation Behavior of a(Low-Density Polyethylene)/ (Intumescent Flame Retardant) System

Zhiping Wu,1 Yunchu Hu,1 Wangen Shu2 1 School of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha 410004, China
2

School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China

The thermal degradation behavior of low-density polyethylene (LDPE), LDPE treated with an intumescent ame retardant (LDPE/IFR), and LDPE treated with an intumescent ame retardant and ultrane zinc borate (LDPE/IFR/UZB) was studied by (thermal gravimetric)(differential thermal) analysis (TG-DTA) and cone calorimetry. The results of TG-DTA showed that the initial degradation temperature increased, thermal degradation rate decreased, and the residual char amount increased substantially during the Pyrolysis process when ultrane zinc borate was introduced into the LDPE/IFR system. The mass-loss rate (MLR) curves and mass curves obtained by cone calorimetry showed that UZB could decrease the MLR and signicantly enhance the residual char amount of LDPE/IFR during the combustion process. The results of Fourier transform infrared spectroscopy implied that a graphite-like char and aromatic structures containing P-O-P, P-O-C, and B-O-B bonds were formed when LDPE/IFR/UZB was heated at high temperature. Scanning electronic micrographs of residual chars showed that ultrane zinc borate improved char quality. X-ray diffraction Studies implied that boron orthophosphate (BPO4) formed in the residual char may play an important role in improving the structural properties of the char and is responsible for its good quality. J. VINYL ADDIT. TECHNOL., 15:260265, 2009. 2009 Society of Plastics Engineers

INTRODUCTION Low-density polyethylene (LDPE) possesses good electrical insulation Properties, low cost, and easy processability but facile combustibility (LOI \ 18), The limiting oxygen index of a material is determined as: LOI 100 3 [O2]/([O2] [N2]), where [ ] is the volume concentration

Correspondence to: Z. P. Wu; e-mail: wuzhiping02@163.com DOI 10.1002/vnl.20215 Published online in Wiley InterScience (www.interscience.wiley. com). 2009 Society of Plastics Engineers JOURNAL OF VINYL & ADDITIVE TECHNOLOGY 2009

of each gas in the air stream. Melt dripping limits its applications. It is essential to improve the ame retardancy of LDPE for reducing the hazard of re. The traditional method to improve the ame retardancy of LDPE is to introduce a halogen-containing ame retardant into the polymer matrix. However, LDPE treated with halogen-containing ame retardants would produce harmful and corrosive hydrogen halide and dense smoke. Intumescent ame retardant (IFR) and inorganic ame retardant are effective halogen-free ame retardants [14]. The ame-retarding behavior of IFR for the polymer is the formation of an expanded charring layer at the burning surface, so that oxygen and heat transfer toward the undecomposed bulk are prevented. The typical IFR formulation constitutes a carbonic agent, carbonic catalyst, and blowing agent. In recent years, polyethylene treated with IFR has attracted some interest [5, 6]. Zinc borate is an effective inorganic ame retardant and possesses the characteristics of ame retarding, smoke suppression, extinguishing dripping, promoting charring, etc. [7, 8]. Reduction of particle size is necessary for improving the compatibility which is related to the high tensile strength and elongation of composites. The effect of ultrane zinc borate (UZB) and IFR on the mechanical and ame-retarding properties of LDPE has been described elsewhere [9, 10]. In order to understand further the synergist ame-retarding mechanism of UZB and IFR in LDPE, it is important to study the inuence of ultrane zinc borate on the thermal degradation behavior of the LDPE/IFR system. Thermogravimetric-(differential thermal) analysis (TGDTA) was often used to investigate the thermal degradation behavior and ame-retarding mechanism of ameretarding polymers [11, 12]. In recent years, Fourier transform infrared (FTIR) spectroscopy was frequently employed to study the functional groups of residual char, which can give more information on the thermal degradation behavior of polymers [13, 14]. Scanning electron micrographs (SEMs) were also used to study the structure

TABLE 1. Composition of samples and the results of LOI and UL94 tests. * Ultrane zinc borate 0 0 4.2

Sample LDPE LDPE/IFR LDPE/IFR/UZB

*

LDPE 100 100 100

IFR 0 30 25.8

LOI 17.8 24.5 26.2

UL-94 rating Burning V-1 V-0

The mass ratio of compositions.

of residual char, which can provide positive evidence for the thermal stability mechanism [15]. This work was devoted mainly to studying the inuence of ultrane zinc borate on the thermal degradation behavior of an LDPE/IFR system on the basis of LOI, UL-94 tests, TG-DTA, FTIR, and cone calorimeter tests. Analyses by SEM and XRD were also employed to understand further the thermal stability mechanism. EXPERIMENTAL Materials Low-density polyethylene (LDPE 1F7B) was supplied by Beijing Yanshan Petrochemical Co. Ammonium polyphosphate (APP; average particle distribution 10-55 lm, degree of polymerization [ 1500) was supplied by Zhejiang Longyou GD Chem. Co. Pentaerythritol (PER) was obtained from Shanghai Chemical Agent Station. The IFR (blends of APP and PER, the mass ratio of APP to PER was 3:2), and ultrane zinc borate (2ZnO.3B2O3.3.5H2O) were prepared in our laboratories (average diameter 73 nm and 90% particle diameter below 100 nm) [16]. Sample Preparation The compositions of samples were as listed in Table 1. The IFR or the complex of IFR and UZB were mixed with LDPE in a two-roll mixer (SK-160B, Shanghai, China) at 1201308C for 20 min. The mixed samples were pressed into 3-mm sheets in a vulcanizing press (DLB500 3 500, Wuxi, China) at 1301408C for 4 min, and samples of various sizes were obtained according to the testing standard. Measurements The limiting oxygen index (LOI) test was performed according to ISO 4589 in an oxygen index tester (JF-3, Nanjin, China); the samples were 130 3 6.5 3 3.0 mm3 in size. The UL-94 test was performed according to ANSI/ UL-94-1985 in a vertical burning tester (CZF-2, Nanjin, China); samples were 130 3 13.0 3 3.0 mm3 in size. The TG-DTA was conducted from ambient temperature to 8008C at a heating rate of 108Cmin21 in static air

by using a differential thermal analytical balance (HCT-2, Beijing, China). Samples weighing about 7.5 mg were analyzed in ceramic pans. Cone calorimeter tests were performed by using a Stanton Redcroft cone calorimeter following the procedure dened in ASTM E 1354. The samples were put in horizontal orientation at an incident ux of 35 kWm22. Sample size was 100 3 100 3 3 mm3, and the sample area exposed to the incident irradiance was 88.4 cm2. The results are the average values from three tests, and the variation of each test was less than 15%. The residual char of LDPE, LDPE/IFR, and LDPE/ IFR/UZB heated at different temperatures for 30 min was characterized via FTIR (Nicolet 380 FT-IR, Thermo Electron Corporation, USA) by using KBr pellets. The ratio of KBr to residual char was (100-200):1, and the mixture was ground uniformly in an agate mortar under infrared light. Films were obtained by compression molding. The micrographs of residual char were observed with a scanning electron microscope (JEOL JSM-6360LV scanning electron microanalyzer). The residual chars obtained from LDPE/IFR and LDPE/IFR/UZB heated at 4008C and 5508C for 30 min were coated previously with a conductive gold layer. The XRD patterns of residual char obtained from LDPE/IFR/UZB heated at 5508C for 30 min were obtained with an X-ray diffractometer (D/Max 2500PC, Japan) using Cu Ka1 0.154056 nm radiation.

RESULTS AND DISCUSSION LOI Value and UL-94 Test The data presented in Table 1 indicate that the ame retardancy of LDPE increased substantially when 30% of the IFR was introduced into the LDPE. The LOI value of the LDPE/IFR was 24.5. Although the LOI value of the LDPE/IFR/UZB (26.2) only increased a little compared to that of the LDPE/IFR, the UL-94 test of the LDPE/IFR/

FIG. 1. TG curves of LDPE, LDPE/IFR, and LDPE/IFR/UZB.

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FIG. 2. DTA curves of LDPE, LDPE/IFR, and LDPE/IFR/UZB.

UZB reached the V-0 rating, compared to the V-1 rating of the LDPE/IFR.

Thermogravimetric-(differential thermal) Analysis (TG-DTA) Thermal analytical techniques are effective methods to investigate the thermal degradation behavior of ameretarding materials. The TG and DTA curves are shown in Fig. 1 and Fig. 2. The thermal parameters of LDPE, LDPE/IFR, and LDPE/IFR/UZB are presented in Table 2. It can be seen from Fig. 1 and Table 2 that the initial degradation temperature T1% (T1% is dened as the temperature at which 1% of the initial weight has been lost [12]) of LDPE/IFR (2258C) is lower than that of neat LDPE (2508C). However, the maximum mass-loss rate of neat LDPE (1.20%8C21) is larger than that of LDPE/IFR (1.05%8C21), a result which implies that the IFR can decrease the initial degradation temperature and promote earlier charring. The initial degradation temperature T1% of LDPE/IFR/UZB is 2448C, a nding which implies that UZB can improve the heat stability of the LDPE/IFR system. The TG curves of LDPE/IFR and LDPE/IFR/UZB are almost overlapping below 5408C. However, the massloss rate of the latter is obviously lower than that of the former above 5408C, and the maximum mass-loss rate of the latter (0.09%8C21) is lower than that of the former (0.14%8C21) during this stage (5408008C). The residual char amount of LDPE/IFR/UZB (16.4%) is higher than that of LDPE/IFR (9.44%) at 8008C, thus implying that

UZB can protect char and decrease its oxidation speed at high temperature. The shape of the TG curves is interesting in explaining the thermal degradation behavior of LDPE, LDPE/IFR, and LDPE/IFR/UZB. The TG curve of neat LDPE can be divided into two mass-loss stages; the rst stage (250 4658C) is the major mass-loss stage. Oxygen-initiated pyrolysis produces a large amount of combustible gas and leads to a huge exothermic peak that appears in the DTA curve of LDPE. The second stage is attributed to the small amount of residual char oxidizing with increased temperature, but the exothermic peak is small. The protection effect of char on the inner matrix can be ignored owing to minimal aromatized char formation during the pyrolysis process. The TG curves of LDPE/IFR and LDPE/IFR/UZB can be divided into three mass-loss stages. The plateau after the rst mass-loss stage of LDPE/IFR/UZB (3504058C) is more nearly horizontal and broader than that of LDPE/IFR (3553808C), thereby indicating that the char of LDPE/IFR/UZB gives better protection of the inner LDPE compared to that of LDPE/ IFR. The second mass-loss stage can be attributed to the oxidation of char and the degradation of the inner LDPE at the increased temperature. The third mass-loss stage can be attributed to the oxidation (combustion) of the char at high temperature. The mass loss of LDPE/IFR/UZB is smaller than that of LDPE/IFR in the third stage, a result which implies that the antioxidation of the char increased substantially at high temperature when UZB was introduced into the LDPE/IFR system. Interactions among the compounds of a mixture can be revealed by comparing the experimental TG curve with a theoretical TG curve calculated as a linear combination of the TG curves of the mixture ingredients weighted by their contents [17]. The experimental and theoretical TG curves of LDPE/IFR/UZB are presented in Fig. 1. Curve LDPE/IFR/UZB (theoretical) (12b) 3 TG (LDPE/IFR) b 3 TG (UZB), where TG (LDPE/IFR), and TG(UZB) represent the experimental values of LDPE/IFR and UZB in the TG test, respectively, and b represents the mass percent of UZB in the LDPE/IFR/ UZB (b 4.2/130 3 100%). Curve LDPE/IFR/UZB (experimental) represents the experimental values of LDPE/ IFR/UZB in the TG test. Above 6008C, the experimental curve exceeds the theoretical curve. The residual char amounts of the former and the latter are 16.4% and

TABLE 2. Thermal analysis parameters of LDPE, LDPE/IFR, and LDPE/IFR/UZB. Sample LDPE LDPE/IFR LDPE/IFR/UZB T1%/8C 250 225 244 Tmax/8C (DTG/%8C21)1 423 (1.20) 470 (1.05) 455 (1.06) R300/% 94.05 93.67 95.23 R450/% 13.55 63.60 62.51 Tmax(DTG/%8C21)2 520 (0.23) 610 (0.14) 650 (0.09) R800/% 0.50 9.44 16.40

T1%:T1% is dened as the temperature at which 1% of the initial weight has been lost, which can be regarded as the initial degradation temperature; Tmax(DTG)1 and Tmax(DTG)2 correspond to the temperature and mass-loss rate at the maximum mass-loss in the rst and second stage, respectively. R300, R450, and R800 represent the residue % at 3008C, 4508C, and 8008C.

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FIG. 5. Mass curves of LDPE, LDPE/IFR, and LDPE/IFR/UZB. FIG. 3. HRR curves of LDPE, LDPE/IFR, and LDPE/IFR/UZB.

11.1% at 8008C, respectively. The comparison of theoretical and experimental TG curves provided positive evidence that ultrane zinc borate can promote the charring of LDPE/IFR and increase the residual char amount at high temperature. The DTA curves presented in Fig. 2 show that the order of exothermicity is LDPE [ LDPE/ IFR [ LDPE/IFR/UZB. The TG-DTA results show that UZB can play an important role in the thermal degradation behavior of the LDPE/IFR system.

was introduced into the LDPE/IFR system. The mass curves presented in Fig. 5 illustrate that the mass loss of LDPE/IFR/UZB was the smallest (55.4%) when compared with those of LDPE/IFR (70.3%) and LDPE (94.3%) during the whole combustion process. The mass variation in the cone calorimeter tests implies that ultrane zinc borate can improve the charring structure and thus play an important role in protecting the inner matrix from combusting, thereby leading to the reduction of mass-loss rate and the increase of residual char. Fourier Transform Infrared Spectroscopy

Cone Calorimeter Analysis The heat release rate (HRR) is recognized to be the most important parameter for measuring the development and spreading of re. The HRR curves of LDPE, LDPE/ IFR, and LDPE/IFR/UZB are presented in Fig. 3. It illustrates that the PHRR (peak of HRR) of LDPE/IFR/UZB is the smallest (131 kWm22), The PHRR decreased by 72% when compared with that of the LDPE (466 kWm22), and by 46% when compared with that of the LDPE/IFR (244 kWm22). Mass-loss rate (MLR) curves and mass curves of LDPE, LDPE/IFR, and LDPE/IFR/UZB during the whole combustion process are presented in Fig. 4 and Fig. 5. It can be seen from Fig. 4 that the order of the MLR peak values is LDPE/IFR/UZB (0.08 gs21) \ LDPE/IFR (0.12 gs21) \ LDPE (0.2 gs21). These results show that the MLR decreased signicantly when ultrane zinc borate

The FTIR spectra of the residual char of various LDPE formulations heated at 4008C and 5008C for 30 min are presented in Fig. 6 and Fig. 7, respectively. It can be seen from Fig. 6 that the absorption peak of -(CH2)n- n [ 4 (719 cm21) still exists when LDPE, LDPE/IFR, and LDPE/IFR/UZB are heated at 4008C for 30 min. However, the intensity of the absorption peak is LDPE \\ LDPE/IFR \ LDPE/IFR/UZB, an order which demonstrates that better protection of the inner matrix can be obtained when LDPE is treated with the intumescent ame retardant and, especially, with the intumescent ame retardant and ultrane zinc borate. The absorption peaks at 1460 cm21, 1650 cm21, and 515 cm21 are assigned to the aromatic skeleton vibration and its C-H out of plane bending, observations which imply the formation of an aromatic hydrocarbon. The relative intensity of these absorption peaks is LDPE \ LDPE/IFR \

FIG. 4. MLR curves of LDPE, LDPE/IFR, and LDPE/IFR/UZB.

FIG. 6. FTIR spectra of residual char of LDPE, LDPE/IFR, and LDPE/ IFR/UZB heated at 4008C for 30 min.

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and -(CH2)n- n [ 4 (719 cm21) decreased for the residual char of LDPE/IFR/UZB. However, both of these stretching vibration peaks disappeared for the residual char of LDPE/IFR, thereby implying that complete degradation occurred in LDPE/IFR and incomplete degradation occurred in LDPE/IFR/UZB when the samples were heated at 5008C for 30 min. The FTIR results demonstrate that ultrane zinc borate plays an important role in protecting the inner matrix.
FIG. 7. FTIR spectra of residual char of LDPE/IFR and LDPE/IFR/ UZB heated at 5008C for 30 min.

Scanning Electron Micrographs (SEMs) The scanning electron micrographs of the residual chars of LDPE/IFR and LDPE/IFR/UZB heated at 4008C and 5508C for 30 min are shown in Fig. 8. It can be seen from Fig. 8 that the structure of the residual char of LDPE/IFR/UZB heated at 4008C is more condensed than that of LDPE/IFR. The hills and valleys topography and worm graphite structure can be observed from the SEM of the residual sample from LDPE/IFR/UZB and cannot be observed from that of LDPE/IFR after heating at 5508C for 30 min. The ndings of Duquesne et al. [18]

LDPE/IFR/UZB. The stretching vibration peaks of PO (1360 cm21), P-O-P (1100 cm21), and P-O-C (997 cm21) bonds are found in the residual char of LDPE/IFR and LDPE/IFR/UZB, thus indicating that the intumescent char layer contains P-O-P and P-O-C. The stretching vibration peak of B-O-B (629 cm21) is found in the residual char of LDPE/IFR/UZB, a result which implies that borate remained in the residual char. It can be seen from Fig. 7 that the intensity of the stretching vibration peaks of -CH2- (29003000 cm21)

FIG. 8. SEMs of residual char of (a) LDPE/IFR, (b) LDPE/IFR/UZB heated at 4008C and (c) LDPE/IFR, (d) LDPE/IFR/UZB heated at 5508C for 30 min, respectively.

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The FTIR, SEM, and XRD results showed that ultrane zinc borate can cause LDPE/IFR to form a graphitelike char containing aromatic hydrocarbons when exposed to high temperature, and that it can also improve the quality of the char. Boron orthophosphate in the residual char may play an important role in improving its structural properties and is responsible for the good char quality. ACKNOWLEDGEMENT This project was supported by the Creative Funds of Central South University of Forestry & Technology (07Y17) and the National Natural Scientic Funds of China (30871976). REFERENCES
1. O. Mauerer, Polym. Degrad. Stab., 88, 70 (2005). 2. M. Le Bras, G. Camino, S. Bourbigot, and R. Delobel, Fire Retardancy of Polymers: The Use of Intumescence, Royal Soc. Chem. (1998): Cambridge. 3. A. R. Horrocks and D. Price, Fire retardant materials, Woodhead Publishing Limited (2001): Cambridge. 4. T. R. Hull and B. K. Kandola, Fire retardancy of polymers, New strategies and mechanisms, Royal Soc. Chem. (2008): Cambridge. 5. B. Li, S.Y. Sun, and X.C. Zhang, Chem. J. Chinese Univ., 20, 146 (1999). 6. F. Xie, Y.Z. Wang, and B. Yang, Macromol. Mater. Eng., 29, 247 (2006). 7. D.M. Schubert, U.S. Patent 5,472,644 (1995). 8. M. Le Bras, S. Bourbigot, and S. Duquesne, Fire Retardancy of Polymers: New Applications of Mineral Fillers, Royal Soc. Chem. (2005): Cambridge. 9. Z.P. Wu, W.Y. Shu, and Y.C. Hu, China Plast., 20, 69 (2006). 10. Z.P. Wu, W.Y. Shu, and Y.C. Hu, J. Appl. Polym. Sci., 103, 3667 (2007). 11. C. Marazzato, Y. Peneva, and E. Lefterova, Polym. Testing, 26, 526 (2007). 12. W.H. Wu, H.Q. Qu, and Z.J. Li, J. Vinyl Addit. Technol., 14, 10 (2008). 13. J.H. Xu, J.W. Hao, and Y. Zhao, Modern Chem. Indus., 22, 34 (2002). 14. Q. Yao and C.A. Wilkie, J. Vinyl Addit. Technol., 7, 26 (2001). 15. Q.X. Dong, Q.J. Chen, and W. Yang, J. Appl. Polym. Sci., 109, 659 (2008). 16. Z.P. Wu, W.Y. Shu, and Y.C. Hu, China Plast., 19, 83 (2005). 17. F. Samyn, S. Bourbigot, S. Dueuesne, and R. Delobel, Thermochim. Acta., 456, 134 (2007). 18. S. Duquesne, R. Delobel, and M. Le Bras, Polym. Degrad. Stab., 77, 333 (2002). 19. M. Jimenez, S. Duquesne, and S. Bourbigot, Thermochim. Acta, 449, 16 (2006).

FIG. 9. XRD pattern of residual char of LDPE/IFR/UZB heated at 5508C for 30 min.

demonstrated that hills and valleys topography and worm graphite structure favor protection of the inner matrix. The SEMs provide positive evidence that the quality of the char from LDPE/IFR/UZB is superior to that of the LDPE/IFR char, thereby favoring protection of the inner matrix and slowing down the matrix thermal degradation.

X-Ray Diffraction (XRD) The XRD pattern of the residual char of LDPE/IFR/ UZB heated at 5508C for 30 min is presented in Fig. 9. Boron orthophosphate (BPO4) is found in this residual char according to the X-ray diffraction results and JCPDS card No. 34-0132. Jimenez et al. [19] found borophosphate by using solid-state NMR when a mixture of boric acid and coated ammonium polyphosphate was heated at 250, 300, and 4508C. Samyn et al. [17] revealed by using XRD and solid-state NMR that zinc phosphate and borophosphate were formed when zinc borate and ammonium polyphosphate were heated at 5808C. They proposed that borates provide the good structural properties of the char owing to the formation of borophosphate, which is a hard material and also shows good thermal stability. So, boron orthophosphate may play an important role in improving the structural properties of the char and may be responsible for its good quality. CONCLUSIONS The ame retardancy could be improved, and especially, the UL-94 test could reach the V-0 rating when ultrane zinc borate was introduced into the LDPE/IFR system. The TG-DTA and cone calorimeter results showed that the mass-loss rate decreased and the residual char amount increased substantially during the pyrolysis and combustion process when ultrane zinc borate was introduced into the LDPE/IFR system.

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