Thermogravimetric Studies of the Decomposition Kinetics of Four Different Hevea Rubber Clones using Ozawa’s Approach Eliton S. de Medeiros', Rogério M. B. Moreno?, Fabio C. Ferreira’, Neri Alves’, Aldo E. Job’, Paulo S. Goncalves* and Luiz H. C. Mattoso?* ‘Departamento de Engenharia de Materiais, Universidade Federal de Sao Carlos, 13.565-905, Sao Carlos-SP, Brazil. 7Embrapa Instrumentacado Agropecuaria, C.P.741,13. 560-970, Sao Carlos-SP, Brazil. ? Departamento de Fisica, Quimica e Biologia, Universidade Estadual Paulista, C.P. 467, 19.060-900, Presidente Prudente-SP, Brazil. “Instituto Agronémico de Campinas, C.P. 28, 13.001-970, Campinas-SP, Brazil. Received: 25 May 2003 Accepted: 8 July 2003 ABSTRACT Thermal degradation behavior of rubber from four rubber clones (RRIM 600, PB. 235, GT1 and IAN 873) of the Hevea brasiliensis species was studied by thermogravimetry (TG) using Ozawa’s approach to assess the kinetic parameters of the decomposition process. These parameters indicated that the thermal behavior of natural rubber depends on the type of rubber clones studied. The order of reaction was found to be dependent on the degree of conversion indicating that both the early and the latter stages of rubber degradation follow zero or pseudo- zero order kinetics whereas the intermediate stages follow a first order kinetics and the activation energy was found to be dependent on the degree of conversion and the type of clone used ragging from 148 to 236 kJ/mol, Rubber from clones [AN 873, GT1 and RRIM 600 presented the best overall thermal stability whereas the clone PB 235 presented the lowest thermal stability, therefore in agreement with the plasticity retention index (PRI) behavior. 1. INTRODUCTION In recent years natural rubber (NR) has been increasingly utilized in quite widespread applications favored by its unique properties and the ever- “Corresponding author: mattoso@cnpdia.embrapa.br Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003 189ES. de Medeiros, R.M.B. Moreno, F.C. Ferreira, N. Alves, A.E. Job, P.S. Goncalves and L.H.C. Mattoso increasing need to deduce residues accumulation from synthetic polymers, which are difficult to degrade and are not environmental friendly materials. Natural rubber is a high-molecular-weight cis-1,4-polyisoprene that can be obtained from different species of plants. However the most outstanding species is Hevea brasiliensis due to its facility of plantation and adaptation to different climates, and high rubber content (30-36%) in the latex. This natural occurring polymer is extensively cultivated in many countries due to its elastic behavior after deformation in tension or compression and high resistance to aggressive environments — completely maintenance free"), Brazilian researchers have used genetic improvement of the Hevea species in order to increase the production and to develop new clones more appropriated to Brazil's soil and climate, suchas the clone IAN 873 developed by Instituto Agronémico do Norte (IAN), a secondary clone whose parental ones are PB 86 and FB1717 (primary clones). With an average high production, the first harvests of IAN 873 can be expected with trees that are only three years old, two years earlier than the normal harvest period of other commercially available clones), Natural rubber properties depend on many factors such as clonal and seasonal variations, which may affect the polymer performance in use. An important property that must be understood is its thermal behavior, since in many applications such as in flexible pipes used in chemical industries, natural rubber may be in direct contact with hot substances. The understanding of polymer thermal behavior is very important because several conventional techniques used in plastic processing industry are, in general, carried out at high temperatures and, furthermore, several physical properties and technological applications are influenced by temperature resistance®. One well-known fact is that rubber degradation occurs during storage manufacture and service leading to a significant loss in mechanical and thermal properties. In this sense, thermogravimetry (TG) has been carried out and Ozawa’s approach" have been used to assess the kinetics parameters in order to understand the thermal behavior of the natural rubber extracted from the clones RRIM 600, PB 235, GT1 and IAN 873. 2. EXPERIMENTAL Latex from 12 rubber trees of each of four clones analyzed (RRIM 600, PB 235, GT1 and AN 873) from Votuporanga plantations located at Sao 190 Progress in Rubber, Plastics and Recycling Technology. Vol. 19, No. 4, 2003Thermogravimetric Studies of the Decomposition Kinetics of Four Different Hevea Rubber Clones using Ozawa's Approach Paulo state, Brazil, were extracted, stabilized and subsequently dried to produce the rubber used in TG measurements. Characterization of the samples used in this study has been reported earlier'67), TG analyses were carried out on a NETZSCH TG 209. Dynamic scans where conducted in a temperature range of 25-600°C, at constant heating rates of 5, 10, 15 and 20°C/min, under nitrogen atmosphere at a flux rate of 15 mL/min. For sample preparation, approximately 10 mg of NR was used in an AIO, crucible. The thermogravimetric curves were analyzed according to Ozawa’s approach in order to obtain the kinetic parameters of rubber degradation. 3. THEORY Many techniques such as differential thermal analysis (DTA), differential scanning calorimetry (DSC) and thermogravimetry (TG) have been largely used to evaluate the thermal degradation parameters of polymers", However, TG has become the most used technique to investigate materials undergoing thermal decomposition", In order to determine the kinetic parameters such as activation energy and reaction order of the thermal decomposition processes, several approaches have been proposed based on empirical Arrhenius-type equations. These approaches use either isothermal or non-isothermal experiments. Since the main disadvantage of the isothermal methods is the time duration required, non-isothermal methods of programmed rates of temperature change have become widely used"). Consider a solid polymeric material undergoing thermal decomposition according to the reaction aA,, — bB,, + cC,,. If the decomposition starts at a temperature (T,) and it is carried out by thermogravimetry at a linear increasing in temperature (T=T,+Bt), where B is the constant heating rate (B= 2, then the time rate of consumption of reagent a(} can be defined by &— pantry (1) Mo-m ™Mo- my with a = being the fraction of A thatundergoes decomposition. Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003 191E.S. de Medeiros, R.M.B. Moreno, F.C. Ferreira, N. Alves, A.E. Job, P.S. Goncalves and L.H.C. Mattoso In this equation, m is the sample mass (subscripts, 0 and f, refer to values at the beginning and at the end of the weight loss due to thermal decomposition). The functions f(o) and k(T) are, respectively, functions of conversion and temperature. In the usual manner, the temperature dependence of the rate of weight loss is assumed to reside in the rate constant through an Arrhenius relationship given by KT) =A ox #) (2) where E is the activation energy, A the pre-exponential factor and R the gas constant. The simplest and most frequently used method for f(a)" is f(a) = (1- ay" (3) where n is the order of reaction. Insertion of the equations 2 and 3 into equation 1 results in da we ptt a- an acne 5 =| 4) RT Integrating this equation from an initial temperature (T,), corresponding to initial degree of convention (a=0), to a temperature (T), which corresponds to any degree of convention (a>0), results in equation 5 fda _f~ da _Af} -E V fen lacar> a] ae) (5) The right-hand side of equation 5 may be solved using the following power series expansion", which results in sai lai elf 3 | ele [eas ay ee] (e+ Ix42) (e+ 1x4 2x43) (6) where x=E/RT. The logarithm of the above expansion was used byThermogravimetric Studies of the Decomposition Kinetics of Four Different Hevea Rubber Clones using Ozawa’s Approach Doyle®® to obtain the equation none f 85 $e (j a )=t(£) (7) 0 The term p(E/RT) in equation 7 is the temperature integral defined by Doyle for 20 eao7 * 6597 + 6697 = 6797 + 6897 © 6907 * 7087 7197 16 20 28 32 24 In(B) 36 196 Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003Thermogravimetric Studies of the Decomposition Kinetics of Four Different Hevea Rubber Clones using Ozawa's Approach Figure 2 (Continued) Plots of In{-In[1-o(T)]} versus In(B) for the rubber clones: d) RRIM 600 Temperature} In{-In[1-o(T)]} 3e Table 1 Values of Ozawa's exponent as a function of temperature for the ruber clones studied Temperature Ozawa's exponent te) GT TAN 873 | PB235_ | RRIM600 327 0.6340.07 | 0.3240.02 | 0.48:0.02 | 0.4340.07 337 0.6940.07 | 0.4540.02 | 0.6120.02 | 0.5520.06 347 0.7840.06 | 0.56+0.03 | 0.75#0.02 | 0.6840.05 357 0.8940.06 | 0.714012 | 0910.02 | 0.8220.05 367 0.9940.11 | 0.834010 | 1.0520.01 | 0.9620.05 377 1.04+0.13 | 0.8640.09 | 1.08#0.03 | 1.0120.04 387 0.940.14 | 0.74£0.08 | 0.97#0.08 | 0.892003 397 0.72#0.14 | 0.6240.09 | 0.7620.11 | 0,700.06 407 0.492012 | 0.4720.10 | 0550.11 | 0510.06 417 0.3140.10 | 0.37£0.09 | 0.39#0.07 | 0.4020.04 0.2140.08 | 0.34£0.06 | 0.3320.06 | 0.3740.02 0.1620.06 | 0.38%0.06 | 0.3120.07 | 0.3340.03 Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003 197ES. de Medeiros, R.M.B. Moreno, F.C. Ferreira, N. Alves, A.E. Job, P.S. Goncalves and L.H.C. Mattoso Table 1 shows that the Ozawa’'s exponent is considerably low at the beginning of the degradation process, increased with increasing temperature up to a maximum close to unity, and subsequently decreased to a lower value near zero at the completion of the reaction. This indicates that both the early and the latter stages of rubber degradation follow zero or pseudo-zero order kinetics whereas the intermediate stages follow a first order kinetics. This behavior has been reported in the literature using Wallace plasticity measurements”. Li et al.” and Oliveira et al.'28) have also confirmed that rubber degradation is not a single-step reaction based only on qualitative observations of thermogravimetric curves. Polymer degradation isa complex phenomenon involving many reactions that are difficult to analyze separately, During the early stages of degradation random scission occurs along the main chains with simultaneous oxidation and crosslinking, and therefore becomes an autocatalytic process with the reaction course®?*”, As the reaction proceeds, the increasing in weight fraction of decomposed sample as well as many concurrent degradation processes such as oxygen uptake, peroxide formation, crosslinking and volatiles liberation contribute to a reduction in reaction order until it reaches a minimum at higher degree of conversion ®.?11.29), Figure 3 shows the plots of In(B) versus 103/T for the computation of the activation energy (E) as a function of the conversion degree, o(T). The values of activation energy as a function of the conversion degree are shown in Table 2. Figure 3 Plots of In(B) versus 10°/T for the rubber clones: a) GT 1 140 785) 150) 155 160) 165, 103/T[K"] 198 Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003Thermogravimetric Studies of the Decomposition Kinetics of Four Different Hevea Rubber Clones using Ozawa’s Approach Figure 3 (Continued) Plots of In(B) versus 10°/T for the rubber clones: b) IAN 873; c) PB 235; d) RRIM 600 59800938 10*/T[K"] Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003 199E.S. de Medeiros, R.M.B. Moreno, F.C. Ferreira, N. Alves, A.E. Job, P.S, Goncalves and L.H.C. Mattoso Table 2 Values of activation energy as a function of the conversion degree for the rubber clones studied (1) (%) Activation energy, E (kJ/mol) GT 1 IAN 873 PB 235 | RRIM 600 10 170.7£11.4 | 195.447.5 | 161.2£10.6] 148.8+10.0 20 188.5+31.4 | 238.6+7.8 | 167.149.0 | 170.2£6.0 30 183.8+23.4 | 244.247.8 | 166.748.0 | 174.9461 40 175.4£20.4 | 262.8478 |1711+105| 1814571 50 182.4+16.4 | 253.647.8 | 164.148.6 | 175.449.2 60 198.5#17.1 | 229.6¢7.7 | 170.027.8 [_188.427.3 71 203.0+17.5 | 234.8£7.7 |180.4£11.1| 202.0465 80 236.1+38.9 | 224.3+7.5 | 218.8+23.8| 210.2412.1 90 211.8422.1 | 211.2+7.4 [231 3449.4 | 222.3421.2 Table 2 shows that the activation energy increased with increasing degree of conversion for rubber from clones GT 1, PB 235 and RRIM 600 while for IAN 873 the value of activation energy increased to degrees of conversion up to ca. 40% and decreased to higher degrees. This variation in activation energy values was already expected because when more than one degradation process is occurring the activation energy will be not always constant2”. Since that activation energy should be computed in the early stages of the degradation process, its average values for low conversion degree (a<40%) are 183 + 6, 249+ 2, 168+ 2and 175+ 6kJ/mol, respectively for rubbers extracted from clones GT1, IAN 873, PB 235 and RRIM 600, being therefore in the same range of values reported in the literature***”, These values follow the same trend of the average PRI (Plasticity retention index) values, i.e., 59, 73, 58 and 76, respectively for GT1, IAN 873, PB 235 and RRIM 600°”. The rubber clone developed by Instituto Agronémico do Norte (IAN 873) presented good thermal stability; its performance can be compared to that of the rubber extracted from GT1 and RRIM 600. Rubber from the clone PB 235 presented the lowest activation energy indicating, therefore, the lowest thermal stability. 200 Progress in Rubber, Plastics and Recycling Technology, Vol, 19, No. 4, 2003‘Thermogravimetric Studies of the Decomposition Kinetics of Four Different Hevea Rubber Clones using Ozawa's Approach 4. CONCLUSIONS The Ozawa's exponent indicated that both the early and the latter stages of rubber degradation follow zero order kinetics whereas the intermediate stages follow a first order kinetics. The activation energy increased with increasing degree of conversion for rubber from clones GT 1, PB 235 and RRIM 600 while for IAN 873 the value of activation energy increased to degrees of conversion up to 40% and decreased to higher degrees. The rubber from clones IAN 873, GT 1 and RRIM 600 presented the best overall thermal stability whereas the clone PB 235 presented the lowest activation energy, hence indicating the lowest thermal stability. 5. ACKNOWLEDGEMENTS The authors gratefully acknowledge the financial support provided by CAPES, CNPq and FAPESP. 6. REFERENCES 1. N.M. Matthew, physical and technological properties of natural rubber, in: M.R. Sethuraj; N.M. Mathew (eds.), Natural rubber: biology, cultivation and technology, chapter 18, Elsevier, Amsterdam, (1992), 399-486. 2. A. Stevenson, engineering properties and applications of rubber, in: MLR. Sethuraj; N.M. Mathew (eds.), Natural rubber: biology, cultivation and technology, chapter 19, Elsevier, Amsterdam, (1992), 487- 517. 3. F. W. Billmeyer Jr., Textbook of polymer science. 3rd. ed. John Wiley & Sons, New York, (1984). 4. L.H. Sperling, Introduction to physical polymer science, 2nd ed., John Wiley & Sons, New York, (1992). 5. W.Hofmann, Rubber technology handbook, Hanser, Munich, (1996). R.M. B. Moreno, M. Ferreira, P. S. Gongalves, L. H. C. Mattoso, Pesq. Agropec. Bras., 38 (2003), 583-590. 7. M. Ferreira, R.M. B. Moreno, P. S. Gongalves, L. H. C. Mattoso, Rubb. Chem. Tech., 75 (2002), 1-7. Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003 201E.S. de Medeiros, R.M.B. Moreno, F.C. Ferreira, N. Alues, A.E. Job, P.S. Goncalves and L.H.C. Mattoso 8. Y. Le Roux, E. Ehabe, J. Sainte-Beure, J. Nkengafac, J. Nkeng, F. Ngolemasango, S. Gobina, J. Rubb. Res., 3 (2000), 142-156. 9. J.J. Cunneen, Degradation of natural rubber during manufacture, storage and service, Proceedings of NR technology seminar, 4-5 December, (1978), 199-216. 10. T. Ozawa, Bull. Chem. Soc. Japan, 38 (1965), 1881-1886 11. J.H. Flynn, Thermogravimetric analysis and differential thermal analysis, in: H.H.G. Jellinek (ed.), Aspects of degradation and stabilization of polymers, Chap. 12, Elsevier, New York, (1978), 573-615. 12. S.G. Viswanath, M.C. Gupta, Thermochim. Acta, 285 (1996), 259- 267. 13. J.-H. Chan; T.S, Balke, Polym. Degrad. Stab., 57 (1997), 135-149. 14. C. Albano, E. Freitas, Polym. Degrad. Stab., 61 (1998), 289-295. 15. N.A. Liu, W.C. Fan, Themochim. Acta, 338 (1999), 85-94. 16. J.J.M. Orfao, F.J.A. Antunes, J.L. Figueiredo, Fuel, 78(1999), 349- 358. 17. A.Bajpai, J. Simon, Themochim. Acta, 334 (1999), 73-87, 18. A.M.A. Nada, M. L. Hassan, Polym. Degrad. Stab., 67 (2000), 111- 115. 19. P. Jandura, B. Riedl, B.V. Kokta, Polym. Degrad. Stab., 70 (2000), 387-394. 20. C.D. Doyle, Nature, 207 (1965), 290-291 21. M. Avrami, J. Chem. Phys., 8(1940), 221-224. 22. E.S. Medeiros, R. S. Tocchetto, L.H.Carvalho, I.M.G. Santos, A.G. Souza, J. Therm. Anal. Calorim., 66 (2001), 523-531. 23. E.S. Medeiros, R. S. Tocchetto, L.H.Carvalho, M.M. Conceigao, A.G. Souza, J. Therm. Anal. Calorim., 67 (2002), 279-285. 24. E. S. Medeiros, J. A.M. Agnelli, K. Joseph, L. H. Carvalho, L. H.C. Mattoso, accepted to publication in J. Appl. Polym. Sci., (2003). 25. M.S. Shambhi, J. Nat. Rubb. Res, 3, 2 (1988), 107-114. 26. L.H. Gan, S.C. Ng, K.K. Chee, Rubb. Chem. Tech., 65 (1991), 1- 6. 27. S.-D. Li, H.-P. Yu, Z. Peng, C.-S. Zhu, P.-S. Li, J. Appl. Polym. Sci., 75 (2000), 1339-1344. 202 Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003Thermogravimetric Studies of the Decomposition Kinetics of Four Different Hevea Rubber Clones using Ozawa’s Approach 28. L.C.S. Oliveira, E.J. Arruda, R.B. Costa, P.S. Goncalves, A. Delben, Thermochim. Acta, 398 (2003), 259-263. 29. R. L. Feller, Accelerated aging: photochemical and thermal aspects, The J. Paul Getty Trust editors, (1994). 30. L. Nasdala, Oxidative aging of filled elastomer, In: Dieter Besdo, Robert H. Schuster, and Jérn, Ihlemann( eds.), Constitutive Models for Rubber II, A. A. Balkema, Lisse, 2001, 205-211. 31. T. Kashiwagi, Twenty-Fifth Intemational Symposium on Combustion/ The Combustion Institute, (1994), 1423-1437 32_.1.T. South, PhD Thesis, Virginia Polytechnic Institute, Blacksburg, (2001). Progress in Rubber, Plastics and Recycling Technology, Vol. 19, No. 4, 2003 203E.S. de Medeiros, R.M.B, Moreno. F.C. Ferreira, N. Alves, A.E, Job, P.S. Goncalves and L.H.C. Mattoso 204 Progress in Rubber, Plastics and Recycling Technology. Vol. 19, No. 4, 2003