Materials Science and Engineering B 168 (2010) 237241

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Materials Science and Engineering B

journal homepage: www.elsevier.com/locate/mseb

Simulation of curing of a slab of rubber

P.M. Abhilash a , K. Kannan a, , Bijo Varkey b
a b

Department of Mechanical Engineering, IIT Madras, Chennai 600036, India Advanced Design Department, MRF Ltd., Chennai 600019, India

a r t i c l e

i n f o

a b s t r a c t
The objective of the present work is to predict the degree of curing for a rectangular slab of rubber, which was subjected to non-uniform thermal history. As the thermal conductivity of rubber is very low, the temperature gradient across a slab is quite large, which leads to non-uniform vulcanization, and hence non-uniform mechanical propertiesan inhomogeneous material. Since curing is an exothermic reaction, heat transfer and chemical reactions are solved in a coupled manner. The effect of heat generation on curing is also discussed. 2009 Elsevier B.V. All rights reserved.

Article history: Received 7 August 2009 Received in revised form 22 November 2009 Accepted 6 December 2009 Keywords: Natural rubber Vulcanization Dings chemical kinetics Heat conduction Crosslink density Heat generation

1. Introduction Rubber is a sticky, liquid-like substance at room temperature, and cannot be used for making rubber products in its natural form. Natural rubber is blended with many chemicals such as sulphur, a crosslinking agent, accelerator, which increases the rate of chemical reactions, activators such as zinc oxide, retarders such as phthalimide, which delay the onset of crosslinking reactions, and llers such as carbon black and silica for improving mechanical properties of the vulcanized rubber products. The blended mixture which is liquid-like, is vulcanized at about 140 C. A vulcanized material cannot be processed in an extruder, mixer, or any device, which requires the material to ow. Therefore, the vulcanization is done after the blended mixture has taken its nal shape or form. Vulcanization process triggers a cascade of chemical reactions, which result in the formation of chemical crosslinks, a three-dimensionally networked polymer with suitable material properties. The current developmental procedure for a new tire involve arriving at the amount of various chemicals (initial concentration of natural rubber, sulphur, accelerator and retarder) and maintaining a required temperature history at the boundary of a tire in a curing press by a trial and error process until a product with required mechanical properties is achieved. Any change in mix design and

Corresponding author. Tel.: +91 44 2257 4708; fax: +91 44 2257 4652. E-mail address: krishnakannan@iitm.ac.in (K. Kannan). 0921-5107/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.mseb.2009.12.035

mold temperature will affect the chemical reactions, and therefore the nal density of crosslinking, and hence the mechanical properties. In other words, by controlling the amount of chemicals in the rubber mixture along with temperature at the surface of a mold, one could control the mechanical properties of a cured product. A trial and error process is both expensive and time-consuming because it involves many full-scale experiments. Modeling and simulation of this process will cut down on product development cost and time. To that end, one needs to develop appropriate equations describing the chemical reactions (refer to [1] for a detailed description). Modeling of chemical kinetics developed by Ding et al. [2] is simplistic, in that, it is a lumped model and cannot be used for designing the composition of chemicals. However for a xed chemical composition, the model developed by Ding and Leonov [3] could be used for designing the curing process (boundary condition for temperature and the time for completion of curing process). Therefore, due to simplicity, we resort to chemical kinetics to that developed by Ding and Leonov [3]. The modeling of this process is extremely important for any rubber industry, and particularly for a tire industry. As the thermal diffusivity of rubber is very low, temperature gradient across the cross-section of a tire is quite large. This leads to non-uniform vulcanization. One needs to determine the curing time in such a way that the required distribution of degree of cure is achieved. As simulating the progression of cure for a tire is quite complicated, we chose a much simpler geometry, namely, a large rectangular slab. Such a simpler geometry can still provide insight into the progression of cure.

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P.M. Abhilash et al. / Materials Science and Engineering B 168 (2010) 237241 Table 1 Ingredients used in natural rubber mixture. All values are in part per hundred (phr) grams natural rubber. Accelerator used in the mixture is Ntert-butyl-benzothiazole-2-sulphenamide (TBBS) and the retarder used is N-cyclohexylthio pthalimide (CTP). Ingredient Natural rubber Carbon black (N330) Sulphur (rhombic, S8 ) Accelerator (TBBS) Retarder (CTP) Zinc oxide Anti-oxidant Concentration (phr) 100 50 1.58 1.4 0.2 5 3

2. Experimental Oscillating disc rheometry (ODR) is a technique for measuring the shear modulus of a material that is structurally changing. Using suitable theories, one could estimate the crosslink density of a rubber sample using the measured shear modulus. The equipment used for the ODR runs is Rubber Process Analyzer (RPA)-2000 made by Alpha technologies. One could vary the amplitude and frequency of oscillation of the upper disc, and temperature of the sample as a function of time. The basic construction of RPA-2000 is described below: the bottom die is xed and the top die oscillates. The shape of the pair of dies is in such a way that the sample takes the shape of a bi-conical discthe cone angle is very small. Such a geometry ensures that the strain undergone be a material at any radius from the center of disc is constant. The blended natural rubber mixture is set in the die cavity, and is heated to a required curing temperature. The top die oscillates at a predened amplitude and frequency, and the torque is measured. The natural rubber mixture behaves like a viscoelastic liquid. Theory of linear viscoelasticity is used obtain the storage and loss shear modulus. This information is used to calculate the storage and the loss shear modulus of the material during the curing process. As the rubber sample cures, the torque required to bring about the same elastic deformation increases, which results in increase of storage shear modulus, i.e., the more the density of crosslink, the more the storage modulus. From this point onwards, we shall refer to storage shear modulus as shear modulus. Carbon black (ller) is an essential ingredient for most rubber formulations. In automobile tires, carbon black improves wet traction amongst other properties. The addition of carbon black in the powder form (30100 nm) to a rubber mixture signicantly improves many mechanical properties of vulcanized rubber products. This is a result of adsorption of polymeric molecules of rubber on to the surface of carbon black particles (llerrubber interactions) [4,5]. Further, carbon ller forms a network (llerller interactions), which resists deformation. To estimate the degree of chemical crosslinking in carbon black lled rubber mixtures, the measured shear modulus has to be corrected for llerrubber and llerller interactions. Medalia [6] suggested that the volume fraction of ller in the familiar GuthGold equation should be replaced by effective volume fraction of ller, i.e.: Gg = (1 + 2.5Veff + 14.1Veff 2 )Gm , (1)

Table 2 Run-time for homothermal tests. Temperature in C 128 138 148 158 Time in minutes 140 70 70 60

in mole/m3 , R is the universal gas constant and T is the absolute temperature of the sample. 2.1. Preparation of sample The samples were prepared by mixing natural rubber and the other chemicals together in a Branbury mixer (see Table 1). The mixing is done until the mixture reaches a temperature of about 100 C. Then, the blended sample is rolled into sheets in a rolling milleight to ten passes are required. The sheets are immersed in water to bring the temperature of the sheets to about room temperature. The density of the blended sample is 1130 kg/m3 . These samples are used in determining storage and loss modulus using a disc rheometer. 2.2. Experiments at homothermal condition A portion of a rolled sample of blended rubber is placed in between the pair of dies. The temperature is brought to the required temperature, and is maintained at that temperature. For all these experiments, the top die is oscillated at a strain amplitude of 7% at the periphery of the disc, and at a frequency of 1.6 Hz. Table 2 illustrates the conditions at which the tests were performed. The storage modulus and loss modulus were recorded during curing of a sample, and the degree of cure is calculated, after correcting for ller interactions, as a function of time using the procedure outlined earlier in this section. 3. Results and discussion 3.1. Modeling of chemical reactions The cascade of chemical reactions that occur during vulcanization is very complicated. Ghosh et al. [1] developed a comprehensive model taking into account 111 reactants and products. In this article, we only consider chemical reaction mechanisms in a simplistic fashion. These models do not include all the reactants and products in the reaction scheme. Only the most important species are retained and some of the species may be lumped, and the number of moles of certain species produced is chosen in such a way that the mass-balance is satised. Coran [9] proposed such a model for vulcanization of rubber. In this model, Coran considered four species, namely, a sulphurating species, A, vulcanization precursor, B, an activated vulcanization precursor, B , and the vul-

where Veff represents effective volume fraction of ller, Gg represents equivalent shear modulus of gum rubber (without ller) and Gm represents the storage modulus (shear) of lled rubber mixture. One can determine the effective volume fraction of ller as follows: a rubber mixture was prepared without adding ller and the sample was cured at 138 C, and shear modulus is measured as the sample cures. Thus the gum-state shear modulus is determined. Using the shear modulus data for lled and unlled rubber mixture, using Eq. (1), and by only using the plateau shear modulus of gum-state rubber mixture, the effective volume fraction is determined to be 0.28. The actual volume fraction of added ller is only about 0.18. Further, we assume that the effective volume fraction remains unchanged at all temperatures. Once the equivalent shear modulus of gum rubber is estimated, Gaussian statistical theory of rubber network [7] is invoked, assuming crosslinks to be tetra-functional in nature (For details, see Lee et al. [8]), to estimate the density of crosslinks, i.e.: Vuchem =
o Gg Gg

2RT

(2)

o is shear modulus where Gg is the shear modulus of gum rubber, Gg of uncrosslinked rubber mixture, Vuchem is the number of crosslinks

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canizate, Vu. The reaction scheme is as follows: ABB Vu and A + B B.

k4 k1 k2 k3

(3a)

(3b)

Reaction Eq. (3a) represents the basic steps that occur during vulcanization. It has been observed experimentally that the entire accelerator is consumed before the formation of crosslinks. Reaction Eq. (3b) was proposed by Coran to emulate the experimental observations. For a sufciently large rate parameter k4 , one could ensure that all of accelerator is consumed before the formation of crosslinks (induction period). Ding et al. [2] introduced a competitive reaction Eq. (3c) to account for the decrease in the concentration of the vulcanizate at higher temperatures, i.e.: B D
k5

(3c)

Later, Ding and Leonov [3] added a reaction to account for the phenomenon of reversion, which was observed during the vulcanization of natural rubber, i.e.: Vu D,
k6

Fig. 1. Prediction of Ding and Leonovs model at various temperatures.

(3d) are solved using a stiff equation solver in MATLAB. In order to nd the values of the rate constants through k1 , k2 , k3 , k4 , k5 and k6 the following objective function is minimized:
N i (Vui exp Vumodel ) 2

which results in ve non-linear coupled differential equations, i.e.: d[A] = k1 [A] k4 [A][B ], dt d[B] = k1 [A] k2 [B] + k4 [A][B ], dt d[B ] = k2 [B] (k3 + k5 )[B ] k4 [A][B ], dt d[Vu] = k3 [B ] k6 [Vu], dt and d[D] = (k5 [B ] + k6 [Vu]), dt (4e) (4a) (4b) (4c) (4d)

= 100

1 N

i=1

Vui exp

(5)

where [A], [B], [B ], [Vu] and [D] are the concentrations of appropriate species. The coefcients , and are stoichiometric coefcients, introduced as a result of lumping of various chemical species. Using mass-balance, these coefcients were determined to be =1, =2 and =1 (refer to Ding and Leonov [3]). The ve non-linear, coupled, differential equations are solved with nonzero initial condition for species A and zero initial conditions for the rest of the species. Referring to Ghosh et al. [1], it is clear that the lumped species A referred to in Coran, Ding and Leonov and Ding et al. [2,3,9] represents active sulphurating agent, which is formed as a result of interaction of accelerator and elemental sulphur. Such an interaction is ignored in the lumped models under consideration. Since one does not know the amount of active sulphurating agent, we assume that the initial concentration of active sulphurating agent is equal to that of initial concentration of sulphur. Accordingly, using the density of the rubber mixture and the amount of sulphur (refer to Table 1), the initial concentration of species A is determined to be 250 mole/m3 . The above equations
Table 3 Reaction constants obtained after optimization procedure. Rate constant (unit) k1 k2 k3 k4 k5 k6 (min ) 1 (min ) 1 (min ) (m3 /mol/min) 1 (min ) 1 (min )
1

where is the objective function, N is the number of experimental i points, Vui exp is the i th experimental value and Vumodel is the i th predicted value by the model. The objective function represents rms error in percentage. An optimization algorithm (LevenbergMarquardt) is invoked for obtaining the numerical values for the reaction constants. Table 3 lists the value of rate constants at various temperatures. Prediction of the model at four different temperature is shown in Fig. 1. In order to predict the density of crosslinks for an arbitrary temperature history, one needs to know how the rate parameters are dependent on temperature. To that end, one may appeal to collision theory, which predicts that k = A0 expEa /RT , where the constants A0 and Ea are collision frequency (or pre-exponential) and activation energy, respectively, R is gas constant and T is absolute temperature. Further, to determine the constants A0 and Ea , curing experiments at homothermal conditions are sufcient, and are obtained from the intercept and slope of the plots ln(k) versus 1/T , respectively. Fig. 2 shows the plot of ln(k) versus 1/T and A0 and Ea are obtained from the best t, which are listed in Table 4.

3.1.1. Modeling of heat transfer The heat conduction process in a slab is approximated as a onedimensional process. Accordingly, assuming Fourier law of heat

128 C 4.1730e 002 1.0174e 001 1.6333e+000 5.0684e 001 5.6595e+000 3.3123e 005

138 C 7.5308e 002 2.2832e 001 4.3531e+000 9.3045e 001 1.6462e+001 1.7960e 004

148 C 1.3215e 001 4.9308e 001 1.1074e+001 1.6525e+000 4.5518e+001 8.9865e 004

158 C 2.2591e 001 1.0275e+000 2.6976e+001 2.8637e+000 1.2005e+002 4.1729e 003

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Fig. 2. A plot used to determine collision frequency, A0 and activation energy, Ea .

conduction, one-dimensional form of heat equation is solved, i.e.: 2 T 1 T Q = + , t K x2 (6)

is the where is the thermal diffusivity of the rubber material, Q rate of heat released per unit volume and K is the thermal conductivity of the rubber sample. We shall assume that the rate of heat released per unit volume is of the following form: = q dVu , Q dt (7)

where q is the rate of heat released per unit volume per unit rate of change of total crosslink density. We have assumed that only the crosslinking reactions contribute signicantly to the heat source. Further, please note that Vu is a function of T and time t , i.e., Vu = Vu(T (x, t ), t ). To obtain the distribution of crosslink density, one need to solve Eqs. (4a) through (4e), together with the partial differential Eq. (6), which are coupled in nature. To solve these equations, apart from initial conditions for Eqs. (4a)(4e), one need both initial conditions of the form: T (x, 0) = f (x), (8)

Fig. 3. Distribution of temperature and corresponding crosslink density. (a) Distribution of temperature in a at slab made of rubber and (b) distribution of crosslink density corresponding to (a).

where f (x) is the temperature distribution of the at plate at time zero, and boundary conditions at the two boundaries of the slab, i.e., at x = a and x = b. We assumed Dirichlet boundary conditions of the following form: T (a, t ) = Ta and T (b, t ) = Tb . 3.2. Simulation Let us consider the case of a at slab of thickness 2 cm, initially at 50 C, and maintained at 140 C on either side for 50 min.
Table 4 Values of A0 and Ea obtained using Fig. 2. Rate constant k1 k2 k3 k4 k5 k6 A0 1.4399e+009 2.7267e+013 5.1313e+017 3.2312e+010 6.4780e+019 4.9494e+025 Ea in Joules 9.7300e+003 1.3322e+004 1.6156e+004 9.9762e+003 1.7598e+004 2.7861e+004

(9)

The initial and boundary conditions are not compatible only at time t = 0. We assume that thermal diffusivity and conductivity of rubber does not depend on temperature and is taken to be approximately 4.2 102 cm2 /min and 0.12 J/min/K (refer to data for HAF black in Hands and Horsfall [10]). The rate of heat generated per unit volume unit rate of change of crosslink density (q) is taken as 1.98 105 J/mol. Such a value for q will make sure that the volumetric heat generated is around 2 104 W/m3 [11], which is assumed to be a typical value for rubber vulcanization. Notice that the heat conduction equation, i.e., Eq. (6) and vulcanization reactions, i.e., Eqs. (4a)(4e), are coupled with each other. First, the heat equation is solved by assuming that the heat source is zero. Second, the temperature history corresponding to every node, associated with the slab, is extracted and is used for solving equations representing vulcanization reactions. Recall that an Arrhenius expression is used for reaction rates, i.e., k1 through k6 , which are function of temperature. Thus, the density of crosslinks realized at the end of the reaction is a function of temperature history. Third, the rate of change of crosslink density, associated with every node, computed in the second step, is used to re-calculate

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The temperature distribution of the at slab as function of time is shown in Figs. 3(a) and 4(a), and its corresponding crosslink distribution is shown in Figs. 3(b) and 4(b), respectively. If one wants to obtain uniform crosslink density, it is obvious from Fig. 4(b) that a curing time of about 50 min is required. After 50 min, temperature reaches about 140 C throughout the slab. However, crosslink density shows a slight non-uniformity because the temperature history associated with every point is different. Further, as expected, a heat source term in the heat equation causes a higher temperature distribution to exist in a slab compared to that of a heat equation (with the same material parameters) without a heat source (see Fig. 4(a)). Referring to Fig. 4(b), at 40 and 45 min, the degree of cure is slightly higher compared to that of a model for curing without a heat source and, however, at 50 min, the trend is reversed. The reason for this behavior is attributed to a large heat source, which causes reversion. 4. Summary and conclusions The distribution of crosslink density for a at slab was predicted using Ding and Leonovs model. It was found that this model describes the curing behavior adequately. The presence of a heat source term in the heat equation did not alter the results significantly. Using such a model, one could estimate the curing time and study the possibility of reduction of curing time, and thereby enhancing the productivity. Should one be interested in predicting the subsequent mechanical response of a cured rubber product, such as in the case of an automobile tire, one could use this model, for a given temperature history, to estimate the distribution of crosslink density. In other words, the inhomogeneity can be predicted. Acknowledgment P.M. Abhilash and K. Kannan thank MRF for sponsoring research in this area. References
[1] P. Ghosh, S. Katare, P. Patkar, J. Caruthers, V. Venkatasubramanian, Rubber Chemistry and Technology 76 (2003) 592694. [2] R. Ding, A. Leonov, A. Coran, Rubber Chemistry and Technology 69 (1996) 8191. [3] R. Ding, A. Leonov, Journal of Applied Polymer Science 61 (1996) 455463. [4] J. Diani, B. Fayolle, P. Gilormini, European Polymer Journal 45 (2009) 601612. [5] J.L. Leblanc, Progress in polymer science 27 (2002) 627687. [6] A.I. Medalia, Rubber Chemistry and Technology 46 (1973) 877896. [7] L.R.G. Treloar, The Physics of Rubber Elasticity, Oxford University Press, Oxford, 1958. [8] S. Lee, H. Pawlowski, A. Coran, Rubber Chemistry and Technology 67 (1994) 854864. [9] A. Coran, Rubber Chemistry and Technology 37 (1964) 689697. [10] D. Hands, F. Horsfall, Rubber Chemistry and Technology 11 (1977) 253265. [11] M. Juma, M. Bafrnec, Chemical Papers 58 (2004) 2932.

Fig. 4. The effect of heat source on temperature distribution and density of crosslinks. (a) Temperature prole and (b) total crosslink density.

the heat source term. Cubic splines are used to obtain interpoat arbitrary x and t . Fourth, using the known lated values for dVu dt heat source term, new temperature eld is computed. Finally, the entire procedure is repeated until one obtains identical temperature and crosslink density eld. The heat equation, i.e., Eq. (6) is solved using a suitable initial and boundary condition in MATLAB.