COMPOSITES SCIENCE AND TECHNOLOGY

Composites Science and Technology 67 (2007) 16661673 www.elsevier.com/locate/compscitech

Finite element modeling of polymer curing in natural ber reinforced composites

T. Behzad a, M. Sain
a

b,*

Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ont., Canada M5S 3E5 b Faculty of Forestry/Chemical Engineering, 33 Willcocks Street, University of Toronto, Ont., Canada M5S 3B3 Received 22 November 2005; received in revised form 16 June 2006; accepted 29 June 2006 Available online 2 October 2006

Abstract Plant-based bers have been selected as suitable reinforcements for composites due to their good mechanical performances and environmental advantages. This paper describes the development of a simulation procedure to predict the temperature prole and the curing behavior of the hemp ber/thermoset composite during the molding process. The governing equations for the non-linear transient heat transfer and the resin cure kinetics were presented. A general purpose multiphysics nite element package was employed. The procedure was applied to simulate one-dimensional and three-dimensional models. Experiments were carried out to verify the simulated results. Experimental data shows that the simulation procedure is numerically valid and stable, and it can provide reasonably accurate predictions. The numerical simulation was performed for a three-dimensional complex geometry of an automotive part to predict the temperature distribution and the curing behavior of the composite during the molding process. 2006 Elsevier Ltd. All rights reserved.
Keywords: Natural ber composite; B. Curing; B. Modeling; C. Finite element analysis (FEM)

1. Introduction Natural bers such as hemp, ax, jute, wood, and several waste cellulosic products have been used as suitable alternatives to synthetic reinforcements for composites in many applications. These bers oer specic benets such as low density, low pollutant emissions, biodegradability, high specic properties, and low cost [1,2]. Many studies have been carried out to develop dierent manufacturing processes and to study the mechanical performances of natural ber composites [37]. The successful production of thermoset composite parts depends upon a proper cure cycle during the molding process that leads to uniform curing and compaction. A few reports in the literature employed numerical analysis to study curing behavior and temperature distribution of synthetic ber composites during autoclave, resin transfer molding
*

Corresponding author. Tel.: +1 416 946 3191; fax: +1 416 978 3834. E-mail address: m.sain@utoronto.ca (M. Sain).

(RTM), and other manufacturing processes. For instance, Guo et al. [8] conducted a one-dimensional transient heat transfer analysis during the autoclave cure cycle for thick carbon ber/epoxy laminates using a commercial nite element (FE) software. It was found that the conventional curing cycles should be modied to prevent temperature overshoot. The temperature proles of a thick unidirectional glass/epoxy laminate during an autoclave vacuum bag process were predicted by Oh and Lee [9] using three-dimensional transient heat transfer FE analysis. Then, the viscosity proles, degree of cure, and resin pressure distribution in the laminate were obtained from the results of the heat transfer analysis. Joshi et al. [10] performed a transient heat transfer analysis using a general purpose FE software and two user programs to simulate resin cure kinetics of a thick graphite/epoxy laminate. The results showed excellent agreement with the experimental data. The modeling and simulation of resin ow, heat transfer, and the curing of multilayer thermoset composites during autoclave processing were investigated by

0266-3538/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.compscitech.2006.06.021

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Blest et al. [11]. The simulation was performed with varying composite thicknesses and conrmed the approximate validity of the model. Liu et al. [12] developed a numerical procedure for the simulation of temperature and cure proles for the pultrusion process. A commercial general purpose FE package was combined with a user program to solve the convection heat transfer and the resin reaction. A one-dimensional non-linear cure simulation model was developed by Pantelelis et al. [13] to track the temperature evolution in thick composites. Moreover, an optimization algorithm was coupled to the model to design the cure cycle. Cheung et al. [14] presented a three-dimensional thermo-chemical cure simulation employing the Galerkin FE method. Several numerical examples were depicted for dierent synthetic bers and resins in at or curve shaped parts. Park et al. [15] studied modeling for cure simulation of composite structures with an arbitrary geometry under non-uniform autoclave temperature distribution. No signicant work has been reported concerning the simulation of heat transfer and cure kinetics of natural ber thermoset polymer composites during the molding process. Rouison et al. [16] presented only a one-dimensional model using nite dierence (FD) method to predict the temperature distribution and cure behavior of natural ber composites in the RTM process. Most of the commercially used nite element software are not applicable for temperature and cure behavior simulation of thermoset composites during the molding process. In this case, either some user programs should be combined with the commercially available software or a non-linear transient heat transfer nite element model should be coded. In the present study, a nonlinear transient heat transfer nite element model is introduced to simulate the curing behavior of natural ber thermoset polymer composites. The model is dened for one and three-dimensional analysis using only a commercially available multiphysics software (COMSOL 3.2) without utilizing user written programs. It is assumed that no resin

ow or thickness reduction occurs during the curing process. The temperature and degree of cure proles inside the composite can be evaluated by solving the non-linear anisotropic heat conduction equation including the internal heat consumption as a result of the chemical reaction. The internal heat consumption can be expressed in terms of the cure rate. The minimum curing time required to completely solidify the composite can also be predicted. Hemp ber/ acrylic composites were considered and thermo-physical properties and the equation for the cure rate were studied. 2. Experimental An environmentally friendly acrylic polymer was obtained from BASF Company; Ontario, Canada. Hemp bers were supplied by Hempline Company, Ontario, Canada. In order to prepare prepreg mats, hemp bers were randomly oriented on a perforated screen and the acrylic resin solution was circulated to impregnate the bers with the solution. Vacuum ltration was applied to remove the excess solution. After circulation of the resin solution, the wet mat was displaced on a polyester sheet and then kept in the oven at 50 C for 48 h to remove all the moisture content and to complete the thickening process [17,18]. Heat compression molding experiments were conducted to verify the validation of the simulation. A metallic block mold with dimension of 15 15 1.2 cm3 was sprayed with the released agent. Total of ten prepreg plies were placed inside the mold to completely compact the composite. In order to verify the numerical modeling, temperature proles at ve dierent points inside the composite block were recorded through the experiment and compared with the numerical results. Fig. 1 illustrates the schematic diagram of the experimental set-up used to measure the temperature evolution during the molding process. The thermocouples were placed at dierent locations inside the composite and connected to a data acquisition system to monitor

Fig. 1. Schematic diagram of the experimental set-up.

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the temperature versus time. The mold temperature was kept at 175 C under the constant pressure for 25 min. The evolution of the heat capacity with temperature for hemp bers was measured using a dierential scanning calorimeter (DSC) in a TA instruments DSC Q 1000. The non-cured resins heat capacity was obtained by a similar experiment. 3. Analysis 3.1. Governing equations In compression molding, the reinforcement was already saturated with the resin and the resin was uniformly distributed through the mat. Therefore, the convective heat transfer eect caused by the resin ow is negligible. Moreover, it was assumed that the geometry, the thickness, and the resin mass remain constant during the molding process. It was also assumed that the curing reaction takes place after closing the mold. Moreover, the thermo-physical properties of the resin and composite were considered to be independent of the degree of cure. With these assumptions, the transient non-isothermal heat transfer is governed by the following equation in the Cartesian system [19]:       oT o oT o oT o oT oQ qc C pc Kx Ky Kz ot ox ox oy oy oz oz ot 1 where qc, Cpc, and Ki (i = x, y, z) are density, specic heat, and thermal conductivity of the material in three orthogonal directions, respectively. The endothermic eect of the resin cure reaction  repreoQ sents by the internal heat consumption sink term . ot Ignoring the eect of resin ow in the material, the term   oa can be directly related to the rate of cure by the folot lowing equation: oQ oa qr V r H R ot ot 2

where k is the reaction constant and is usually assumed to be in the Arrhenius form, A is frequency factor, Ea is the activation energy, R is the universal gas constant, T is the absolute temperature, and n is order of the reaction. This expression can be written in the logarithmic form:   oa Ea ln n ln1 a 5 ln A ot RT A multilinear regression can be performed to calculate the values of A, Ea, and n. In a previous study, the total heat of reaction and the kinetic parameters of the resin have been investigated [22]. The kinetic parameters of the resin are shown in Table 1. 3.3. Thermo-physical properties To predict the curing behavior of the composite accurately, the thermo-physical properties of the composite have to be well-known. The densities of the non-cured and cured resin, qr, were measured 1.53 g/cm3 and 1.45 g/cm3, respectively. The density of the hemp ber, qf, was assumed to be 1.48 g/cm3. The density of the composite, qc, was calculated using the rule of mixture as follows: qc tf qf 1 tf qr 6 where tf is the volume fraction of ber. The variations of the bers heat capacity, Cpf, could be tted quite well by a polynomial of the second order as follow in J/g K [22]: C pf 2 105 T 2 0:0008T 1:0812 7

where T is the absolute temperature. The heat capacity of the non-cured resin increased linearly with temperature in the range of 35190 C [22]. These variations could not be neglected in the model and the following linear relationship was used as the resins heat capacity, Cpr, in J/g K: C pr 0:0149T 0:459 8 To predict the temperature variations in the composite during the molding process, the heat capacity of the composite materials is required. Therefore, the heat capacity of the composite, Cpc, was evaluated using the rule of mixture as follows: C pc T C pf T tf C pr T 1 tf 9

where, qr is the density of resin, Vr is the resin volume fraction of composite, and HR is the total heat of reaction, and a is the degree of cure. 3.2. Cure kinetics One of the most widely accepted methods to study the cure kinetics of a thermoset resin system is dierential scanning calorimetry (DSC) [20,21]. The reaction rate, ra, and the degree of cure are related as follows: oa ra ot 3

where tf is the volume fraction of the ber. The transverse conductivity of the composite, Kt, (zdirection in Fig. 1) was calculated based on the thermalelectrical analogy technique for elliptical laments and a
Table 1 Resin kinetic parameters used in modeling Total heat of reaction (J/kg) 491,000 Frequency factor (1/s) 18,033 Activation energy (J/mol) 46,700 Order of reaction 1.4

The rate of the curing reaction is often described according to the following equation: ra k1 a AeEa =RT 1 a
n n

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square packing array unit cell model (ES model) [23]. It can be expressed as follows:  p p d d 2 c2  Kt   2 10 1 1=c p=2d c=d d c2 ln     Km c where pKm is the thermal conductivity of matrix, c pl=tf =2, d = l(1/b 1), and b = Kf/Km. Where l is the geometry ratio of the ller (l = a/b), where a and b are the axial lengths of the ellipse along the x-axis and y-axis, respectively, tf is ber volume fraction of the composite, and Kf is the conductivity of ber. When l = 1 (i.e., a = b), the present model can be simplied as the cylindrical laments in a square packing array unit cell model. The in-plane longitudinal conductivity of the composite, Kl (x- and y-directions in Fig. 1) was experimentally measured at dierent volume fractions of ber. Experimental procedure and results were reported in detail elsewhere [24]. The longitudinal thermal conductivity of the composite versus the volume fraction of bers can be expressed by the following linear relationship: K l 0:724tf 0:4033 where tf is the volume fraction of ber. 3.4. Finite element modeling of heat transfer The temperature distribution in the composite during the curing process can be obtained using a non-linear transient heat transfer analysis including the internal heat consumption (Eq. (1)). The model is dened based on nite element method (FEM) using only a commercially available software with multiphysics environment (COMSOL 3.2) and without adding any user written programs. First, the transient heat transfer model is dened in the heat transfer module of the software to obtain the temperature. Then, a general form equation is considered separately in the partial dierential equation (PDE) module to evaluate the cure kinetics and degree of cure reached in each element. The above mentioned governing equations can be solved considering the initial and boundary conditions. At t = 0, T = T0 and a = a0 (a0 = 0), where T0 and a0 are the initial temperature and degree of cure of the material, respectively. For the heat transfer model, the temperature of boundaries is set to the temperature of mold. The Neumann boundary conditions are considered for the kinetic model. The rule of mixture is used to calculate the density and heat capacity of the composite (Eqs. (6) and (9)). The thermal conductivity of the composite at dierent directions is obtained using dierent models (Eqs. (10) and (11)). The energy and kinetic equations are coupled where the rate of cure reaction is a function of temperature which leads to a non-linear system. The rates of internal heat sink are calculated from the rates of cure at each time step for all the nodal elements. These are then applied as heat sinks at the respective nodal points for the nite element transient heat transfer analysis in the next time step. The execu11

tion of the nite element analysis is repeated until the completion of the cure cycle. 4. Results and discussion 4.1. One-dimensional cure modeling The one-dimensional cure modeling of the composite was carried out considering the transient heat transfer analysis combined with cure kinetics. The eect of number of elements and time steps on the temperature distribution of the composite was investigated. Little variation with respect to the mesh density and time step conrmed the stability and convergence of the procedure. It means that the results are not sensitive to either the mesh density or time step. To validate the present procedure (FEM) it was compared to the one-dimensional result obtained from nite dierence method (FDM). For the nite dierence method, a code in MATLAB was developed to simulate the heat transfer and cure kinetic for a one-dimensional model. The code employed a nite dierence solution technique to predict the temperature and degree of cure proles for thin at composites. Detail descriptions of the FDM procedure and results were published elsewhere [22]. A onedimensional model with 1.2 cm thickness with the same number of elements for both procedures was considered. A time step of 1 s was selected to achieve the desired accuracy. The temperature results for the central point of the composite by FDM and the present procedure (FEM) were compared; see Fig. 2. A very good agreement was observed during the rst and the last part of the curing cycle. A few degree discrepancies in the intermediate stage of the curing cycle can be observed. The degree of cure at the center of the composite versus time is presented in Fig. 3. The FDM technique predicts the degree of cure with slower rate compared to FEM which can be due to dierences in the estimated temperatures. In FDM, the CrankNicholson technique was applied followed by a dichotomy method to obtain the

180 160 Temperature (C) 140 120 100 80 60 40 20 0 0 100 200 300 Time (second) 400 500 600

FDM FEM

Fig. 2. Temperature proles at the center of the composite versus time obtained by dierent numerical methods.

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1 Degree of cure

180 160 Temperature (C) 140 120 100 80 60 40 20 0 0 200 400 600 800 1000 Time (second)
Fig. 5. Temperature proles at the center of the composite in 1D and 3D model.

0.8 0.6 0.4 0.2 0 0 100 200 300 Time (second) 400 500 600

FDM FEM

1D 3D

Fig. 3. Degree of cure proles at the center of the composite versus time obtained by dierent numerical methods.

temperature and degree of cure at each time step. Whereas, in FEM, the NewtonRaphson method was employed which results in a dierent temperature and degree of cure at each time step due to dierent numerical errors. 4.2. Three-dimensional cure modeling for a block In three-dimensional heat transfer analysis, due to anisotropic nature of the material, it is necessary to provide thermal conductivity of the material in three orthogonal directions. For the three-dimensional analysis, a simple block (15 15 1.2 cm3) was used which composed of 600 solid elements and the time step was selected to be 10 s. The temperature of all outer surfaces was set to the mold temperature. Fig. 4 represents the meshed nite element model for the analysis. The model was simulated in both 1D and 3D heat transfer models. Fig. 5 compares one-dimensional and threedimensional temperature simulations at the center of the block. It shows that there is good agreement between 1D and 3D temperature proles from heat transfer models. This result indicates that for the center of block, a 1D heat transfer model can precisely predict the temperature prole. As one moves from the center to corner of the block, discrepancies between the temperature obtained in 1D

and 3D heat transfer model will arise due to boundary conditions. Fig. 6 shows the temperature evolution versus time at the center and corner of the block using the 3D heat transfer model. As it can be seen, the simple 1D heat transfer model is not applicable and 3D model has to be considered to predict the results accurately. In order to verify the three-dimensional modeling, the temperature proles at ve points inside a block of composite with 15 15 1.2 cm3 dimensions were measured experimentally and compared with the numerical results. Fig. 7 shows the temperature proles at two dierent locations; center and corner of the block obtained by the simulation and experiment. The predicted temperature proles were in good agreement with the experimental results. There are a few degree discrepancies which can be due to the assumptions considered for the modeling such as constant thickness, constant density, and ignoring the eect of degree of cure on heat capacity and thermal conductivity. In addition, the thermocouples could be displaced from their initial location during the experiment in compression molding.

200 180

Temperature (C)

160 140 120 100 80 60 40 20 0 0 200 400 600 800 1000

Corner Center

Time (Second)
Fig. 4. Finite element model of a block of the composite (all units are in meters). Fig. 6. Temperature proles at the center and corner of the composite in 3D model.

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a
Temperature (C)

200 180 160 140 120 100 80 60 40 20 0 0 200 400

Experiment Model

600

800

1000

Time (second)

b
Temperature (C)

200 180 160 140 120 100 80 60 40 20 0 0 200 400

Experiment Model

Fig. 8. Finite element mesh for a segment of an automotive mirror case (all units are in meters).

600

800

1000

Time (second)
Fig. 7. Comparison of experimental and predicted temperature proles of the hemp ber acrylic composites at two dierent locations (a) center and (b) corner.

4.3. Three-dimensional cure modeling for an automotive mirror case To demonstrate the ability of the three-dimensional model, the numerical simulation was performed for a complex three-dimensional geometry of an automobile part to predict the temperature distribution and cure behavior of the composite during the molding process. A transient heat transfer three-dimensional simulation was conducted for a real automotive mirror case geometry. The mold temperature was selected to be 185 C. Due to the symmetry of the part, to save the computation time only a segment of the corner of the structure was considered. The thickness of the part is dierent at the corner, edge, and top sections of the model. The governing equation is solved subjected to the mold-wall temperature conditions and the isothermal condition on symmetry boundaries: T T m on mold surfaces oT 0 on symmetry surfaces k on 12 13
Fig. 9. Temperature distributions (C) at dierent curing times in various slides of the structure: (a) curing time = 50 s and (b) curing time = 500 s (units of axis are in meters).

Fig. 8 shows the nite element model of the geometry at dierent views. The numerical model was performed at different number of tetrahedral meshes (7296, 11,269, 15,112) and time steps (100, 50, 10). Although there was no signicant dierence in temperature proles, but applying 15,112

elements and 10 s for time step, the model shows more stable and smoother proles. Figs. 9 and 10 show the temperature distribution and degree of cure of the structure at dierent slides inside the composite after 50 and 500 s.

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an automotive mirror case. The temperature and degree of cure proles were predicted for the structure. The cure behavior of a structure with dierent geometries, curvatures, and thicknesses can be simulated using the multiphysics software. Acknowledgments The authors would like to thank Network of Centre of Excellence-Auto 21 Canada for their nancial support. References
[1] Joshi SV, Drzal LT, Mohanty AK, Arora S. Are natural ber composites environmentally superior to glass ber reinforced composites? Compos Part A: Appl Sci Manuf 2004;35:3716. [2] Mohanty AK, Misra M, Drzal LT. Sustainable bio-composites from renewable resources: opportunities and challenges in the green materials world. J Polym Environ 2002;10:1926. [3] Herrera-Franco PJ, valadez-Gonzalez A. mechanical properties of continuous natural bre-reinforced polymer composites. Compos: Part A 2004;35:33945. [4] Cantero G, Arbelaiz A, Llano-Ponte R, Mondragon I. Eects of bre treatment on wettability and mechanical behavior of ax/polypropylene composites. Compos Sci Technol 2003;63: 12471254. [5] Jacob M, Thomas S, Varughese KT. Mechanical properties of sisal/ oil palm hybrid ber reinforced natural rubber composites. Compos Sci Technol 2004;64:95565. [6] Julson JL, Subbarao G, Stokke DD, Gieselman HH. Mechanical properties of biorenewable ber/plastic composites. J Appl Polym Sci 2004;93:248493. [7] Mehta G, Mohanty AK, Thayer K, Misra M, Drzal LT. Novel biocomposites sheet molding compounds for low cost housing panel applications. J Polym Environ 2005;13(2):16975. [8] Guo ZS, Du S, Zhang B. Temperature distribution of thick thermoset composites. Modell Simul Mater Sci Eng 2004;12:44352. [9] Oh JH, Lee DG. Cure cycle for thick glass/epoxy composite laminates. J Compos Mater 2002;36(1):1944. [10] Joshi SC, Liu XL, Lam YC. A numerical approach to the modeling of polymer curing in bre-reinforced composites. Compos Sci Technol 1999;59:100313. [11] Blest DC, Duy BR, McKee S, Zulkie AK. Curing simulation of thermoset composites. Compos: Part A 1999;30:1289309. [12] Liu XL, Crouch IG, Lam YC. Simulation of heat transfer and cure in pultrusion with a general-purpose nite element package. Compos Sci Technol 2000;60:85764. [13] Pantelelis N, Vrouvakis T, Spentzas K. Cure cycle design for composite materials using computer simulation and optimization tools. Forsch Ingenieurwesen 2003;67:25462. [14] Cheung A, Yu Y, Pochiraju K. Three-dimensional nite element simulation of curing of polymer composites. Finite Elem Anal Des 2004;40:895912. [15] Park HC, Goo NS, Min KJ, Yoon KJ. Three-dimensional cure simulation of composite structures by the nite element method. Compos Struct 2003;62:517. [16] Rouison D, Sain M, Couturier MR. Resin transfer molding of natural ber reinforced composites: cure simulation. Compos Sci Technol 2004;64:62944. [17] Behzad T, Sain M. Thermo durable and high performance natural ber molded composites manufacturing process. US pat. Publication No. 2005-0245161. [18] Behzad T, Sain M. Process for manufacturing a high performance natural ber composite by sheet molding. SMe Technical paper 2005.

Fig. 10. Degree of cure distributions at dierent curing times in various slides of the structure: (a) curing time = 50 s and (b) curing time = 500 s (units of axis are in meters).

As it can be seen, corners are the last sections which reach to the nal temperature of curing due to their greater thickness. Consequently, the corners are the last areas to completely solidied and cured. From the simulation results it can be estimated that the molding time to achieve 100% cure for the entire structure is approximately 500 s. Hence, the simulation model is capable to display the cure behavior of any complex geometry. 5. Conclusion A non-linear transient heat transfer analysis combined with a cure kinetic model based on nite element procedures was developed. In order to accurately predict the result, the thermo-physical properties of the composite were investigated. The temperature and degree of cure distribution for hemp ber/acrylic composites during the molding process were developed for a one-dimensional model and compared with previous results from a nite dierence method. A three-dimensional model was developed for a simple block of the composite and compared with experimental results. Experimental data shows that the simulation procedure is numerically valid and stable, and provides reasonably accurate predictions. To demonstrate the simulation model for a complex geometry, the model was carried out for a segment of

T. Behzad, M. Sain / Composites Science and Technology 67 (2007) 16661673 [19] Eckert ERG, Drake RM. Analysis of heat and mass transfer. McgraHill: Hemisphere Publishing Corporation; 1972. Part A Heat conduction. [20] Salla JM, Ramis X. Comparative study of the cure kinetics of an unsaturated polyester resin using dierent procedures. Polym Eng Sci 1996;36(6):83550. [21] Chu F, Mckenna T, Lu S. Curing kinetics of an acrylic/epoxy resin system using dynamic scanning calorimetry. Eur Polym J 1997;33(6):83740.

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[22] Behzad T, Sain M. Cure simulation of hemp ber acrylic based composites during sheet molding process. Polym Polym Compos 2005;13(3):23543. [23] Zou M, Yu B, Zhang D, Ma Y. Study on optimization of transverse thermal conductivities of unidirectional composites. J Heat Transfer 2003;125:9807. [24] Behzad T, Sain M. Measurement and prediction of thermal conductivity for hemp ber reinforced composites. Polym Eng Sci, 2006; in press.