Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris

Modeling Heat Barrier Efficiency of Flame Retarded Materials

Serge Bourbigot*, Maude Jimenez and Sophie Duquesne Laboratoire Procds dElaboration des Revtements Fonctionnels (PERF), LSPES UMR/CNRS 8008, Ecole Nationale Suprieure de Chimie de Lille (ENSCL), Avenue Dimitri Mendeleev Bt. C7a, BP 90108, 59652 Villeneuve dAscq Cedex, France
*Corresponding author: serge.bourbigot@ensc-lille.fr

Abstract: In this paper, different approaches for modeling heat transfer in materials are examined: (i) heat anisotropy in styreneacrylonitrile (SAN) copolymer provided by the nanodispersion and the orientation of single wall carbon nanotubes (SWNT), (ii) heat protection of aluminum plate using nonwoven made with high performance fibers (polyacrylonitrile or PAN), and (iii) fire protection using intumescent paint on steel plate. It is shown that Comsol Multiphysics provides a great flexibility to solve coupled physical problems including those with moving boundaries and permits to simulate accurately the experiments. Keywords: heat transfer, ALE, weak form, fluid dynamic, fire protection, intumescence.

In this paper, different approaches are examined implying the formation of a protective heat barrier: (i) heat conductivity anisotropy in styrene-acrylonitrile (SAN) copolymer provided by the nanodispersion and the orientation of single wall carbon nanotubes (SWNT), (ii) heat protection of aluminum plate using Nonwoven (NW) made of high performance fibers (polyacrylonitrile or PAN), and (iii) fire protection using intumescent paint on steel plate. All modeling and simulation presented in this work are done using the heat transfer module of Comsol Multiphysics V.3.2b.

2. Heat conductivity PAN/SWNT film

anisotropy

in

1. Introduction
Today the probability of a catastrophic fire razing an entire town in peacetime is remote. Due to the plethora of mainly governmental legislation fire protection plays an extremely important role in reducing fire risk. Nevertheless, the development of science and technology provides the availability of sophisticated products but concurrently, increases the use of combustible materials [1]. Various methods can be used to protect materials more effectively against attack by fire. An efficient way is to use flame retardants and/or particles (micro or nanodispersed) directly incorporated in the materials (e.g. thermoplastics or thermosets) or in a coating covering their surface (e.g. structural steel or textiles) [2]. This approach is very often preferred to provide low flammability to polymeric materials because it is an acceptable compromise between cost and properties and because it brings great flexibility to design materials with multifunctional properties. The mode of action is generally attributed to the formation of a heat barrier at the surface of the materials decreasing heat transfer from the flame and/or from the external heat flux to the substrate.

Carbon-nanotubes (CNT) discovered in 1991 by Sumio Iijima [3] have demonstrated superior mechanical, electrical and thermal properties [4][5], and so enable new material applications. Thermal conductivities of 300-6600 W/m.K in the axial direction of isolated (10,10) carbon nanotubes calculated from molecular simulation together with experimental measurements of 1750-5850 W/m.K for CNT mats suggest that CNTs may have application for thermal management in polymer composites [6]. The high heat conductivity of CNT when they are nanodispersed in a polymer should permit to make materials diffusing heat more rapidly than pure polymers. Based on this concept, SAN/SWNT films with highly oriented SWNT (orientation in one direction) were prepared to make protection in elbow of firefighters clothing (films were prepared at NIST, Gaithersburg, MD USA) [7]. The purpose here is to avoid the accumulation of heat in localized parts of the clothing. To evaluate the efficiency of the concept, experimental set-up includes an IR camera (ThermaCAM SC2000, FLIR Systems) with a spectral range from 7.5 m to 13 m used for the image acquisition. The films were clamped between two copper frames and held horizontally. The heat flux was supply by a

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris

light bulb to one side of the sample, and the IR images were recovered from the other side of the sample (Figure 1). Typical results are shown in Figure 2.
IR camera Sample

bulb

Sample holder

Table 1. Parameters and their values used in the computation Parameter Value 1100 kg/m3 Density - Heat capacity - cp 1700 J/kg.K Heat conductivity - k Pure SAN: k = 5 W/m.K (isotropic) SAN/SWNT: k is anisotropic kxx = 50 W/m.K kyy = 5 W/m.K kzz = 5 W/m.K External heat source 1300 W/m

& q

Figure 1. Experimental set-up to measure temperature gradient in SAN and in SAN/SWNT films undergoing a heat flux of 5.2 kW/m

External temperature Text Temperature of the surrounding - Tamb Emissivity Stefan Boltzmann constant Convection coefficient

300 K 300 K 0.92 5.67.10-8 W/m.K-4 10 W/m.K

In the computation, we assume that heat flux is applied in one point of the film. It was implemented in our model using weak forms in a point located in the middle of the film as 4 & q + h (Text T ) + Tamb T 4 . The resulting

Figure 2. Temperature gradient in PAN film measured by an IR camera

simulation shows that heat propagates mainly in one direction (as expected) in the case of SAN/SWNT film (Figure 3 (a)) while a temperature gradient forming a circle is obtained in pure SAN film (Figure 3 (b)).

The simulation of the experiments is done in 3D using the thin shell mode (heat transfer in films are indeed modeled) implemented in Comsol Multiphysics. The relevant equation is the heat diffusion equation (Equation 1) without heat source associated with its boundaries (Equation 2) written with the usual notations: T .c p . + ( kT ) = 0 t
Equation 1 Equation 2

(a)

r 4 & n ( kT ) = q + h (Text T ) + Tamb T 4

The values used in the computation are shown in Table 1. Note we assumed in the calculation that SWNTs were well aligned in only one direction (x-direction). This assumption is reasonable according to our observation about the dispersion of SWNT in SAN.

(b)
Figure 3. Simulated temperature gradient in SAN/SWNT film (a) and in pure SAN film (b) at t= 10s

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris

Comparing the experimental results with our simulations (not shown), simulated temperature gradients and temperatures agree relatively well with the measured ones. It is noteworthy that the measured temperature gradient in SAN/SWNT film does not exhibit a flat elliptic shape but a deformed circle in the x-direction probably because the alignment of SWNT was not completely in only one direction.

backside of the plate allows accurate measurement of the surface temperature of the plate using an infrared pyrometer. The infrared pyrometer is at a constant distance from the aluminum plate and the beam is pointed on the center of the plate. It detects the temperature on the non heated face of the steel plate and records the time / temperature curve on a computer (Figure 4). NW as heat barrier is put on the aluminum plate. PAN nonwoven can be assimilated to a porous medium constituted by air and fibers. Several assumptions are made: (i) convective fluid (air) and porous medium in local thermal equilibrium (Ts = Tf = T ; s = solid and f = fluid), (ii) fluid (air) and porous medium are homogeneous and isotropic, (iii) air is an ideal gas and (iv) heat conduction takes place in parallel so that there is no net heat transfer from one phase to the other. Heat diffusion equations can be written for the two phases (solid (Equation 3) and fluid (Equation 4)) as:

3. Heat protection of aluminum plate by nonwoven

Nonwoven (NW) is a generic term used to describe a fabric that is produced differently from a fabric made by weaving or, more broadly, a fabric that is different from traditional woven or knitted fabrics. Like all fabrics, NW is planar structures that are relatively flat, flexible, and porous. Our purpose here is to use NW made in high performance fibers (PAN) as potential flexible heat barrier for materials. PAN exhibits superior thermal resistance [8] and it is used to heat protect an aluminum plate.

(1 )( c p ) s
Equation 3

Ts = (1 ) (k s Ts ) t

Heat radiator Steel plate

( c p ) f

T f t

+ ( c p ) f u T f = (k f T f )

Equation 4

where is the porosity defined as the fraction of the total volume of the medium.
Infrared pyrometer Connected to computer

Figure 4. Small scale test to measure the efficiency of a heat barrier

Setting Ts = Tf = T: T ( c p ) m + ( c p ) f u T = (k mT ) where t the subscript m means the medium (here fluid + solid), ( c p ) m = (1 )( c p ) s + ( c p ) f and
1 k m = k s .k (weighted geometry mean of ks f

In our laboratory, we have recently developed small scale test permitting to measure the efficiency of a heat barrier recording on the backside of the material to be protected the temperature as a function of time when undergoing the upper side to an external heat flux [9]. The heat source is a heat radiator. Aluminum plates used are squares of 5*5 cm and 3.5mm thick. A black coating, provided by Medtherm Corporation (Huntsville, Al), resistant to 800C and having a constant emissivity of 0.92 is applied on the non-heated side of the aluminum plates. The constant emissivity of the

and kf). The convection of fluid u is calculated coupling Navier-Stokes equation (Equation 5) and the equation of continuity for a compressible flow (air) (Equation 6) with the heat diffusion equation assuming that (i) air confined in NW leads to small density variations due to temperature differences, and that (ii) there are low velocities and no compression/expansion of the fluid (air) resulting in substantial internal work or heat effects:

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris

u + (u )u = pI + (u + (u)T ) (2 / 3 )( u)I t

Equation 5

+ ( u) = 0 t

where p is the pressure, is the dynamic viscosity and is the dilatational viscosity.
nj ni i R Aj, Tj j dAj

Equation 6

Heat radiator
cos i cos j 1 dAi dA j Ai Ai Aj R2

Ai , Ti

Fi,j =
dAi

Radiosity J: J=(1-).G + T4 G = (T, view factor F)

Radiative heat transfer between 2 surfaces

Figure 6. Temperature gradient in PAN nonwoven undergoing an external heat flux at t = 13s
Exp. 460 Temperature (K)

Convection (h) and radiation () on sides (Al + PAN)

Outflow/pressure conditions on sides and no slip (u=0) at the interface Al/PAN

Simulated 420

Figure 5. Boundaries used in the model

The equations presented above are implemented in Comsol Multiphysics (general heat transfer module and non isothermal flow) and were solved in 3D using boundaries described in Figure 5 and with the values of Table 2.
Table 2. Parameters and their values used in the computation Parameter Value Density - PAN = 1200 kg/m3 air = p.28.8.10-3/(8.314.T) kg/m3 Heat capacity - cp cp_PAN = 3000 J/kg.K cp_air = 1100 J/kg.K Heat conductivity - k kPAN = 10 W/m.K kair = 10(-3.723+0.865.log10(abs(T))) W/m.K Surface temperature of 1000 K the heat radiator Porosity 0.75 Emissivity 0.92 Stefan Boltzmann 5.67.10-8 W/m.K-4 constant Convection coefficient hside = 10 W/m.K hsurface = 20 W/m.K

380 340 300 0 400 800 Time (s) 1200

Figure 7. Comparison of the evolution of simulated and experimental temperatures as a function of time on the backside of the assembly aluminum + PAN

4. Fire protection intumescent paint

of

steel

using

The resulting simulation is shown in Figure 6 and it can be seen that it agrees very well experimental data (Figure 7).

When heated beyond a critical temperature, an intumescent material begins to swell and then to expand [10]. The result of this process is a foamed cellular charred layer on the surface which protects the underlying material from the action of the heat flux and/or of the flame (Figure 8). Intumescent paint can be used for protecting steel and so, for avoiding the collapse of the structure of the building in the case of fire. Using the same device as above (Figure 4), heat transfer in an intumescent coating applied on steel is evaluated.

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris

Figure 8. Intumescent coating prepared from a paint undergoing an external heat flux

Intumescence means swelling of a carbonaceous structure as a function of time with a strong modification of the thermophysical parameters. It is a typical problem of heat transfer including moving boundaries. Our first approach of this problem (further work is in progress) is to take into account the dynamic of the problem using ALE method implemented in Comsol Multiphysics V.3.2 coupled with heat transfer and fluid dynamic. The relevant equations are the heat diffusion with a heat source to model the degradation and a convective term (Equation 7) and the Navier-Stokes equation (Equation 8) for an incompressible flow (Equation 9):

In Equation 7, the heat source Q permits to model the degradation of the material. Kinetic parameters associated to the degradation (frequency factor and activation energy) were calculated using thermogravimetry via a kinetic analysis. It is also noteworthy that in Equation 8, the vector F is used to simulate internal forces taking place during the swelling of the material. In this calculation, phenomenological laws were used but they do not correspond to real physical phenomenon (further work is still in progress). The only goal here was to mimic the swelling of intumescence. The equations were then solved in 2D (Figure 9) in the ALE frame using boundaries similar as those described in Figure 5 and with the values of Table 3. Note that the thermal properties of the intumescent char (subscript intu) and of the steel (subscript steel) are taken constant (mean values) in this work while they vary as a function of temperature [11].
Table 3. Parameters and their values used in the computation Parameter Value Density - intu = 1500 kg/m3 steel = 7850 kg/m3 Heat capacity - cp cp_intu = 3000 J/kg.K cp_steel = 475 J/kg.K Heat conductivity - k kintu = 1 W/m.K ksteel = 44.5 W/m.K Surface temperature of 1000 K the heat radiator Latent heat - L 106 J Frequency factor - A 3.1010 s-1 Activation energy - E 1.8.105 J/mol Heat source - Q -A.intu.exp(-E/RT).L Gravity - g 9.81 m/s Internal force - F Fx = -g.x.exp(-t/0.01) Fy = -g.y.0.75.exp(-t/0.01) Emissivity 0.92 Stefan Boltzmann 5.67.10-8 W/m.K-4 constant Convection coefficient 10 W/m.K

.c p .

T + ( kT ) = Q .c p .u.T t

Equation 7

u + (u )u = pI + (u + (u)T ) + F t

Equation 8

u = 0

Equation 9

Figure 9. Mesh of the experimental set-up in 2D consisting of 1320 elements

The results of the computation show that our approach permits to simulate the expansion (intumescence) of the paint when undergoing an external heat flux (Figure 10). Nevertheless the height of the expansion is not as high as observed during the experiment because only phenomenological law was implemented in our model. The expansion starts at the earliest times as it was observed experimentally and provides the protection of interest to steel. We have to

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris

remind the reader that structural steel loses a significant part of its load-carrying ability when its temperature exceeds 500 C and that the fire protection parameter is defined as the time for which the temperature reaches 400 C [12]. So, an intumescent paint should avoid that steel temperature reaches 400C for a time as long as possible (usually more than one hour). Figure 11 compares the calculated temperatures at the interface paint/steel and at the surface of virgin steel. It can be seen that intumescent paint provides a large protection to steel since a temperature difference of 200C is calculated at 150s. The temperature of steel does not reach 400C at this time. It is also noteworthy that the temperature evolutions are similar as those measured experimentally except that the time scale is shorter due to the phenomenological law implemented in the model.

5. Conclusions
In this paper, different problems of heat transfer were examined and modeled using the software Comsol Multiphysics. Comsol Multiphysics provides a great flexibility to solve coupled physical including those with moving boundaries and permits to simulate accurately the experiments.

6. References
[1] S. Bourbigot, M. Le Bras and J. Troitzsch in International Plastic Flammability Handbook, 3rd edition, Edited by J. Troitzsch, Published by Hanser Verlag, Munich, pp. 3-6, (2004) [2] M. Lewin in Fire Retardancy of Polymers: The Use of Intumescence, Edited by M. Le Bras, G. Camino, S. Bourbigot and R. Delobel, The Royal Chemical Society, Cambridge, pp. 3-11, (1998) [3] S. Iijima, Nature, 354, 56-58, (1991) [4] B.G. Demczyk, Y.M. Wang, J. Cumings, M. Hetman, W. Han, A. Zettl, and R.O. Ritchie, Mater. Sci. Eng, A334, 173-178, (2002) [5] M.-F. Yu, O. Lourie, M. J. Dyer, K. Moloni, T. F. Kelly, R. S. Ruoff, Science, 287, 637640, (2000) [6] R. Andrews, D. Jacques, M. Minot, and T. Rantell, Macromol. Mater. Eng., 287, 395403, (2002) [7] J.W. Gilman, S. Bellayer, L.M. Hanssen, S. Bourbigot, X. Flambard and S. Kumar, SAMPE 2006, Edited by A. Pilato and S. Kliger, Published by SAMPE, Long beach, CA, in press, 2006 [8] S. Bourbigot and X. Flambard, Fire Mater., 26, 155-168, (2002) [9] M. Jimenez, S. Duquesne and S. Bourbigot, Ind. Eng. Chem. Res., in press, (2006) [10] S. Bourbigot, M. Le Bras, S. Duquesne, M. Rochery, Macromol. Mat. Eng. 289(6), 499511, (2004) [11] S. Bourbigot, S. Duquesne and J.M. Leroy, J. Fire Sci., 17, 1-15, (1999) [12] M. Jimenez, S. Duquesne and S. Bourbigot, Ind. Eng. Chem. Res., 45, 4500-4508, (2006)

Figure 10. Simulation of the swelling and of the temperature gradient in an intumescent coating undergoing an external heat flux

800

700

Temperature (K)

600

500

400

300 0 20 40 60 80 100 120 140

Time (s)

Figure 11. Temperature as a function of time at the interface steel paint (solid line) and at the surface of steel without paint (dashed line)

Excerpt from the Proceedings of the COMSOL Users Conference 2006 Paris

7. Acknowledgements
Drs. Jeff W. Gilman and Sverine Bellayer from BFRL/NIST (Gaithersburg, MD USA) are gratefully acknowledged for helpful collaboration and discussion. The authors are indebted to Miss Aurore Vannier from our group for participating in this work and for helpful discussion. This work was partially supported by the European project FLEXIFUNBAR (Multifunctional barrier for flexible structure).