Research Article

Received: 8 September 2011 Revised: 4 November 2011 Accepted: 9 November 2011 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/pi.4160

Design and optimization of an intumescent ame retardant coating using thermal degradation kinetics and Taguchis experimental design
Zahra Derakhshesh,a Manouchehr Khorasani,b Shahin Akhlaghi,c Bahram Keyvania and Ali Asghar Sabbagh Alvanib
Abstract
Two supplementary approaches in terms of thermal degradation kinetics and Taguchis experimental design were employed toward developing a design effort for intumescent coatings. A model intumescent system including ammonium polyphosphate (APP), pentaerythritol (PER), melamine (MEL), thermoplastic acrylic resin and liquid hydrocarbon resin was chosen and then subjected to thermogravimetric analysis and heat insulation tests to provide experimental data. Kinetic analysis of the thermogravimetric data based on the Friedman and Kissinger methods revealed that activation energy (Ea ) and reaction order (n) could be used as parameters to accurately judge whether the selected intumescent components represented coordinated thermal characteristics. Examination of the calculated Ea and n values showed that the decomposition of thermoplastic acrylic resin and liquid hydrocarbon resin occurred rst and that the APP, PER and MEL components were degraded immediately after. Such a degradation sequence was quite consistent with the functional mechanism of intumescent systems. In addition, simultaneous implementation of analysis of variance and mean effect assessment on the Taguchi data demonstrated that the designed formulation, based on the optimized coupling of 10 g MEL into APP/PER 25 g/11 g, exhibited the highest reproong time among the prepared coating samples. The APP content had the most important contribution to the ame retardant behaviour, and APP versus PER interactions showed the highest severity index. Scanning electron microscopy showed that the higher ame retardancy of the optimized sample was related to the presence of a large number of micropores in the expanded charring layer structure. c 2012 Society of Chemical Industry Keywords: intumescent coating; thermal degradation kinetics; Taguchi method; ANOVA

INTRODUCTION
The increasing awareness towards the re protection of structural steel, as a construction material widely used in civil buildings, chemical plants and other facilities, has led to the development of various classes of ame retardants. Intumescent coatings represent an efcient, environment-friendly and economic way to provide passive re protection, combined with an attractive aesthetic feature.1 3 An intumescent ame retardant system is commonly composed of three active additives including an acid donor (normally ammonium polyphosphate, APP), a carbon donor (such as pentaerythritol, PER) and a blowing agent (e.g. melamine, MEL) which are bound together with a polymeric binder.1 3 It is generally accepted that when an intumescent coating is exposed to re the binder initially melts to provide a exible basis for foam formation.4 Thereafter, the acid donor breaks down to yield a mineral acid which takes part in the dehydration of the carbon donor and the carbon char formation.4 Such charring layer, when associated with the gaseous products of the blowing agent decomposition, gradually swells to form an expanded multicellular char layer on top of the material.4 The resultant intumescent layer can act as an insulation barrier which shields

the underlying material against the heat generated by ame, consequently maintaining the structural integrity of the building.5 Owing to increasingly stringent re safety regulations within the construction industry, intumescent ame retardants are still under development and new technologies are urgently required. Although various compounds have been proposed to formulate new intumescence compositions, many of these cannot meet the re protection requirements for steel.6 In this regard, many attempts have been made to elucidate the probable reasons for inefciency of such intumescent coatings.7 9 The overall

Correspondence to: Manouchehr Khorasani, Amirkabir University of Technology, Color and Polymer Research Center, Tehran, Iran. E-mail: khorasani.m@aut.ac.ir

a Islamic Azad University, Saveh Branch, Faculty of Engineering, Chemistry Department, Save, Iran b AmirkabirUniversityofTechnology,ColorandPolymerResearchCenter,Tehran, Iran c Department of Polymer Engineering, South Tehran Branch, Islamic Azad University, Tehran, Iran

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www.soci.org conclusion emerging from these studies relies on two major lines of argument. First, a satisfactory intumescence phenomenon is only ensured by the occurrence of an array of chemical and physical processes in appropriate sequence.7 Thereby, the intumescent coating additives must be chosen in such a way that their thermal behaviours are suitably matched together. For example, Camino et al.7 showed that urea failed to act as a blowing agent for the combination of APP with PER, since it evolves gaseous degradation products at a temperature lower than that at which the APP/PER system forms the char layer. However, Gu et al.8 reported that the decomposition temperatures of MEL, APP and PER were contiguous and that a steady intumescent layer was formed over the whole range of the degradation process. On the other hand, since the ame retardant mechanism of intumescent systems depends signicantly on the composition of the components, the concentration of each particular additive in the formulation should be optimized to attain a desirable re protection.9 For example, Antia et al.9 found that the nal products structure of the chemical reaction between APP and PER depended heavily on the PER/APP molar ratio. As the authors stated, the maximum carbon content in the char which resulted in the highest efciency of the intumescent coating was observed with a PER/APP molar ratio of 6 : 1. However, even with such helpful guidelines, there is still no practical procedure that guarantees the efciency of an intumescent ame retardant formulation from both the design and optimization points of view. Therefore, with regard to the vital contribution of the thermal properties and composition of additives in the ame retardancy of intumescent coatings, in this paper we employed two supplementary approaches toward developing an effective design system for such coatings. First, because the kinetic parameters of the thermal decomposition process provide direct information about the thermal behaviour of materials, the data obtained from the thermal degradation kinetics analysis were used to accurately judge whether the selected additives represented coordinated thermal characteristics. In keeping with this, an inexpensive and easy-to-operate experimental strategy based on Taguchis parameter design was further adopted to optimize the composition of the intumescent formulation components for manifestation of the most desirable ame retardancy. For this purpose, an intumescent system containing APP, PER, MEL, a thermoplastic acrylic resin (TAR) as binder, a liquid hydrocarbon resin (LHR) as plasticizer and titanium dioxide (TiO2 ) as pigment was prepared. In order to follow the thermal degradation kinetics of the additives, TGA was individually performed on each of the formulation components at various heating rates. A Taguchi orthogonal array was then selected for the experimental plan and the optimization process was carried out for the reproong time obtained from the heat insulation test. Finally, the morphology of the residual coal of the selected samples was studied by SEM.

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Table 1. Factor

Selected factors and their respective levels Level 1 (g) 10 1.5 21 9 10 Level 2 (g) 11.5 2.5 23 10 11 Level 3 (g) 13 3.5 25 11 12 Level 4 (g) 14 4.5 27 12 14

TAR content LHR content APP content MEL content PER content

a solid content of 58% 1% and viscosity at 25 C of 10 00015 000 cP (1015 Pa.S) was supplied by Taak Resin Co., Tehran, Iran. TiO2 powder (Kronos 2300) with a density of 4.1 g cm3 , brightness L of 97.4 and tone B of 1.5 was purchased from Kronos International Inc., Leverkusen, Germany. LHR (Novares LA 700) with a density of 1.011.05 g cm3 and OH content of 2.3%2.8% was purchased from Rutgers GmbH, Duisburg, Germany. Also, the substrates used in this study were steel 304 grade panels having dimensions 3 70 150 mm3 . All the test substrates were degreased with pure acetone and polished with 180 grit sandpaper prior to coating application.

Experimental design The common approach in the research plan is to change one parameter at a time, which involves numerous experimental runs to wholly explore the effect of the entire parameter on the output results. However, the experimental design using the Taguchi approach, Patnaik A et al.10 can be used as a powerful analysis tool to minimize the number of experiments while retaining quality of data collection.10 In addition, analysis of variance (ANOVA) on the data collected from the Taguchi experimental design can be used to optimize the performance characteristics.10 According to the objectives of the present study, ve factors were introduced as affecting the ame retardant behaviour of the intumescent coatings; these were the APP, PER, MEL, TAR and LHR loadings. Each of these factors was considered to be varying at several levels that are summarized in Table 1. Consequently, from the number of factors and levels that have been selected, an orthogonal array of L16 type was used as shown in Table 2.

EXPERIMENTAL
Material APP (Exolit AP 422) with a phosphorus content of 31%32% (w/w) and nitrogen content of 14%15% (w/w) was purchased from Clariant GmbH, Sulzbach, Germany. PER (Penta tech) with a molecular weight of 142.5 g mol1 and OH value of 1615 mg KOH g1 was supplied by Perstorp Co., Bruchhausen, Germany. MEL with a molecular weight of 126.12 g mol1 was obtained from BASF-AG, Ludwigshafen, Germany. Acrylic resin (Tacryl MC25) with

Sample preparation At rst, TAR and LHR were mixed through vigorous agitation at room temperature. At the same time, APP, PER, MEL and TiO2 were mixed and ground for about 1 h in a ball-mill to reach a particle size under 10 m. The resulting compounds, with the formulations presented in Table 2, were mixed together in a high-speed disperse mixer for 3 h. It should be noted that the TiO2 weight was constant (5 g) in all the compounds. Since the prepared intumescent coatings had a high solid concentration, an airless spray method was used to apply the coating on steel substrates. For each of the samples, three layers of coatings were applied including an epoxy primer (60 m thick), an intumescent coating (1000 m thick) and a top coat (60 m thick) to protect the re retardant as well as the desired colour shade. The coated panels were then exposed to fresh air to dry for at least 1 week. After the coatings were entirely dry, they were pulverized on a Retsch ZM-1 hammer mill and sieved to obtain a powder for TGA experiments.
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Design of an intumescent ame retardant coating

www.soci.org following expression:12 ln d dt = ln A + n ln(1 ) Ea RT (4)

Table 2. The L16 orthogonal array for selected factors and levels and the corresponding mean reproong time for each trial Trial no. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 TAR (g) 10 10 10 10 11.5 11.5 11.5 11.5 13 13 13 13 14 14 14 14 LHR (g) 1.5 2.5 3.5 4.5 1.5 2.5 3.5 4.5 1.5 2.5 3.5 4.5 1.5 2.5 3.5 4.5 APP (g) 21 23 25 27 23 21 27 25 25 27 21 23 27 25 23 21 MEL (g) 9 10 11 12 11 12 9 10 12 11 10 9 10 9 12 11 PER (g) 10 11 12 14 14 12 11 10 11 10 14 12 12 14 10 11 Mean reproong time (min) 46.7 120.3 66.3 54 89.3 53.3 87.3 69 104 125.7 116.3 88.3 89 55.3 50.7 56

For each value, the plot of ln(d/dt) versus T 1 , obtained from thermograms recorded at several heating rates, should be a straight line whose slope allows the evaluation of Ea . The plot of ln(1 ) against T 1 would also give the n value from the maximum slope of the line. Another technique used to determine the degradation kinetics parameters is the Kissinger method, Kissinger HE.13 The rate equation in this method can be expressed as follows:12 ln
2 Tmax

= ln

AR Ea + ln n(1 max )n1 Ea RTmax

(5)

Characterization methods TGA TGA studies of the samples was carried out using a Polymer Laboratories TGA-PL apparatus at the temperature range of 30600 C under oxygen atmosphere with owing rate of 30 mL min1 and the sample size of 0.6 mg. Conventional constant heating rate measurements were run at 5, 10, 20 and 40 C min1 to cover a wide range of thermal conditions. TGA tests were carried out in aluminum crucibles (5.9 4.7 mm) where samples were placed without any previous treatment and experiments were run immediately. Kinetics models All the degradation kinetics studies begin with a fundamental rate equation which describes the conversion () rate d/dt through a temperature-independent function of the conversion, f(), and a temperature-dependent constant rate of reaction K, i.e.11 d = Kf() dt (1)

where , Tmax and max are the heating rate in the TGA experiments, the temperature and the conversion at the maximum conversion rate (d/dt)max , respectively. The slope of the linear plot of ln(/T 2 max ) versus 1/Tmax yields the Ea value, and its intercept I is12 AR (6) I = ln + ln n(1 max )n1 Ea The n value can then be calculated from the equation12 n= (1 max ) exp(E/RTmax ) Ea exp(I) R(d/dt) (7)

Heat insulation test A custom-made furnace according to DIN4102 part 8 was used to perform heat insulation tests on the coated steel plates. Temperature changes of the plates were recorded every 2 min to form the temperaturetime plots. The reproong time for each of the samples was reported as the time taken for the tested plate temperature to reach 500 C. SEM SEM was performed with a Tescan VEGA-II apparatus equipped with an energy beam of 20 kV. The selected samples were fractured in liquid nitrogen and then coated with gold by vapour deposition using a vacuum sputter prior to SEM observations.

The temperature dependence of the rate constant is expressed in terms of the Arrhenius equation as11 K = A exp Ea RT (2)

RESULTS AND DISCUSSION

Thermal decomposition analysis Thermal degradation of the intumescent coating additives was studied using TGA under an O2 atmosphere, which is the same as in the event of a real re exposure. Figures 1 and 2 illustrate the TGA and differential thermogravimetry (DTG) curves of the pure TAR, LHR, APP, PER and MEL samples, respectively, at a rate of 10 C min1 . A two-step degradation process was observed for the pure TAR (see Fig. 2). The rst step with marginal weight loss (36%) could be related to the evaporation of physically absorbed water and residual solvent from 30 C to 165 C.14 It was previously established that the main weight loss in the range 250450 C is attributed to decomposition of the polymer (Fig. 1).14 In the case of pristine LHR, a sharp reduction in weight was detected in the 250400 C temperature range, leading to evolution of carbon dioxide.15 The degradation process was followed more gradually at temperatures above 400 C until the whole material

where A is a frequency factor corresponding to the incidence of molecular collisions that should be obtained to produce a chemical reaction. In addition, Ea , R and T are the activation energy, the gas constant and the absolute temperature, respectively. The simplest and most frequently used form of f() assumes that the rate of conversion is proportional to the nth order of the material concentration:11 f() = (1 )n (3)

where n is the order of reaction. By inserting Eqns (2) and (3) into Eqn (1), rearranging and taking logarithms, Friedman provided the
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Figure 1. The TGA curves of the selected intumescent additives.

Figure 2. The DTG curves of the selected intumescent additives.

was eliminated at 700 C (see Fig. 1). LHR is believed to serve as a plasticizer to ensure the exibility of the charring layer for the necessary thickness to be achieved. Thermal degradation of pure APP also occurred in two major stages (see Fig. 2). These stages were involved in an analogous degradation mechanism but with a different rate of decomposition.16 In both stages, the APP structural groups were degraded with the release of NH3 and H2 O molecules and formed

POP crosslinks, as shown in Scheme 1(A).16 Complete hydrolysis of the crosslinked units would give strongly and weakly acidic groups, depending on the relative rate of hydrolysis of the bonds involved (Scheme 1(B)).16 The elimination of NH3 and H2 O results from the partial degradation of the crystalline form of APP (I) to the more stable form (II) under the inuence of heat.16 Since loss of NH3 was previously reported to accelerate the crystalline transition,16 the rate of decomposition increases upon rise of

Scheme 1. The schematic presentation of the formation of POP crosslinks (A) and complete hydrolysis of the crosslinked units (B).

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Design of an intumescent ame retardant coating ammonia evolution in the second stage (500700 C) compared with the rst one (210485 C). Thermal degradation of the pure PER began at 230 C and was followed by a dramatic weight reduction up to 350 C (see Fig. 1). It is known that such a weight loss is ascribed to the elimination of water molecules in early stages of the degradation process and intramolecular dehydrogenization of the PER chains.15 Finally, the pure MEL sample appeared to decompose in the 250350 C temperature range (Fig. 1). Upon heating, part of the MEL instantly sublimes at the same time as the other part loses ammonia and undergoes a series of ammonia-losing condensations to yield NH, linking two-, three- and multiple-ringcontaining products, namely melamine, melem (-2,5,8-triamino 1,3,4,6,7,9,9beptaazaphenalene) and melon (poly [8-amino1,3,4,6,7,9,9b-Heptaazaphenalene-2,5-diyl] imino), respectively.15 As postulated by other authors,14,17 the sublimed melamine vapours and the released ammonia are not merely ame inhibitors themselves, but also blow the char formed by the APP/PER system to get an intumescent layer at the nal stage. From the thermal decomposition analysis of the components above, one can infer that the degradation temperature ranges of TAR, LHR, APP, PER and MEL are contiguous and properly consistent with the functional mechanism of intumescent ame retardants. Kinetics of thermal degradation Application of the TGA method holds great promise as a tool for unravelling the kinetic parameters of the chemical reactions that are involved in the degradation process of the materials. The thermal degradation kinetics of TAR, LHR, APP, PER and MEL based on the Friedman and Kissinger techniques are presented here. Fitting the TGA data at heating rates of 5, 10, 20 and 40 C min1 in the Friedman equation (Eqn (4)), we obtain plots of ln(d/dt) versus T 1 and ln(l ) versus T 1 at different conversions of the entire additives. According to the thermal decomposition analyses presented in the previous section, unlike the PER and MEL components, the TAR, LHR and APP additives show twostep degradation proles, meaning the occurrence of plural degradation reactions. Nevertheless, since the initial stage of thermal degradation ( < 0.5) of the formulation components has a crucial role in the design system, we merely considered the thermal characteristics of the rst degradation step for the kinetic studies. Figure 3 illustrates the ln(d/dt) versus 1000/T and ln(l ) versus 1000/T plots at values of 0.2, 0.4, 0.6 and 0.8 for the APP component, as an example. The two sets of straight lines tted exhibited a good correlation coefcient (R2 > 0.98), conrming the applicability of the Friedman method for studying the degradation kinetics of the intumescent coating components. In addition, ln(/T 2 max ) versus 1000/Tmax plots were obtained from application of the Kissinger model (Eqn (5)) to the TGA data. A representative Kissinger plot for the APP component is shown in Fig. 4. Reasonable straight lines were obtained for the entire experiments. The average values of Ea and n for the selected additives were obtained from Friedman and Kissinger plots based on the procedure discussed earlier and are listed in Table 3. Obviously, the kinetic parameters calculated by the two methods did not show signicant differences. One must note, however, that a slight disagreement between the results obtained from the Friedman and Kissinger models might be ascribed to the different mathematical approaches used to calculate the parameters.
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Figure 3. The Friedman graphs for the APP component: (A) ln(d/dt) versus 1000/T; (B) ln(1 ) versus 1000/T.

Table 3. The Friedman and Kissinger Ea and n values of selected intumescent additives Friedman Sample TAR LHR APP MEL PER Ea (kJ mol1 ) 71 76 129 165 153 n 0.83 1.02 0.79 2.01 1.84 Kissinger Ea (kJ mol1 ) 73 77 137 161 156 n 0.85 1.11 0.82 1.97 1.86

Since Ea can be dened here as the minimum amount of energy required to initiate the degradation process, one can consider Ea as a quantitative parameter to assess the occurrence sequence of the decomposition reactions of the intumescent additives. We believe that the Ea value is a more accurate criterion than degradation onset temperature for evaluating the initial thermal behaviour, because the calculation of Ea requires TGA data at various heating rates. In other words, unlike the degradation onset temperature, the Ea parameter considers the effect of heating rate on the degradation process. The most interesting point concerning the

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Table 4. The mean effects of various levels of the studied factors on reproong time of the prepared intumescent coatings Mean effect Factor TAR content LHR content APP content MEL content PER content Level 1 71.8 82.2 68.1 69.4 73.0 Level 2 74.7 88.7 87.2 98.7 91.9 Level 3 108.6 80.2 89.0 84.3 74.2 Level 4 62.8 66.8 73.7 65.5 78.7

Table 5. Estimation of the SI values of the factor interactions for reproong time of the prepared intumescent coatings Interaction Figure 4. The Kissinger graph for the APP component. APP vs PER APP vs MEL PER vs MEL TAR vs LHR TAR vs APP TAR vs PER LHR vs APP LHR vs PER MEL vs TAR MEL vs LHR 69.4 58.2 39.7 38.1 35.5 23.8 23.8 15.3 14.3 6.7 SI (%)

calculated kinetic data was that the Ea values of the samples were in the order MEL > PER > APP > LHR > TAR (see Table 3). This nding can be taken into account as further evidence for the appropriate order of the degradation reaction of the intumescent formulation components. Bearing in mind that the n value is directly related to the consumption rate of the reactants in the degradation reaction, such a kinetic parameter could provide a precise insight into the degradation period of the materials. The decomposition process of a sample with lower n value is slower than that of one with higher n value. It is apparent that the calculated n values are in the order MEL > PER > LHR > TAR > APP (see Table 3). Interestingly, the APP which must efciently contribute to the formation of the basic char structure during the whole intumescent process exhibited the lowest n value of all the additives. Of course, charring production is initiated at the beginning of the intumescent process and continues to the end of it. Therefore, the APP as mainly responsible for charring production should possess the slowest degradation reaction to be able to cover such a long time process. In contrast, the highest n value belonged to the MEL component, which was expected due to the short-time performance of the blowing agent in the intumescence phenomenon. Taguchis experimental design Mean effect assessment The results obtained regarding the reproong time of all the prepared samples are listed in Table 2. In order to investigate the role of the selected factors on the samples reproong time, the main effect of each factor must be taken into account at every level. The mean effect (F) of a dened factor at each of the levels (Ln , n represents the level number 1, 2, 3 and 4) is obtained by adding the results of all trial conditions ( yi ) at the level considered and then dividing by the number of data points added (N):18 FLn = yi N (8)

clearly indicates that the selected levels for the studied factors were properly designed and all the optimum conditions were in the chosen ranges. From Table 4, when the TAR weight was between 10 g (level 1) and 13 g (level 3), the mean effect on the reproong time was increased to 108.5. In contrast, as the TAR weight reached 14 g (level 4), the mean effect decreased remarkably. It seems that at TAR contents higher than 14 g the residue char was too loose to have a protective effect, leading to faster heat transfer. This phenomenon can also be observed as the LHR content increased over 2.5 g (see Table 4), which might be related to the deterioration effect of excess LHR on the mechanical stability of the char layer. A close inspection of the Taguchi data in Table 4 indicates that the optimum heat insulation behaviour occurred at an MEL content of 10 g coupled with APP/PER 25 g/11 g. The interactive analysis was also performed on selected factors to evaluate the inuence of two individual formulation components at various levels of the interaction.18 The calculated severity index (SI), as a measure of the extent of interaction between two chosen factors, is listed in Table 5. Among the 10 interaction pairs studied, the SI values ranged between 69.4% and 6.7%. Obviously, the APP and PER content interaction showed the highest SI value, while the MEL content versus the LHR content exhibited the minimum SI value (see Table 5). ANOVA results After successful analysis of the mean effects, ANOVA was performed on the Taguchi data to estimate the error variance and to determine the relative importance of the studied additives.18 The standard ANOVA began with calculation of the total value of
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Table 4 shows the main effects of the TAR, LHR, APP, MEL and PER contents on the reproong time of the intumescent coatings with a 95% condence level. For all the additives, the reproong time increased with increase in the additive content up to a certain value and then decreased on further addition of the additive. This

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Table 6. ANOVA table for reproong time of the prepared intumescent coatings Factor TAR content LHR content APP content MEL content PER content SS 1009.5 898.9 4832.0 1255.2 2754.8 Variance 336.49 299.63 1610.66 418.40 918.27 P (%) 9.39 8.36 44.94 11.67 25.62

responses (T) calculated from19

m r

T=
i=1 j=1

yij

(9)

where m is the total number of trials (16) and r is the total number of repetitions (3). Thereafter, the correction factor (CF) was determined from19 r2 (10) N where N is the total number of experiments (16 3 = 48). The total sum of the squared deviations (SST ) was then calculated from the equation19 CF =
m r 2 yij CF i=1 j=1

SST =

(11)

Furthermore, the sum of squares (SS) due to a factor F was obtained through19 SS =
2 FL1

N FL

2 FL2

N FL

2 FL3

NFL3

2 FL4

N FL

CF

(12)

where NFL , NFL , NFL and NFL are the number of trials with factor 1 2 3 4 F at levels 1, 2, 3 and 4, respectively. SS can be calculated for each of the factors, i.e. SS1 , SS2 , SS3 , SS4 and SS5 , which are related to the sum of squares due to the TAR, LHR, APP, MEL and PER contents, respectively. The error sum of squares can be represented by the equation18 SSe = SST (SS1 + SS2 + SS3 + SS4 + SS5 ) (13)

where subscript e indicates the error term. Finally, the percentage contribution (P) of each factor is given by19 P= where SS = SS (Ve 5) (15) Morphological studies The physical structure of the charring layer is of a great importance in the performance of an intumescent coating. The morphology of the nal foam of samples 1, 5 and 10 was investigated using SEM. Samples 1 and 10 exhibited the lowest and highest reproong time, respectively, and sample 5 had a reproong time between those of the other samples. As can be seen from Fig. 5(C), there are many irregular micron-sized pores in the charring layer of sample 10. The air molecules trapped in these small pores could effectively decrease the heat transfer rate and protect the substrate from re.14,15 In contrast, such morphology is lacking in sample 1 and Ve is the error variance, equal to SSe /5 here. The ANOVA results determined by the above procedure are presented in Table 6. The order of P for the studied factors was as follows: APP > PER > MEL > TAR > LHR. The APP content was the most inuential factor (P = 44.94%) for maximum heat insulation behaviour. This is expected since APP had the longest functional time among the selected additives, apart from its key role in the char formation process. Since the TAR and LHR components only play a marginal role in the ame retardancy mechanism of the intumescent coatings, the low P value of these factors (P = 8.36% for LHR content and P = 9.39% for TAR content) was anticipated.
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SS 100 SST

(14)
Figure 5. SEM micrographs of samples 1 (A), 5 (B) and 10 (C).

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www.soci.org where several big channels can be observed in the charring layer (Fig. 5(A)). From these apertures, the gas and molten mass can overow to the entry of the re zone, leading to deterioration of ame retardancy. The relation between char pore sizes and reproong time can be clearly followed as the nal char structure of sample 5 is compared with those of samples 1 and 10. As can be seen from Figs 5(A)5(C), the reproong time improved upon increase of the char porosity.

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1 Chen L, Song L, Lu P, Jie G, Tai Q, Xing W, et al, Prog Org Coat 70:5966 (2011). 2 Wang G and Yang J, Prog Org Coat 70:150156 (2011). 3 Han Z, Fina A, Malucelli G and Camino G, Prog Org Coat 69:475480 (2010). 4 Levchik SV and Weil ED, J Fire Sci 24:345364 (2006). 5 Zhang S and Horrocks AR, Prog Polym Sci 28:15171538 (2003). 6 Tao K, Li J, Xu L, Zhao X, Xue L, Fan X, et al, Polym Degrad Stab 96:12481254 (2011). 7 Camino G, Costa L and Martinasso G, Polym Degrad Stab 23:359376 (1989). 8 Gu JW, Zhang GC, Dong SL, Zhang QY and Kong J, Surf Coat Technol 201:78357841 (2007). 9 Antia EK, Baldry PJ and Hirschler MM, Eur Polym J 18:167178 (1982). 10 Patnaik A, Abdulla MD, Satapathy A, Biswas S and Satapathy BK, Mater Design 31:837849 (2010). 11 Paik P and Kar KK, Polym Deg Stab 93:2435 (2008). 12 Li XG and Huang MR, J Appl Polym Sci 71:19231931 (1999). 13 Kissinger HE, Anal Chem 29:17026 (1957). 14 Li G, Liang G, He T, Yang Q and Song X, Polym Degrad Stab 92:569579 (2007). 15 Li G, Yang J, He T, Wu Y and Liang G, Surf Coat Technol 202:31213128 (2008). 16 Camino G, Costa L and Trossarelli L, Polym Degrad Stab 12:203211 (1985). 17 Ducrocq P, Duquesne S, Magnet S, Bourbigot S and Delobel R, Prog Org Coat 57:430438 (2006). 18 Mahapatra SS and Patnaik A, Mater Design 30:27912801 (2009). 19 Majdzadeh-Ardakani K, Navarchian AH and Sadeghi F, Carbohydrate Polym 79:547554 (2010).

CONCLUSION
This study set out to examine a design procedure for intumescent ame retardant coatings based on thermal degradation kinetics and Taguchis experimental design. For this purpose, a model intumescent system consisting of APP, PER, MEL, TAR and LHR was chosen. The thermal characteristics of selected additives and reproong time of the coatings prepared based on the L16 orthogonal array were investigated using TGA and heat insulation experiments, respectively. The analysis of the thermal degradation kinetics using the Friedman and Kissinger methods revealed that the calculated Ea and n values for the selected components were contiguous and suitably consistent with the functional mechanism of intumescent ame retardants. According to the results obtained from Taguchis parameter design, APP and PER contents were the most signicant factors for designing an optimized formulation of the studied intumescent system model. In addition, among the 10 interaction pairs studied, the APP versus PER and APP versus MEL interactions had the highest SI values. The morphological characterization of the residual char of the samples with the lowest and highest reproong time showed that the ame retardancy behaviour was improved with increased amount and decreased size of the micropores in the char structure.

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