Textile Flame Retardancy Through Surface-Assembled

Chapter 22

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Textile Flame Retardancy Through Surface-Assembled Nanoarchitectures Federico Carosio,* Jenny Alongi, Alberto Frache, Giulio Malucelli, and Giovanni Camino Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, Alessandria Campus, Viale T.Michel 5, 15121 Alessandria, Italy *E-mail: [email protected]

Single step and multi-step adsorption processes have been investigated in order to enhance flame retardancy of poly(ethylene terephthalate) fabrics and their blends with cotton. The first strategy concerns single step nanoparticle adsorption in a finishing-like process upon plasma surface activation. This approach aims at evaluating the effectiveness of nanoparticle simple adsorption on fabric combustion properties and the enhancement promoted by the plasma surface activation performed at different processing conditions. Subsequently, the layer by layer assembly technique has been investigated as an evolution of the nanoparticle adsorption. This technique, which consists in a multi-step adsorption process, allows the build-up of coatings made of different kinds of nanoparticles and polymers, each one bearing a specific functionality. By using the multi-step approach, hybrid organic-inorganic or completely inorganic coatings have been deposited on selected fabrics and subjected to flammability and combustion tests.

Introduction Nowadays fabric flammability still represents a severe threat to the safety of people and buildings. The use of natural and synthetic fibers involves different problems: the former can catch fire very easily and burn with vigorous flame, while the latter can melt during combustion, leading to the formation of incandescent drops that are able to spread the fire to other ignitable materials. © 2012 American Chemical Society In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Since 1950, chemists have been continuously developing flame retardant treatments able to reduce fabric flammability; in particular, the 1950-80 period is often referred as “the golden age” for what concerns flame retardancy chemistry (1). This period was really a golden age when the combination of increased fire safety concerns, which led to several legislations and regulations (2–4), and the virtual absence of constraints in the use of chemicals, promoted the development of most of the presently used flame retardants (5–8). Meanwhile, governments started worrying about environmental and health risks related to the use of certain types of flame retardants. As a result, most of the high performing flame retardants developed in the early 1950-80 were banned or limited as far as their application field is concerned (1). As a consequence, during the last decades, scientists had to refine the chemistry of the 50-80’s in order to obtain more cost-effective flame retardants and remove the treatments that have shown an unacceptable level of environmental risk (9, 10). The above scenario opened the way for novel and non-conventional procedures such as surface or bulk modifications achieved by exploiting nanotechnology. However, when applied to the bulk, this technology had to face several problems such as compatibility between polymer and nanoparticles (11), effect on rheology during compounding (12, 13), and a level of achieved flame retardancy often not completely satisfactory (14, 15). On the contrary, a valuable and promising application of nanotechnology has been found in the surface modifications. Indeed, in the last ten years, nanotechnology has been applied for surface modifications in order to develop after-treatments capable of adding flame retardant properties to the selected textiles without significant modifications of the underlying fabric properties. Among the different approaches, techniques based on nanoparticle adsorption such as single- and multi-step (layer by layer) processes can be found. The single step nanoparticle adsorption represents the easiest way for pursuing a surface modification using nanoparticles and simply consists in the immersion of the fabric into a water suspension of nanoparticles in order to promote their adsorption on the fiber surface similarly to a finishing treatment (impregnation and exhaust). The adsorption process can be repeated several times (using different reagents at each adsorption step), leading to a multi-step process known as layer by layer (16). This step-by-step film build-up based on electrostatic interactions was introduced in 1991 for polyanion/polycation films in order to obtain the so-called polyelectrolyte multilayers (17) and subsequently extended to inorganic nanoparticles (18). The procedure for obtaining such multilayer films requires the alternate immersion of the substrate into an oppositely charged polyelectrolyte solution (or nanoparticle dispersion); this process, which leads to a total surface charge reversal after each immersion step (19), creates a structure of positively and negatively charged layers piled up on the substrate surface. Surface adsorption techniques mimic their flame retardant mechanism on that of bulk nanocomposites, for which a physical effect exerted by a ceramic barrier developed during combustion is observed (20–23). Upon adsorption from a suspension, the nanoparticles are already on the surface of the polymer and thus the aforementioned physical barrier can protect the substrate from the very beginning of the combustion. 328 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


In the present work, we discuss different approaches based on surface adsorption techniques, in order to build simple or complex nanoarchitectures able to enhance the flame retardancy of poly(ethylene terephthalate) (PET) fabrics and their blends with cotton. The first strategy concerns the single step adsorption of nanoparticles (namely hydrotalcite, silica and sodium montmorillonite) in a finishing-like process. Furthermore, the effects of cold plasma pre-treatment (etching), that should enhance the surface interaction and favor the nanoparticle adsorption, will be discussed (24, 25). Subsequently, the layer by layer assembly technique will be presented as an evolution of the single-step adsorption for depositing simple or complex architectures characterized by completely inorganic or hybrid organic-inorganic compositions (26–29).

Results and Discussion Single-Step Adsorption This approach consists in the fabric immersion from 30 min to 1 h in a 0.3 to 1 wt.-% water suspension of nanoparticles. The surface morphology changes after the immersion and subsequent thermal treatment have been investigated by Scanning Electron Microscopy (SEM). Figure 1 shows the typical micrographs of PET treated by a single step adsorption of hydrotalcite (HT), silica (SiO2) and sodium montmorillonite (CloNa), respectively.

Figure 1. SEM micrographs of PET fabrics coated by single step adsorption of hydrotalcite (a), silica (b) and sodium montmorillonite (c).

As clearly observable, all the treated samples are characterized by a rougher surface with respect to untreated PET; this finding is ascribed to the presence of adsorbed nanoparticles that are homogeneously distributed on the fabric surface and form agglomerates with dimensions ranging from sub-micrometers to several micrometers. The combustion resistance turns out to be enhanced only in the case of PET fabrics treated with HT and CloNa, as can be seen in Figure 2. 329 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Figure 2. Cone calorimetry data (35 Kw/m2) for neat PET and PET coated by single-step adsorption of hydrotalcite (HT), silica (SiO2) and sodium montmorillonite (CloNa). [data from refs. (24) and (25)]

Indeed, while SiO2 treated samples show a 53 s reduction of Time to Ignition (TTI), this value increases by 68 and 48 s in the presence of HT and CloNa, respectively. Contrasting effects of nanoparticles on TTI of polymer nanocomposites have been previously found in the literature, the reasons for which are not yet understood (30). Furthermore, a 16% reduction of the peak of Heat Release Rate (pkHRR) is observed for HT whereas CloNa unexpectedly on the basis of literature data (31), shows a 17 % increase; SiO2 samples yielded a reduction of 10% which falls in the accepted error of the cone calorimeter measurements. The Fire Performance Index (FPI =TTI/pkHRR), which averages TTI and PkHRR in the evaluation of Fire Risk, increasing when fire risk decreases (32), increases by 69 and 8 % in the case of HT and CloNa, respectively. Thus, with CloNa pkHRR increase is compensated by increase of TTI. On the contrary, in the case of SiO2 the slight reduction in pkHRR does not overcome the TTI decrease, leading to a lower FPI as compared to pure PET. A cold plasma surface treatment has been developed for PET textiles in order to increase the fiber hydrophilicity and produce a suitable substrate for further nanoparticle adsorption. Such different process parameters of the plasma treatment as power (50, 80 and 120 W) and etching time (15, 60 and 180 s) have been investigated and related to the final combustion properties achieved after the subsequent CloNa nanoparticle adsorption. Figure 3 depicts the obtained results. As far as TTI is concerned, it is possible to observe an overall improvement for all the cold plasma-treated fabrics, in particular when the activation is performed for the longest time (180 s) and intermediate power (80 W) in the explored range, with doubling of TTI with respect to untreated PET. Comparing pkHRR values, plasma activated fabrics show average pkHRR values that are within the error range of the reference. As a consequence, all the plasma-etched fabrics have a Fire Perfomance Index greater than 1.76 of the untreated fabric. 330 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Figure 3. Cone calorimetry data for neat PET and PET coated by single-step adsorption of CloNa after cold plasma pre-activation performed at different powers and times. [data from ref. (25)]

Adsorbed CloNa nanoplatelets onto PET fabric surface can delay the sample ignition since they act as a barrier that protects the underlying polymer from heat and traps volatile products released from PET thermal degradation. Plasma etching can further promote this effect by: i) creating a more reactive and hydrophilic surface (33), which increases the amount of nanoparticles adsorbed during the immersion, and ii) developing stronger and more efficient interactions between the surface and the nanoparticles with respect to conventional adsorption phenomena. In addition, it is quite evident that power and etching time play different roles as depicted in Figure 3: indeed, high powers (120 W) combined with long treatment times can have a detrimental effect, while long treatment times can still lead to good properties when performed at lower powers.

Multistep Adsorption of Silica-Based Coatings

As an evolution of the single step process, a multi-step (i.e. layer by layer) adsorption has been applied in order to build up a completely inorganic silica coating on PET fabrics. To this aim, positively charged commercially available alumina coated silica nanoparticles (10 nm) have been coupled with negatively charged silica nanoparticles having different size (30 or 10 nm respectively) in order to build a coating made of bilayered (BL) architectures on the fiber surface (26). The best architectures, combustion behavior of which will be described in the following, turn out to be those made of the smallest nanoparticles (10 nm): their SEM micrographs show the formation of a thin and homogeneous coating, as shown in Figure 4. 331 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Figure 4. SEM micrographs of PET fabrics coated by 10 BL silica/silica 10/10 nm coating. By vertical flame test, ASTM D6413, samples treated with 5 and 10 BL were found to reduce the burning time by 63 and 94%, respectively. The same samples were also able to suppress the incandescent melt-dripping phenomenon typical of PET fabrics, whereas dripping appears when the number of BL increases up to 20. This behavior suggests that a relationship exists between coating stability and fire performance achieved. Indeed, 5 and 10 BL treated samples appear to be very stable, unlike 20 BL coatings, which can likely flake off during the test, thus resulting in a less effective fire protection. A similar behavior has been found also during cone calorimetry tests (Figure 5).

Figure 5. Cone calorimetry data (35kW/m2) for neat PET and PET treated by 5, 10 and 20 BL. [data from ref. (26)]

The histograms in Figure 5 indicate that, despite the great variability for TTI, the samples treated with 5 and 10 BL show a TTI increase of 99 and 32 s, respectively. A significant variation of pkHRR values can be appreciated only for 5 BL (-20%); as a consequence of both the great increase of TTI and the reduction 332 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.

of pkHRR, the FPI of 5 BL is strongly increased with respect to the uncoated fabric. Again, an increased number of BL does not necessary lead to better fire performances; this behavior could be ascribed to the coating instability during combustion (26).


Multistep Adsorption of α-Zirconium Phosphate-Based LbL Coatings In the following, LbL will be extended to the use of negatively charged α-zirconium phosphate (ZrP) nanoplatelets with either octapropylammoniumfunctionalized POSS® (POSS/ZrP) or alumina-coated silica nanoparticles (SiO2/ZrP), both bearing positive charges (27). Typical morphologies achieved after deposition of ZrP-based coatings are depicted in Figure 6.

Figure 6. SEM micrographs of PET fabrics coated by 10BL POSS/ZrP (a) and 10BL SiO2/ZrP (b). Inlets: EDS analyses.

Figure 7. Combustion properties of neat PET and PET coated by 5 and 10 BL of POSS/ZrP and SiO2/ZrP assemblies. Cone calorimeter at 35 kW/m2. [data from ref. (27)] 333 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


A strong change in surface morphology is clearly observable after the LbL deposition: in particular, big aggregates are found on the fiber surfaces regardless of the coating composition. EDS analyses shown in Figure 6 suggest that such aggregates are complexes of ZrP and either POSS® or SiO2 respectively, which are generated close to the fiber surface at each deposition step due to an un-optimized washing step. Although the typical LbL morphology is not achieved, the treated fabrics yielded good results when subjected to cone calorimetry tests as reported in Figure 7. As far as POSS assemblies are concerned, a slight TTI increase is observed, while pkHRR is strongly reduced by 26 and 20 % for 5 and 10 BL, respectively. SiO2-based assemblies show an inverse proportionality between BL number and both TTI increase and pkHRR decrease. From an overall point of view, the FPI values of the treated fabrics are higher than for uncoated PET and reach the highest value with 5 BL SiO2/ZrP, due to the strong TTI increase. The smoke parameters are collected in Figure 8.

Figure 8. Smoke parameters of neat PET and PET coated by 5 and 10 BL of POSS/ZrP and SiO2/ZrP. Cone calorimeter at 35 kW/m2. Maxima for CO (pkCO), CO2 (pkCO2) and smoke evolution (pkSPR). [data from ref. (27)]

From a broad point of view, it seems that both the assemblies are capable of influencing the smoke parameters. However, as observed before, when referring to POSS assemblies, it is possible to detect an inverse proportionality between BL number and the smoke reduction efficiency, with 5 BL POSS showing greater effects on both pkCO (-35%) and pkCO2 (-25%) reductions, while 10 BL affects pkCO and pkCO2 for -26% and -14%, respectively. On the contrary, both SiO2based assemblies (5 and 10 BL) seem to affect smoke production at the same level (-20% pkSPR), with a 30% reduction of pkCO and an even larger effect on pkCO2. As clearly understandable from combustion and smoke data, even though each considered assembly did not promote the formation of a homogeneous coating, all the described LbL nanoarchitectures were able to enhance PET flame retardancy by increasing the time to ignition, decreasing the combustion kinetics and reducing the smoke production. 334 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Multistep Adsorption of APP-Based Coatings The layer by layer technique has been also applied to polyester-cotton blends (PET-CO, cotton-rich) in order to enhance their flame retardancy by exploiting the formation of a hybrid organic inorganic coating made of chitosan (Chi) and ammonium polyphosphate (APP) (28). PET-CO blends represent high performance and low price products; unfortunately, from the flame retardancy point of view, they also combine the flaws of both the fibers. The presented Chi/APP assembly should act as an intumescent-like system, in which chitosan represents both the carbon source and the foaming agent, while APP is able to generate phosphoric acid directly in situ at high temperatures (34). After the deposition of 5, 10 and 20 BL on PET-CO blends, a homogeneous surface coverage can be achieved, as depicted in Figure 9.

Figure 9. SEM micrographs of PET-CO fabrics coated by 20BL Chi/APP. Inlets: EDS analyses for PET (a) and cotton fibers (b). Indeed, as clearly observable, the LbL coating homogeneously covers both cotton and PET fibers. Furthermore, it seems that, due to the more hydrophilic nature of cotton with respect to PET, the coating grows thicker on cotton fibers as qualitatively confirmed by EDS analyses (Figure 9). When exposed to a small methane flame, irrespective of the considered BL number, such coatings do not significantly change the burning time of the pure blend but can suppress the afterglow phenomenon typical of the untreated PET-CO blend. In addition, the deposited coatings are able to partially protect the blend during the combustion, yielding a consistent residue that increases by increasing the BL number (3, 5 and 8 % for 5, 10 and 20BL, respectively). Referring to cone calorimetry tests, the deposited coating anticipates the time to ignition (12, 17 and 17 s for 5, 10 and 20BL vs. 22 s for the untreated blend). This behavior can likely be ascribed to the presence of hydroxyl groups in the chitosan molecules that are able to catalyze the thermal decomposition of cotton, as already described in the literature (35). In addition, a similar effect induced by the presence of APP is well documented in the literature (1). Although this could seem a detrimental effect, the anticipation induced by APP could be extremely 335 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


advantageous since it promotes the formation of a thermally stable carbonaceous structure (char) at lower temperatures, avoiding the evolution of volatile species and limiting the further degradation and combustion of the polymer blend. As a consequence of the afore-mentioned mechanism, the Chi/APP pair turns out to significantly reduce the total heat release and the corresponding rate (evaluated as pkHRR) in a remarkable way (162, 138 and 128 kW/m2 for 5, 10 and 20BL vs. 170 kW/m2 for the untreated blend) as reported in Figure 10.

Figure 10. Cone calorimetry data (35 kW/m2) for neat PET-CO and PET-CO coated by 5, 10 and 20 BL of Chi/APP. Time to Ignition (TTI), peak of Heat Release Rate (pkHRR), Total Heat Release (THR). [data from ref. (28)]

On the basis of these results, it is possible to conclude that the higher the BL number, the lower is the combustion rate. The most evident drawback of this system can be found in the significant release of smoke with respect to the pure blend, as depicted in Figure 11.

Figure 11. Smoke parameters of neat PET-CO and PET-CO coated by 5, 10 and 20 BL of Chi/APP. [data from ref. (28)] 336 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Indeed, the formation of carbon monoxide and dioxide is favored for all the treated samples and the CO2/CO ratio is considerably lower than that of the pure blend. This behavior confirms the occurrence of inefficient combustion, as observed in Figure 10, due to the restricted diffusion of oxygen into the pyrolysis zone (36). Again, as discussed for flammability, this effect is able to favor the char formation and yield coherent residue after combustion. SEM analyses performed on the 20BL residue show that the treated fabric is capable of partially maintain its original texture as depicted in Figure 12.

Figure 12. SEM micrographs performed on the cone combustion residue of PET-CO fabrics coated by 20BL Chi/APP. Inlets: EDS analysis.

EDS analysis evidences the presence of phosphorus and carbon, thus indicating that both the coating and the fiber char are partially present after the combustion process.

Hybrid Organic-Inorganic APP Based LbL Complex Architectures

Complex architectures made of chitosan, ammonium polyphosphate and silica have been built up on PET-CO fabrics in order to exploit the good HRR reduction achieved with chitosan and the consistent TTI increase derived from the presence of the above-mentioned silica/silica coating (26, 28). Two different complex architectures containing all these constituents have been assembled, i.e. a quad-layer (QL) unit made of chitosan/ammonium polyphosphate/silica/silica and a bi-layer+bi-layer (BL+BL) unit, which consists of chitosan/ammonium polyphosphate bilayers (5 or 10) covered by silica/silica bilayers (5 or 10) (29). The morphology of the fibers after the LbL treatments has been assessed by SEM observations: some typical micrographs of the 10 QL and 10 BL+BL architectures are shown in Figure 13. 337 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


Figure 13. SEM micrographs performed on PET-CO fabrics coated by 10 QL (a) and 10 BL + BL (b). As far as QL are considered, a continuous and homogeneous coating can be observed on both the fibers; a similar good surface coverage can be detected also for the BL + BL architecture, even though some cracks appear. This finding is likely due to the overloaded coating and therefore the crack formation presumably depends on the BL + BL deposited architecture. Indeed, by comparing the structures of the two assemblies, it is quite evident that QL are potentially more flexible than BL+BL counterparts and thus the former are capable to maintain a good adhesion with both cotton and PET fibers and to prevent the crack formation. When these architectures are subjected to flammability tests, as already observed for Chi/APP-based coatings, they lead to the suppression of the afterglow phenomenon and to an increased residue. In addition, the morphology of the deposited coatings appears to play a key role as far as the combustion behavior is considered; indeed, as reported in Figure 14, the BL + BL architecture shows a detrimental effect for what concerns TTI and pkHRR.

Figure 14. Cone calorimetry data for neat PET-CO and PET-CO fabrics coated by BL+ BL or QL architectures. [data from ref. (29)] 338 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


This finding can be ascribed to the numerous cracks exhibited by the samples that can act as preferential channels for the leakage of the gaseous species produced during heat exposure. On the contrary, TTI increases for both the quadlayer assemblies; indeed, as observed from SEM micrographs, the coating is compact and capable of protecting the substrate during the early stage of heat exposure and during the combustion process. However, only 10 QL, probably because of the high APP content as well as the very low number of cracks, proved to be quite efficient for both TTI and HRR. Conversely, the TSR increase assessed for all the treated fabrics is a clear confirmation of a detrimental effect exerted by the complex LbL architectures on the smoke production (Figure 10).

Conclusions In the present work, we have successfully exploited single- or multi-step surface adsorption techniques, i.e. the adsorption of nanoparticles (namely hydrotalcite, silica, sodium montmorillonite, POSS® and zirconium phosphate) in a finishing-like process or the layer by layer assembly, in order to deposit nanostructures on the surface of poly(ethylene terephthalate) fabrics and of their blends with cotton. Furthermore, the effects of a cold plasma pre-treatment performed on the fabrics prior to the surface adsorption, have been deeply investigated. All the surface treatments turned out to significantly influence the flammability and combustion behavior of the fabrics, according to the adopted adsorption technique, the type, the number and the structure of the deposited nanoparticles and/or nanolayers. Besides the surface-layered nanoparticles, exploitation of the intumescent shield generated by char and foaming precursors of multiple surface nanolayers has been shown to be suitable for fabric protection with potential performance enhancement by combination with inorganic particle layers. The proposed surface adsorption methods have been shown to be quite interesting in promoting the development of novel cost-effective flame retardants with minimized environmental impact.

References 1. 2.

3. 4. 5. 6. 7. 8.

Horrocks, A. R. Polym. Degrad. Stab. 2011, 96, 377–392. U.S. Government of Commerce, DOC FF 3-71, (as amended). Standards for the flammability of children’s sleepwear; Washington, D.C.; 1971. Now 16 CFR Part 1615. The nightdress (safety) regulation, S.I. 839:1967 and the nightwear (safety) regulations S.I. 2043:1985; London, U.K.: HMSO. Bull, J. P.; Jackson, D. M.; Walton, C. Br. Med. J. 1964, 2, 1421–1427. Horrocks, A. R. Rev. Prog. Color. 1986, 16, 62–101. Weil, E. D.; Levchik, S. V. J. Fire Sci. 2008, 26, 243–281. Weil, E. U.S. Patent 3,746,572, 1970. Weil, E. U.S. Patent 3,695,925, 1972. 339

In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.

9. 10.

11. 12.


13. 14.

15. 16. 17. 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34.

Horrocks, A. R. In Textile finishing; Heywood, D., Ed.; Society of Dyers and Colourists: Bradford, U.K., 2003; pp 214−50. National Academy of Sciences. Toxicological risks of selected flameretardant chemicals; Sub-committee on flame-retardant chemicals of the United States National Research Council, Washington, DC; National Academy Press: Washington, DC, 2000. Awad, W. H.; Gilman, J. W.; Nyden, M.; Harris, R. H., Jr; Sutto, T. E.; Callahan, J. Thermochim. Acta 2004, 409, 3–11. Yasue, K.; Katahira, S.; Yoshikawa, M.; Fujimoto, K. In Polymer-Clay Nanocomposites; Pinnavaia, T. J., Beall, G. W., Eds.; Wiley series in Polymer Science; Wiley: Chichester, 2000; pp 111−126. Matayabas, J. C.; Turner, S. R.; Sublett, B. J.; Connell, G. W.; Barbee, R. B. Int. Appl.WO 98/29499, 1998. Gilman, J. W.; Kashiwagi, T. In Polymer-Clay Nanocomposites; Pinnavaia, T. J., Beall, G. W., Eds.; Wiley series in Polymer Science; Wiley: Chichester, 2000; pp 193−206. Gilman, J. W. Appl. Clay Sci. 1997, 15, 31–49. Multilayer thin films, sequential assembly of nanocomposite materials; Decher, G., Schlenoff, J. B. Eds.; Wiley VCH: Weinheim, 2002. Decher, G.; Hong, J. D. Makromol. Chem., Macromol. Symp. 1991, 46, 321–327. Tang, Z.; Kotov, N. A.; Magonov, S.; Ozturk, B. Nat. Mater. 2003, 2, 413–418. Bernt, P.; Kurihara, K.; Kunitake, T. Langmuir 1992, 8, 2486–2490. Tang, Y.; Lewin, M.; Pearce, E. Macromol. Rapid. Comm. 2006, 27, 1545–1549. Hao, J.; Lewin, M.; Wilkie, C. A.; Wang, J. Polym. Degrad. Stab. 2006, 91, 2482–2485. Tang, Y.; Lewin, M. Polym. Degrad. Stab. 2007, 92, 53–60. Lewin, M.; Tang, Y. Macromolecules 2008, 41, 13–17. Tata, J.; Alongi, J.; Frache, A. Fire Mater. DOI:10.1002/fam.1105. Carosio, F.; Alongi, J.; Frache, A. Eur. Polym. J. 2011, 47, 893–902. Carosio, F.; Laufer, G.; Alongi, J.; Camino, G.; Grunlan, J. C. Polym. Degrad. Stab. 2011, 96, 745–50. Carosio, F.; Alongi, J.; Malucelli, G. J. Mater. Chem. 2011, 21, 10370–10376. Carosio, F.; Alongi, J.; Malucelli, G. Carbohyd. Polym. 2012, 88, 1460–1469. Alongi, J.; Carosio, F.; Malucelli, G. Cellulose 2012, 19, 1041–1050. Fina, A.; Camino, G. Polym. Adv. Technol. 2011, 22, 1147–1155. Gilman, J. W. Appl. Clay Sci. 1999, 15, 31–49. Schartel, B.; Bartholmai, M.; Knoll, U. Polym. Adv. Technol. 2006, 17, 772–777. Cioffia, M. O. H.; Voorwalda, H. J. C.; Mota, R. P. Mater. Charact. 2003, 50, 209–215. Zhang, J.; Horrocks, A. R.; Hall, M. E. Fire Mater. 1994, 18, 307–312. 340

In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.


35. Xie, W.; Gao, Z.; Pan, W. P.; Hunter, D.; Singh, A.; Vaia, R. Chem. Mater. 2001, 13, 2979–2990. 36. Kandare, E.; Kandola, B. K.; Price, D.; Nazarè, S.; Horrocks, A. R. Polym. Degrad. Stab. 2008, 93, 1996–2006.

341 In Fire and Polymers VI: New Advances in Flame Retardant Chemistry and Science; Morgan, A., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2012.

Textile Flame Retardancy Through Surface-Assembled

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