Review on flammability of biofibres and biocomposites

Accepted Manuscript
Title: Review on flammability of biofibres and biocomposites
Author: Mfiso E. Mngomezulu Maya J. John Valencia Jacobs

Adriaan S. Luyt
PII: S0144-8617(14)00321-X
DOI: http://dx.doi.org/doi:10.1016/j.carbpol.2014.03.071
Reference: CARP 8733
To appear in:
Received date: 6-11-2013

Revised date: 7-3-2014
Accepted date: 20-3-2014
Please cite this article as: Mngomezulu, M. E., John, M. J., Jacobs, V., & Luyt, A.
S.,Review on flammability of biofibres and biocomposites, Carbohydrate Polymers
(2014), http://dx.doi.org/10.1016/j.carbpol.2014.03.071
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1 Review on flammability of biofibres and
2 biocomposites
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4 Mfiso E. Mngomezulu1,3, Maya J. John1,2,*; Valencia Jacobs1,2; Adriaan S. Luyt3
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6 CSIR Materials Science and Manufacturing, Polymers and Composites Competence Area,
7 P.O. Box 1124, Port Elizabeth 6000, South Africa
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9 Department of Textile Science, Faculty of Science, Nelson Mandela Metropolitan University,
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10 P.O. Box 1600, Port Elizabeth 6000, South Africa
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12 Department of Chemistry, Faculty of Natural and Agricultural Sciences, University of the
13 Free State (Qwaqwa Campus), Private Bag X13, Phuthaditjhaba 9866, South Africa
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15 E-mail addresses:
16 Mfiso E. Mngomezulu: MMngomezulu1@csir.co.za, Tel. numbers: +27(0)415083241

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17 Maya J. John*: MJohn@csir.co.za

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18 Valencia Jacobs: VJacobs@csir.co.za, Tel. numbers: +27(0)415083229

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19 Adriaan S. Luyt: LuytAS@qwa.ufs.ac.za, Tel. numbers: +27(0)587185314

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22 * Author for correspondence:
23 E-mail: MJohn@csir.co.za
24 Telephone numbers: +27(0)41 508 3292
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26 Abstract
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28 The subject on flammability properties of natural fibre-reinforced biopolymer composites has
29 not been broadly researched. This is not only evidenced by the minimal use of biopolymer
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30 composites and/or blends in different engineering areas where fire risk and hazard to both
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31 human and structures is of critical concern, but also the limited amount of published scientific
32 work on the subject. Therefore, it is necessary to expand knowledge on the flammability
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33 properties of biopolymers and add value in widening the range of their application. This
34 paper reviews the literature on the recent developments on flammability studies of bio-fibres,
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35 biopolymers and natural fibre-reinforced biocomposites. It also covers the different types of
36 flame retardants (FRs) used and their mechanisms, and discusses the principles and
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37 methodology of various flammability testing techniques.
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39 Key words:
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40 Flammability, Flame retardants, Biopolymers, Natural fibre, Composite.
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52 Contents Page Number
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54 Abbreviations
55 1. Introduction 7
56 2. Flame retardants (FRs) 9
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57 2.1 Mode of action of flame retardants 11
58 2.2.1 Physical action 11
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59 2.2.2Chemical action 12
60 2.2 Types of flame retardants 13
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61 2.2.1 Phosphorus based flame retardants 13
62 2.2.1.1 Organic phosphorus 14
63 2.2.1.2 Inorganic phosphorus 15
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64 2.2.1.3 Red phosphorus 15
65 2.2.1.4 Intumescent flame retardant system 16
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66 2.2.2Halogen based flame retardants 18
67 2.2.2.1 Halogenated flame retardant additives 19
68 2.2.2.2 Halogenated monomers and copolymers 21
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69 2.2.3 Silicon based flame retardants 21

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70 2.2.3.1 Silicones 22
71 2.2.3.2 Silica 22
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72 2.2.4 Nano-metric particles 23

73 2.2.4.1 Nanoclays 24
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74 2.2.4.2 Carbon nanotubes 25

75 2.2.4.3 Graphene
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76 2.2.4.4 Nano scale particulate additives 27

77 2.2.4.4.1Silsesquioxane 27
78 2.2.4.4.2Metallic oxide particles 29
79 2.2.4.5 Hybrid nanofillers
80 2.2.5 Mineral flame retardants 25
81 2.2.5.1 Hydroxycarbonates 31
82 2.2.5.2 Metal hydroxide 32
83 2.2.5.3 Borates 35
84 3. Flammability testing techniques 35
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85 3.1 Cone calorimetry 35
86 3.2 Pyrolysis combustion flow calorimetry (PCFC) 38
87 3.3Limiting oxygen index (LOI) 42
88 3.4 Underwriter laboratories 94 (UL 94) 43
89 3.5Ohio State University heat release apparatus (OSU) 45
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90 4. Flammability of biofibres and biocomposites 49
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91 4.1Biofibres (natural fibres) 49
92 4.2Biopolymers 63
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93 4.3Biofibre reinforced biopolymer composites 74
94 5. Summary 81
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95 6. Acknowledgement 82
96 7. References 82
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122 Abbreviations
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124 APP Ammonium polyphosphate
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125 ATH Aluminum tri-hydrate
126 BAl Boehemite aluminum
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127 BDP Bisphenyl A bis(diphenyl phosphate)
128 DNA Deoxyribonucleic acid
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129 DTG Derivative thermogravimetric analysis
130 EG Expandable graphite
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131 EVA Ethylene vinyl acetate
132 FRs Flame retardants
133 FRAs Flame retardant agents/additives
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134 HPCA Hyperbranched polyamine charring agent
135 HBCD Hexabromocyclododecane
136 HRR Heat release rate
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137 HRC Heat release capacity (ηc)

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138 IFR Intumescent flame retardant

139 LOI Limited oxygen index
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140 LDPE Low density polyethylene

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141 MA Melamine
142 MCC Microscale combustion calorimetry
143 MH or MDH Magnesium hydroxide or Magnesium dihydroxide
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144 MPD methacryloyloxyethylorthophosphorotetraethyl diamidate

145 MA-g-PP Maleic acid grafted polypropylene
146 MMP Melamine phosphate
147 MMB Melamine borate
148 MMT Montmorillonite
149 MLR Mass loss rate
150 MWNTs Multi walled nanotubes
151 NAs Normal additives
152 NFs Natural fibres
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153 NFRBC Natural fibre reinforced biopolymer composites
154 OSU Ohio State University
155 PMMA Polymethyl methacrylate
156 PCFC Pyrolysis combustion flow calorimetry
157 PA6 Polyamide 6
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158 PU Polyurethane
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159 PC Polycarbonate
160 PP Polypropylene
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161 PE Polyethylene
162 PS Polystyrene
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163 POSS Polyhedral oligomeric silsesquioxane
164 PCL Polycaprolactone
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165 PLA Polylactic acid
166 PHBV Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
167 PBT Poly(butylene terephthalate)
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168 PBAT Poly(butylene adipate-co-terephthalate)
169 PTT Poly(trimethylene terephthalate)
170 PPTA Poly(p-phenylenediamineterephthalamide)
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171 PBDE Polybromodiphenyl ether

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172 PHRR Peak heat release rate

173 PEBAX Polyether blockamide
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174 PC Polycarbonate
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175 RAs Reactive additives

176 RTM Resin transfer moulding
177 SPR Smoke production rate
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178 SPDPM Spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine

179 SEA Soot extinction area
180 SEM Scanning electron microscopy
181 SWNTs Single walled nanotubes
182 TBBPA Tetrabromobisphenol A
183 TBPA Tetrabromophthalic anhydride
184 TTI Time to ignition
185 THR Total heat release
186 TPOSS Trisilanolphenylpolyhedral oligomeric silsesquioxane
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187 UL 94 Underwriter laboratories 94
188 UV Ultraviolet
189 ZB Zinc borate
190 1. Introduction
191
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192 In recent years, the research on biofibre reinforced biopolymer composites has advanced.
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193 This development is motivated by factors such as shortage of and high fossil energy cost, and
194 the current shift towards environmentally tolerant or “green” composite materials. The shift
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195 towards environmentally friendly biocomposite materials is due to environmental legislation,
196 the REACH Act (Registration, Evaluation, Authorization and Restriction of Chemical
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197 substances), comparable properties to synthetic fibre counterparts, green attribution and low
198 cost. Most of the components in biocomposites are based on agricultural products as a source
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199 of raw materials. Thus, their use provides solution for waste disposal, reduction in
200 agricultural residues and hence environmental pollution resulting from the burning of these.
201 Additionally, it offers an economical solution for farming and rural areas in developing
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202 countries (Anandjiwala et al., 2013; Chapple & Anandjiwala, 2010; Faruk, Bledzki, Fink &
203 Sain, 2012; Horrocks, 2011; Jang, Jeong, Oh, Youn & Song, 2012; John & Thomas, 2008;
204 Kandola, 2012; Sahari & Sapuan, 2011; Satyanarayana, Arizaga & Wypych, 2009).
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206 Biofibre reinforced biopolymer composite materials largely have appealing properties. They
207 are renewable, recyclable (partially or completely), relatively cheap, biodegradable and thus
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208 environmentally friendly. However, there are some inherent disadvantages such as their
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209 hydrophilic nature and poor flammability properties (i.e. poor fire resistance). The attractive
210 properties clearly outweigh the undesirable ones and the latter have remedial measures. For
211 example, remedies may be chemical and/or physical modifications such as the incorporation
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212 of flame retardant additives (FRAs) to improve flammability of biocomposites (John &
213 Thomas, 2008).
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215 Previous research observed limitations in the use of biofibre reinforced biopolymer
216 composites, especially in areas that pose fire hazard and risk.This is because natural fibre
217 reinforced biopolymer composites are largely used in the packaging and automotive
218 industries where fire safety regulatory requirements are not as stringent as those in the
219 aerospace industry. Therefore, to broaden the range of applications of these biocomposites
220 into other sectors of advanced engineering (i.e. aerospace, marine, electronics equipment and
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221 construction), both their flammability characteristics and fire retardance strategies need more
222 research (Bourbigot & Fontaine, 2010; Chapple & Anandjiwala, 2010; Kandola, 2012).
223
224 There are different strategies that can be demonstrated for fire retardancy of biocomposites.
225 Fire retardancy is the phenomenon in which materials such as plastics and/or textiles are
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226 rendered less likely ignitable or, if they are ignitable, should burn with less efficiency (Price,
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227 Anthony & Carty, 2001). It may be achieved by use of several approaches. These may be
228 chemical modification of existing polymers, addition of surface treatment to the polymers,
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229 use of inherently fire resistant polymers or high performance polymers, and direct
230 incorporation of flame retardants (FRs) and/or micro or nanoparticles in materials. The direct
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231 incorporation of flame retardants is achieved through use of various additives. These flame
232 retardance strategies may range from the use of phosphorus additives (e.g. intumescent
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233 systems), halogen additives (e.g. organobromine), silicon additives (e.g. silica), nanometric
234 particles (e.g. nanoclays) and minerals based additives (e.g. metal hydroxide). The broader
235 information on flame retardant additives (FRAs) in natural polymers, wood and
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236 lignocellulosic materials has been reviewed by Kozlowski and Wladyka-Przybylak (2001).
237 Thus, the primary duty of flame retardant systems is to prevent, minimize, suppress or stop
238 the combustion of a material (Laoutid, Bonnaud, Alexandre, Lopez-Cuesta & Dubois, 2009;
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239 Morgan & Gilman, 2013; Price et al., 2001; Wichman, 2003).
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241 Flame retardant systems can either act chemically or physically in the solid, liquid or gas
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242 phase. These mechanisms are dependent on the nature of the flame retardant system. The
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243 chemical mode of action may be manifested by reaction in the gaseous and condensed
244 phases, whereas the physical mode occurs by a cooling effect, formation of a protective layer
245 or by fuel dilution. FRs may be classified into three classes. They are normal additives (NAs),
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246 reactive additives (RAs) and a combination of FRs (Laoutid et al., 2009; Price et al., 2001;
247 Wichman, 2003).
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249 The flammability of fire retarded materials may be tested through different fire testing
250 techniques. The most widely used laboratory flammability testing techniques have been
251 reported in literature (Laoutid et al., 2009; Price et al., 2001; Wichman, 2003). A number of
252 small, medium and full scale flammability tests are used in both academic and industrial
253 laboratories. They are employed for either screening the materials during production or
254 testing the manufactured products. These techniques are cone calorimetry, pyrolysis
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255 combustion flow calorimetry (PCFC), limiting oxygen index (LOI), and underwriters’
256 laboratories 94 (UL94) and Ohio State University (OSU) heat release rate tests.These
257 techniques involve the measurement of various flammability parameters by appropriate tests
258 depending on the targeted application of a polymeric material. The flammability of polymers
259 can be characterized by parameters such as ignitability (ignition temperature, delay time,
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260 critical heat flux), burning rates (heat release rate, solid degradation rate), spread rates (flame,
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261 pyrolysis, and smoulder), product distribution (emissions of toxic products) and smoke
262 production (Carvel, Steinhaus, Rein & Torero, 2011; Laoutid et al., 2009; Price et al., 2001).
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264 The flammability properties of natural fibrereinforced biopolymer composites have not been
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265 studied extensively. The aim of this paper is to review the current research and developments
266 related to flammability of biofibre reinforced biopolymer composites for the period 2000 to
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267 2013. This review will explore aspects such as the different types of flame retardants,
268 laboratory flammability testing techniques and recent studies on flammability of biopolymers
269 and biocomposites.
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270
271 2. Flame retardants
272
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273 FRs impart flame retardancy character to materials such as coatings, thermoplastics,
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274 thermosets, rubbers and textiles. These FRs may prevent, minimize, suppress or stop the
275 combustion process of materials. They act to break the self sustaining polymer combustion
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276 cycle shown in Figure 1, and consequently reduce the burning rate or extinguish the flame in
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277 several ways (Guillaume, Marquis & Saragoza, 2012; Grexa & Lübke, 2001; Kandola, 2001;
278 Kandola & Horrocks, 2001; Ke et al., 2010; Kozlowski & Wladyka-Przybylak , 2001;
279 Laoutid et al., 2009; Morgan & Gilman, 2013; Price et al., 2001; Wichman, 2003).
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280
281 The possible ways to reduce the burning rate or extinguish the flames are:i) the modification
282 of the pyrolysis process in order to lower the quantity of evolved flammable volatiles, with
283 normally an increase in the formation of char (less flammable) serving as barrier between the
284 polymer and flame (stage ‘a’, Figure 1); ii) the isolation of the flame from the oxygen/air
285 supply (stage ‘b’); iii) introduction into the polymer formulations those compounds that will
286 release efficient flame inhibitors (e.g. chlorine and bromine) (stage ‘c’); and iv) the lowering
287 of thermal feedback to the polymer to prevent further pyrolysis (stage ‘d’) (Price et al., 2001).
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289
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290 Figure 1. Demonstration of the self sustaining polymer combustion cycle; a–d represent
291 potential modes of flame retardants (adapted from Price et al., 2001)
292 (Intended for colour on the Web and black-and-white in print)
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294 To flame retard polymer materials or to protect them from fire, there are three main
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295 approaches to be considered. These are the engineering approach, use of inherently low
296 flammable polymers and the use of flame retardant additives (FRAs) (Morgan & Gilman,
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297 2013).
298
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299 The engineering approach is cost effective and relatively easy to implement. It requires the
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300 use of a fire protection shield. However, the method has some limitations such as tearing
301 and/or ripping off (of fire proof fabric), loss of adhesion (in metal fire protection), and
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302 scratching away and falling off due to impact or ageing (of intumescent paint). Consequently,
303 the underlying material may be left exposed to fire damage.
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305 The inherently flame retarded polymers can be made in various forms and are easy to
306 implement in different applications. Their use, though, can be limited by high cost and
307 difficulty to recycle (i.e. fibre reinforced polymer composites). As a result, low flammability
308 polymers are less used except for applications demanding their use (e.g. aerospace and
309 military sectors).
310
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311 The use of FRAs is a well known approach, cost effective and relatively easy to incorporate
312 into polymers. The challenges with this approach, however, include potential for leaching
313 into environment, difficulty with recycling and a compromise in reaching a balance in
314 properties of a polymer. Regardless of these problems, FRAs are still used.
315
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316 FRs are classified into three categories. They are normal additives (NAs) flame retardants,
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317 reactive additives (RAs) flame retardants and combinations of FRs. NAs are incorporated
318 during polymerization or during melt mixing processing and react with the polymer only at
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319 higher temperatures at the start of a fire. They are common flame retardant additives and their
320 interaction is physical with the substrate. NAs usually include mineral fillers, hybrids or
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321 organic compounds that can include macromolecules. RAs, on the other hand, are usually
322 introduced into polymers during polymerization or in a post reaction process. During
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323 polymerization, RAs are introduced as monomers or precursor polymers whereas in a post
324 reaction process their introduction is by chemical grafting. These flame retardants chemically
325 bond to the polymer backbone. Combinations of NAs and RAs can produce an additive
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326 (sum), synergistic (higher) or antagonistic (lower) effect. A synergistic effect typically occurs
327 when they are used together with specific flame retardants (Kozlowski & Wladyka-
328 Przybylak, 2001; Morgan & Gilman, 2013; Price et al., 2001; Troitzsch, 1998).
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330 2.1 Mode of action of flame retardants

331
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332 Flame retardant systems can act either chemically or physically in the solid, liquid or gas
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333 phase. Such actions do not occur singly but should be considered as complex processes in
334 which various individual stages occur simultaneously, with one dominating. They are
335 dependent on the nature of flame retardant system in place (Bourbigot & Duquesne, 2007;
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336 Laoutid et al., 2009; Morgan & Gilman, 2013; Price et al., 2001; Troitzsch, 1998; Wichman,
337 2003). Various modes of flame retardants are discussed in subsequent sections.
338
339 2.1.1 Physical action
340
341 The physical mode occurs by (i) cooling effect, (ii) fuel dilution or (iii) via formation of a
342 protective layer (coating) (Chapple & Anandjiwala, 2010; Jang et al., 2012; Kandola, 2012;
343 Laoutid et al., 2009; Price et al., 2001; Troitzsch, 1998; Wichman, 2003).
344
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345 (i) Cooling effect: Some FRAs (e.g. hydrated trialumina and magnesium hydroxide)
346 decompose by an endothermic process and trigger temperature decrease in the system.
347 Cooling of the medium to below the polymer combustion temperatures is effected. Such
348 endothermic reaction is known to act as a heat sink.
349
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350 (ii) Fuel dilution: During decomposition of flame retardants (e.g. aluminum hydroxide), the
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351 formation of gases such as H2O, CO2, and NH3 lead to dilution of the mixture of combustible
352 gases. Consequently, this limits both the concentration of reagents and the possibility of
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353 materials to ignite.
354
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355 (iii) Formation of a protective layer (coating): Some FRAs (e.g. phosphorus and boron
356 compounds) form a protective solid or gaseous layer between the gaseous and solid
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357 combustible phases. This limits the transfer of combustible volatile gases, excludes oxygen
358 necessary for combustion and thus reducing the amount of decomposition gases.
359
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360 2.1.2 Chemical action
361
362 The chemical mode of action may be manifested by reaction in the (i) gaseous and (ii)
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363 condensed phase (Chapple & Anandjiwala, 2010; Jang et al., 2012; Kandola, 2012; Laoutid
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364 et al., 2009; Price et al., 2001; Troitzsch, 1998; Wichman, 2003).
365
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366 (i) Gaseous phase: By incorporation of FRAs that favour the release of specific radicals (e.g.
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367 halogen flame retardants, Cl• and Br•) in the gas phase, the free radical mechanism of the
368 combustion process can be stopped. These radicals can react with highly reactive species
369 such as H• and OH• to form less reactive or inert molecules. The exothermic reactions are
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370 then stopped; the system cools down and the supply of flammable gases is subsequently
371 reduced.
372
373 (ii) Condensed phase: Two types of chemical reaction initiated by FRAs are possible: (a)
374 flame retardants can speed up the rupture of polymer chains and the polymer will drip, thus
375 moving away from the flame action zone; (b) FRs can cause the formation of a carbonized or
376 vitreous layer at the surface of the polymer. This occurs by chemical transformation of
377 degraded polymer chains. The formed char and/or vitreous layer acts as a physical insulating
378 barrier between the gas and condensed phases.
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379
380 2.2 Types of flame retardant agents
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382 FRAs are based on various chemical compounds. This subsection discusses chemical
383 compounds based on phosphorus, halogen, silicon, nanometric particles and mineral
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384 additives. The phosphorus based additives include organic phosphorus, inorganic
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385 phosphorus, red phosphorus and intumescent flame retardant systems. The silicon based
386 additives consist of silica and silicones, the nanometric particles based ones may be carbon
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387 nanotubes, nanoclays and nanoscale particulate additives, and the minerals based flame
388 retardant additives are hydrocarbonates, metal hydroxides and borates.
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389
390 2.2.1 Phosphorus based flame retardants
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392 Phosphorus based FRs include phosphorus into their structure. Their structure can vary from
393 inorganic to organic forms, and with oxidation states of 0, +3, or +5. Phosphorus based FRs
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394 consist of phosphates, phosphonates, phosphinates, phosphine oxide and red phosphorus.
395 These FRAs are used as NAs or RAs incorporated into the polymer chain during synthesis.
396 They are effective with oxygen or nitrogen containing polymers (cellulose, polyesters, and
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397 polyamides). Phosphorated FRs are unique in that they can be condensed phase or vapour
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398 phase FRs depending on their chemical structure and interaction with the polymer under fire
399 conditions (Faruk et al., 2012; Jang et al., 2012; Laoutid et al., 2009).
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400
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401 In the condensed phase, their thermal decomposition leads to the production of phosphoric
402 acid that readily condenses to give phosphorylated structures and gives off water. Released
403 water dilutes the oxidizing gas phase (physical action: fuel dilution). Additionally,
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404 phosphoric acid and pyrophosphoric acid can facilitate a dehydration reaction resulting in the
405 formation of carbon to carbon double bonds and charring. This can then lead to the
406 generation of crosslinked or carbonized structures at high temperatures (Faruk et al., 2012;
407 Jang et al., 2012; Laoutid et al., 2009; Morgan & Gilman, 2013; Troitzsch, 1998).
408
409 At high temperatures both ortho and pyrophosphoric acid are turned into metaphosphoric acid
410 (OPOOH) and their corresponding polymers (PO3H)n. Phosphate anions (pyro and
411 polyphosphates) then partake in char formation (with carbonized residue). This carbonized
412 layer isolates and protects the polymer from the flames, limits the volatilization of fuel,
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413 prevents formation of new free radicals, limits the diffusion of oxygen thus reducing
414 combustion, and insulates the polymer underneath from the heat (Faruk et al., 2012; Jang et
415 al., 2012; Laoutid et al., 2009; Morgan & Gilman, 2013; Troitzsch, 1998).
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417 Phosphorus based flame retardants can also volatilize into vapour phase forming active
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418 radicals (PO2•, PO• and HPO•) and acting as scavengers of H• and OH• radicals. Volatile
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419 phosphorated compounds are among the effective inhibitors of combustion compared to
420 bromine and chlorine radicals. Since phosphorus based flame retardants are significantly
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421 effective in oxygen and nitrogen containing polymers, it is thus important to have these atoms
422 in the polymer chain. In case the used polymer lacks these atoms in its chain and cannot
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423 contribute to charring, a highly charring coadditive {e.g. polyol (pentaerythritol)} has to be
424 introduced in combination with the phosphorated flame retardant. Polymers such as
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425 polyamides and polyurethane can also be used as charring agents in intumescent flame
426 retardant systems (Faruk et al., 2012; Jang et al., 2012; Laoutid et al., 2009; Morgan &
427 Gilman, 2013; Troitzsch, 1998).
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428
429 2.2.1.1 Organic phosphorus
430
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431 Many organic phosphorus derivatives show flame retardancy properties. But, those of
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432 commercial importance are limited by the processing temperature and the nature of the
433 polymer to be modified. Organic phosphorus based FRs can act as NAs or as RAs monomers
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434 or co monomers/oligomers. Their main groups are phosphate esters, phosphonates and
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435 phosphinates. Due to their high volatility and relatively low fire retardant efficiency, the use
436 of alkyl substituted triaryl phosphate (i.e. triphenyl phosphate, TPP, cresyl diphenyl
437 phosphate, isopropylphenyl diphenyl phosphate, tertbutylphenyl diphenyl phosphate or
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438 tricresyl phosphate) is limited in plastics engineering. Oligomeric phosphates with lower
439 volatility and higher thermal stability than triaryl phosphate can be used for plastics
440 engineering. These may be resorcinol bis(diphenyl phosphate) (RDP) and bisphenol A
441 bis(diphenyl phosphate (BDP). The combination of volatile and nonvolatile phosphates can
442 also lead to a synergistic effect. This may be a positive combination of the condensed phase
443 and gas phase of phosphates. The use of reactive phosphorus flame retardants is also a
444 solution for avoiding volatilization during thermal decomposition and migration towards the
445 surface of a polymer. They can be incorporated directly within the polymer chain structure
446 and can be used either as monomers for copolymerization with one or two co-monomers to
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447 get phosphorated polymers or as oligomers that react with polymers to form branched or
448 grafted phosphorated polymers (Faruk et al., 2012; Jang et al., 2012; Laoutid et al., 2009;
449 Morgan & Gilman, 2013).
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451 2.2.1.2 Inorganic phosphorus
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453 A typical example of an inorganic phosphorus salt is a combinationof polyphosphoric acid
454 and ammonia called ammonium polyphosphate (APP). It is either a branched or unbranched
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455 polymeric compound with variable chain length (n). For short and linear chain APPs (where
456 n is less than 100, crystalline form I),they are more water sensitive and less thermally stable,
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457 whereas APPs with longer chain (n is greater than 1000, crystalline form II) exhibit very low
458 water solubility (< 0.1 g/100 ml) (Jang et al., 2012; Laoutid et al., 2009).
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460 The APPs are stable and nonvolatile compounds. Those with long chains start decomposing
461 at temperatures above 300 °C giving polyphosphoric acid and ammonia, whereas the short
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462 chain ones decompose at 150 °C. It is thus important to adapt a crystalline form of APP to the
463 decomposition temperature of a polymer. When an APP is incorporated into a polymer that
464 contains oxygen and/or nitrogen atoms, polymer charring occurs. Thermal degradation of
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465 APP creates free acidic hydroxyl groups that condense by thermal dehydration yielding a
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466 crosslinked structure of ultraphosphate and polyphosphoric acid with a highly crosslinked
467 structure. Polyphosphoric acid reacts with oxygen and/or nitrogen containing polymers and
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468 catalyses their dehydration reaction and char formation. However, the effectiveness of an
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469 APP is dependent on the loading concentration. Low concentrations of APP are not efficient
470 in aliphatic polyamides, but at high concentrations it becomes efficient. In non self-charring
471 polymeric materials, the APP can modify the degradation mechanism of the polymer
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472 (Bourbigot & Fontaine, 2010; Ke et al., 2010; Zhu et al., 2011).
473
474 2.2.1.3 Red phosphorus
475
476 This is the most concentrated source of phosphorus for flame retardancy and is used in small
477 quantities (i.e. < 10%). It is effective in oxygen and nitrogen containing polymers (i.e.
478 polyesters, polyamides and polyurethanes). For oxygen containing polymers only, the mode
479 of action involves specific scavenging of oxygen containing radicals leading to the generation
480 of gaseous fuel species. For oxygen and nitrogen containing polymers, red phosphorus turns
15
Page 15 of 110
481 into phosphoric acid or phosphoric anhydride, which gives polyphosphoric acid upon heating.
482 This happens through thermal oxidation and the formed polyphosphoric acid catalyses the
483 dehydration reaction of the polymer chain ends and triggers char formation (Laoutid et al.,
484 2009; Laoutid, Ferry, Lopez-Cuesta & Crespy, 2006).
485
t
486 Additionally, red phosphorus is also effective in non oxygenated polymers (e.g.
ip
487 polyethylene). Consequently, red phosphorus depolymerizes into white phosphorus (P4). This
488 white phosphorus can volatilize at high temperatures and act in the gaseous phase or it can
cr
489 diffuse from the bulk of the polymer to the burning surface where it oxidizes to phosphoric
490 acid derivatives. These can come into close contact with the flame and form phosphoric acid.
us
491 This acid can act as a char forming agent and therefore physically limiting oxygen access and
492 fuel volatilization (Laoutid et al., 2009).
an
493
494 Red phosphorus is active in both the gas and condensed phase in polyethylene. In the gas
495 phase, the produced PO• radicals quench the free radical process. In the condensed phase, red
M
496 phosphorus lowers the heat of oxidation and also traps the free radicals. This results in
497 improved thermal stability leading to a decrease in fuel production during burning of a
498 material (Laoutid et al., 2009).
d
499
te
500 The disadvantage of red phosphorus is that it releases toxic phosphine (PH3) through reaction
501 with moisture due to its poor thermal stability. However, phosphine formation can be avoided
p
502 by prior encapsulation of red phosphorus to improve its effectiveness as a flame retardant.
ce
503 Alternatively, phosphine formed at high temperatures can be trapped by taking advantage of
504 its capacity to react with metallic salts (i.e. AgNO3, HgCl2, MoS2, HgO, PbO2, CuO,
505 FeCl3·H2O) (Laoutid et al., 2009).
Ac
506
507 2.2.1.4 Intumescent flame retardant system
508
509 Intumescent flame retardant systems were initially developed to protect fabrics, wood and
510 coatings for metallic structures from fire. Intumescent materials are classed into thick or thin
511 film intumescent coatings. The thick films are usually based on epoxy resins, contain agents
512 that intumesce when exposed to heat and are available as solvent free systems. Thin films are
513 available as solvent or water based systems, and are applied by spray or brush roller in thin
514 film coats. An intumescent system is based on the formation of an expanded carbonized layer
16
Page 16 of 110
515 on the surface of a polymer during thermal degradation. This layer acts as an insulating
516 barrier by reducing heat transfer between the heat source and the polymer surface, by limiting
517 the fuel transfer from the polymer towards the flame, and limiting the oxygen diffusion into a
518 material. The formulation of an intumescent system consists of three components: an acid
519 source, a carbonizing agent and a blowing agent. Table 1 tabulates examples of each
t
520 component category (Bourbigot & Duquesne, 2007). The intumescent FRs are widely used
ip
521 due to their advantages of low smoke and low toxicity (Jimenez, Duquesne & Bourbigot,
522 2006; Ke et al., 2010; Laoutid et al., 2009; Morgan & Gilman, 2013).
cr
523
524 An acid source promotes dehydration of the carbonizing agent and results in the formation of
us
525 a carbonaceous layer. It has to be liberated at a temperature below the decomposition
526 temperature of a carbonizing agent and its dehydration should happen around the
an
527 decomposition temperature of a polymer. A carbonizing agent is generally a carbohydrate
528 that can be dehydrated by an acid to form a char. Its effectiveness relates to the number of
529 carbon atoms and the reactive hydroxyl sites containing carbon source agent molecules. The
M
530 quantity of char produced is dependent on the number of carbon atoms present. Reactive
531 hydroxyl (OH) sites determine the rate of the dehydration reaction and thus the rate of
532 formation of the carbonized structure. A blowing agent decomposes and releases gas leading
d
533 to expansion of the polymer and formation of swollen multicellular layer. The gas must be
te
534 released during thermal decomposition of a carbonizing agent in order to trigger the
535 expansion of the carbonized layer (Bourbigot & Duquesne, 2007; Jimenez et al., 2006; Ke et
p
536 al., 2010; Laoutid et al., 2009; Morgan & Gilman, 2013).
ce
537
Ac
17
Page 17 of 110
537
538 Table 1. Examples of components of intumescent systems. Reprinted from Bourbigot
539 and Duquesne (2007), Copyright 2007, with permission from Royal Society of
540 Chemistry.
Inorganic acid source Carbonizing agent Blowing agents
Phosphoric Starch Urea
t
ip
Sulfuric Dextrins Urea-formaldehyde resin
Boric Sorbitol, mannitol Dicyandiamide
cr
Ammonium salts Pentaerythritol, monomer, Melamine
Phosphates, polyphosphates dimer, trimer Polyamides
us
Borates, polyborates Phosphates, polyphosphates
Sulfates Phenol-formaldehyde resins
Halides Methylol melamine
an
Phosphates of amine or amide Char former polymers (PA-
Products of reaction of urea or 6, PA-6/clay nanocomposite
M
guanidyl urea with phosphoric PU, PC, etc.)
acids
Melamine phosphate
d
Product of reaction of ammonia

te
with P2O5
Organophosphorus compounds
p
Tricresyl phosphate
Alkyl phosphates
ce
Haloalkyl phosphates
541
Ac
542 2.2.2 Halogen based flame retardants

543
544 Halogenated FRs are molecules that include elements from group VII of the periodic table (F,
545 Cl, Br and I). Their effectiveness increases in the order F < Cl < Br < I. The type of halogen
546 dictates the effectiveness of the halogenated flame retardant. However, fluorine (F) and
547 iodine (I) are not used because they do not interfere with the polymer combustion process.
548 Fluorinated compounds are more thermally stable than most polymers and do not release
549 halogen radicals at the same temperature range or below the decomposition of the polymers.
550 Iodine compounds are less thermally stable than most commercial polymers and therefore
18
Page 18 of 110
551 release halogen species during polymer processing. Bromine and chlorine can readily be
552 released and partake in the combustion process because of their low bonding energy with
553 carbon atoms (Chen & Wang, 2010; Laoutid et al., 2009; Morgan & Gilman, 2013; Troitzsch,
554 1998).
555
t
556 2.2.2.1 Halogenated flame retardant additives
ip
557
558 Halogenated FRs differ in chemical structure from aliphatic to aromatic carbon substrates or
cr
559 can come in inorganic forms. Of these, the organohalogen compounds are most used as FRs
560 for polymers due to their effectiveness. Organochlorine and organobromine are the mostly
us
561 used, with organobromine compounds being the most commonly used. This is because the C–
562 Br bond is stable enough for environmental exposure and yet heat can easily break it to
an
563 release bromine under fire conditions to inhibit free radical reactions. It is these unique bond
564 strengths that make halogen based FRs mostly vapour phase FRs (Chen & Wang, 2010;
565 Laoutid et al., 2009; Morgan & Gilman, 2013).
M
566
567 Halogenated FR technology has been used since the 1930’s due to advantages of low cost,
568 processability, miscibility and low reduction on the physical/mechanical properties of the FR
d
569 systems. However, its flaws include increased smoke release under fire conditions, the
te
570 release of corrosive gases (i.e. HBr in case of brominated FRs) during burning which leaches
571 to the environment and thus brominated products are currently under environmental scrutiny.
p
572 The increased smoke and corrosive gas release of these compounds is rooted to their flame
ce
573 retardant chemistry. Because it inhibits combustion through the formation of HBr gas, it
574 causes the formation of partially combusted polymer decomposition products as well as
575 carbon monoxide (CO). Halogenated FR systems do not always perform well under very high
Ac
576 heat flux conditions because once a halogen is consumed by fire any remaining polymer will
577 burn if exposed to additional heat. This will happen unless a lot of halogen is present in a
578 polymer which results in higher smoke production and corrosive gas release (Laoutid et al.,
579 2009; Morgan & Gilman, 2013).
580
581 Mode of action
582
19
Page 19 of 110
583 The thermally induced polymer decomposition (during polymer combustion) releases very
584 reactive free radical species (i.e. H• and OH•). These maintain a combustion process by a
585 series of chain reactions in the gas phase.
586
587
t
588
ip
589 The reactive free radical species H• and OH• formed by chain branching are removed by
590 halogenated FR. Initially the flame retardant breaks down into a halogen radical (see below
cr
591 reaction, where X is either Cl or Br):
592
us
593 The formed halogen radical reacts to form a hydrogen halide:
594
an
595 This hydrogen halide consequently interferes with the radical chain mechanism:
596
597
M
598
599 The highly reactive H• and OH• free radical species are removed by reaction with HX and
600 replaced with less reactive X radicals. The actual flame retardant effect is therefore produced
d
601 by HX. The hydrogen halide consumed is regenerated by reaction with hydrocarbon:
te
602
603 As a result, HX is an effective FR species. It is non flammable and can have physical action
p
604 on the combustion mechanism by forming a protective gaseous layer and/or dilution of fuel
ce
605 gases. Furthermore, HX can catalyse the oxidation of the solid phase and the oxidation
606 products tend to cyclize leading to the formation of a solid protective layer (Laoutid et al.,
607 2009; Troitzsch, 1998).
Ac
608
609 The most common halogen FRA compounds are tetrabromobisphenol A (TBBPA),
610 polybromodiphenyl ether (PBDE), hexabromocyclododecane (HBCD) and
611 tetrabromophthalic anhydride (TBPA) (Chen & Wang, 2010; Laoutid et al., 2009; Morgan &
612 Gilman, 2013; Troitzsch, 1998).
613
614 2.2.2.2 Halogenated monomers and copolymers
615
20
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616
617
618
619
620
t
621
ip
622
cr
us
an
M
d
te
p
ce
Ac
21
Page 21 of 110
622
623 The advantages of reactive additive FRs are their ability to be used in relatively low
624 concentrations, and that they can be directly incorporated in the polymer structure.
625 Consequently they can increase compatibility between a polymer and an FRA, they can limit
626 the damage caused by heterogeneous additives to the mechanical properties of the resulting
627 materials, and can reduce the migration of FRAs onto the material surface (Laoutid et al.,
t
ip
628 2009).
629
cr
630 Nevertheless, they need an additional synthesis step that may be a limiting factor on an
631 industrial scale. They can be used as condensation free radical polymerization monomers,
us
632 copolymerized with virgin monomers or grafted onto the polymer chain. Their action is very
633 similar to other halogenated FRAs. In some cases, other mechanisms can be added to the
634 conventional effect of halogenated derivatives and thus changing the degradation pattern of a
an
635 polymer. The effectiveness of a halogenated monomer depends on the composition of the
636 monomer and the copolymer. Increasing the content of halogen atoms in the monomer leads
M
637 to more efficient fire retardance (Laoutid et al., 2009; Morgan & Gilman, 2013).
638
639 Reactive halogenated FRAs may be an alternative to halogenated FRAs that seem to pose
d
640 some toxicological risk to the environment. However, they are less used due to high cost, and
te
641 most of them are limited to a few polymers such as styrenics, acrylates, urethanes and
642 epoxies (Morgan & Gilman, 2013).
p
643
644 2.2.3 Silicon based flame retardants
ce
645
646 The addition of a relatively low amount of silicon based compounds to polymers substantially
Ac
647 improves their fire retardancy. These silicon based compounds are silicones, silicas,
648 organosilicates, silsesquioxanes and silicates. They can be used as fillers incorporated into
649 polymers, as copolymers or as main polymer matrices and are discussed in the following
650 sections.
651
652 2.2.3.1 Silicones
653
654 Silicones {typically polydimethylsiloxane (PDMS) polymers} are known to have excellent
655 thermal stability, high heat release (i.e. 60 to 150 kW m-1) and very limited release of toxic
22
Page 22 of 110
656 gases (i.e. CO) during thermal decomposition. They exhibit a slow burning rate without a
657 flaming drip and, when pure, they do not emit toxic smokes. Silicones have been
658 commercialized since the 1940’s. They are used in various applications in civil engineering,
659 construction building, electrical, transportation, aerospace, defence, textile, and cosmetics
660 industries. They can be used as flame retardants through direct blending with a polymer
t
661 matrix or by synthesizing block/graft copolymers including silicone segments. Their superior
ip
662 flame retardant behaviour is the result of excellent dispersion in polymer matrices and
663 migration towards the material surface during combustion followed by the formation of a
cr
664 highly flame retardant char. Their main advantage as flame retardants is that they have a
665 minimal environmental effect due to their inorganic structure. They are expensive and hence
us
666 used sparingly (Cheng & Wang, 2010; Hamdani, Longuet, Perrin, Lopez-Cuesta &
667 Ganachaud, 2009; Laoutid et al., 2009; Morgan & Gilman, 2013).
an
668
669 2.2.3.2 Silica (silicon dioxide, SiO2)
670
M
671 The flammability reduction mechanism of silica is based on a physical process rather than a
672 chemical reaction. Its effectiveness is dependent on several factors including pore size,
673 particle size, surface silanol concentration, surface area, density and viscosity. Large pore
d
674 volumes may accommodate macromolecular polymer chains, or the presence of silica may
te
675 increase the melt viscosity during pyrolysis, which can trap and/or slow down volatilization
676 and evolution of degradation products. The balance between density and surface area of the
p
677 additive, together with the polymer melt viscosity, determine whether the additive
ce
678 accumulates near the surface of a sample or sinks through the polymer melt layer. If additives
679 accumulate near the sample surface, the possibility is that the additive acts as a thermal
680 insulation layer and also reduces the polymer concentration near the surface in contact with
Ac
681 the flame. The specific area and porous volume can modify the viscosity of the system in the
682 molten state. The control over viscosity seems to be the key factor in the formation of a
683 protective layer (Cheng & Wang, 2010; Kashiwagi et al., 2000; Laoutid et al., 2009).
684
685 Several studies have been conducted where silica was used as flame retardant in
686 thermoplastics (Kashiwagi et al., 2000; Li, Jiang & Wei, 2006; Zhang et al., 2012).
687 Kashiwagi et al. (2000) used various types of silica (i.e. silica gel, fumed silica and fused
688 silica) in polypropylene (PP) and polyethylene oxide (PEO). Their effectiveness and
689 mechanisms were determined. Li et al. (2006) synthesized flame retardants that contain
23
Page 23 of 110
690 silicon elements (together with phosphorus and nitrogen), applied them in PP, and
691 investigated their fire performance. Zhang et al. (2012) investigated the use of silica and
692 ammonium polyphosphate flame retarded wood fibre in polypropylene composites. In all
693 these studies, the silica flame retarded systems showed reduced heat release and burning
694 rates. The mechanism of the reduction in the heat release rate and mass loss rate was due to
t
695 physical action of the silica in the condensed phase.
ip
696
697 2.2.4 Nano metric particles
cr
698
699 Nano metric particles contribute to the enhancement of thermal, mechanical or fire resistance
us
700 properties when used separately and well dispersed within polymer matrices.They allow
701 considerable reduction in loading content as the interfacial area between the polymer and
an
702 nanofiller is greatly increased. The contribution of each type of nanoparticles to flame
703 retardancy varies anddepends on its chemical structure and geometry. These nano-metric
704 particles are classified as layered, fibrous and particulate materials (Laoutid et al., 2009).
M
705
706 Layered materials: represented by nanoclays (e.g. montmorilonite, MMT); one nanometric
707 dimension.
d
708 Fibrous materials: e.g. carbon nantubes (CNTs), sepiolite; elongated structured materials
te
709 with two nanometric dimensions.

710 Particulate materials: e.g. nano scale particulate additives; polyhedral oligosilsesquioxane
p
711 (POSS), spherical silica nanoparticles; three nanometric dimensions.

ce
712
713 2.2.4.1 Nano-clays
714
Ac
715 A lot of work has been done on nanoclay-based polymer composites and some reviews have
716 been published (Bordes, Pollet & Avérous, 2009; Hapuarachchi & Peijs, 2010; Kiliaris &
717 Papaspyrides, 2012; Morgan, 2006; Morgan, Harris Jr., Kashiwagi, Chyall & Gilman, 2002).
718 Morgan (2006) reviewed the flame retarded polymer layered silicate nanocomposites for
719 commercial and open literature systems. Bordes et al. (2009) discussed the recent research
720 and developments in biopolyester/nanoclay systems, whereas Kiliaris and Papaspyrides
721 (2012) presented recent developments on the use of layered silicates (clay) for designing
722 polymer nanocomposites with enhanced flame retardancy. Natural clays must be chemically
723 modified in order to favour the dispersion of clay nanolayers within the polymer matrix. This
24
Page 24 of 110
724 is achieved by using organic cations such as alkylammonium, alkyl phosphonium and alkyl
725 imidazol(idin)ium, and leads to the formation of organo-modified nanoclays (Laoutid et al.,
726 2009).
727
728 Incorporation of low amounts (~10 wt.%) of organomodified nanoclay in a polymer matrix
t
729 creates a protective layer during combustion. During heating, the viscosity of a molten
ip
730 polymer/layered silicate nanocomposite decreases with increasing temperature. This
731 facilitates the migration of clay nanolayers to the surface. Heat transfer promotes thermal
cr
732 decomposition of an organomodifier and creates strongly protonic catalytic sites onto the clay
733 surface, which can catalyse the formation of a stable char residue (Kiliaris & Papaspyrides,
us
734 2012; Laoutid et al., 2009).
735
an
736 Consequently, the accumulation of clay on the surface of a material acts as a protective
737 barrier that limits the heat transfer into the material, limits the volatilization of combustible
738 degradation products, as well as the diffusion of oxygen into the material. Additionally,
M
739 nanoclay migration is enhanced by the formation of gas bubbles initiated by the
740 decomposition of both quaternary ammonium organomodifiers and polymer chains. Such gas
741 bubbles may be nucleated by the surfaces of the nanoclay sheets and could also help in the
d
742 convection of nanoclay sheets to the surface (Kiliaris & Papaspyrides, 2012; Laoutid et al.,
te
743 2009).
744
p
745 There are several factors that play a key role in determining the flammability behaviour of
ce
746 polymer/silicate layered nanocomposites. These may be char formation, morphology of the
747 nanocomposites (intercalated or exfoliated), and the ability of nanoclays to disperse, contents
748 of organomodifier in nanoclays, nanoclay loading and melt viscosity. The main fire
Ac
749 retardancy mechanisms in polymer/silicate layered nanocomposites may be the formation of

750 a barrier against heat and volatiles by migration of clay nanolayers towards the material
751 surface, followed by char formation together with increased melt viscosity for exfoliated
752 nanocomposites. These mechanisms may modify the fire properties of nanocomposites
753 differently depending on the fire test applied. In general, incorporation of nanoclays retards
754 and reduces the peak heat release rate (PHRR), but does not lower the total heat release
755 (THR). This may mean that almost all of the fuel released is combusted, hence almost no
756 change in THR. However, the fuel is released so slowly that HRR stays throughout the
757 burning process (Morgan, 2006). It may also reduce the time to ignition (TTI). In addition, it
25
Page 25 of 110
758 reduces the melt viscosity in exfoliated nanocomposites and thus prevents dripping and
759 promotes char formation (Kandola, 2001; Laoutid et al. 2009).
760
761 Manfredi, Rodríguez, Wladyka-Przybylak & Vázquez (2010) investigated various properties
762 including fire resistance of organically modified clay on jute reinforced vinyl ester and resol
t
763 composites. The composites showed an improvement in their fire performance. Lower fire
ip
764 risk and low heat evolution were observed. Barbosa, Araújo, Melo & Ito (2007) used
765 Brazilian clay [montmorillonite (MMT)] and two types of commercial flame retardants with a
cr
766 polyethylene matrix to evaluate their flammability behaviour. Polyethylene flame retarded
767 nanocomposites were produced via direct melt intercalation. The flammability resistance of
us
768 PE/Brazilian clay nanocomposites was improved due to the barrier effect of the organoclay
769 during the combustion. The nanocomposites were more effective than conventional PE/flame
an
770 retardants systems, and only 3 wt.% MMT reduced the burning rate of the nanocomposites by
771 17%.
772
M
773 Wei, Bocchini and Camino (2013) addressed the combustion behaviour of PLA
774 nanocomposites based on organomodified MMT clays (i.e. Closite 30B and 20A) with N-
775 alkoxy hindered amine as a flame retardant. Si et al., (2007) prepared self-extinguishing
d
776 polymer nanocomposites using Closite 20A with PMMA matrix, decabromodiphenyl ether
te
777 and antimony oxide as flame retardants. Ribeiro, Estevão, Pereira, Rodrigues and Nascimento
778 (2009) imposed some organic chemical treatments on natural Brazilian MMT clay and then
p
779 evaluated the effect of treatments on flame retardancy potential of ethylene-buty acrylate
ce
780 copolymer composites in the presence of APP and PER (pentaerithritol). In all these studies,
781 samples were prepared by melt mixing process and then subjected to various characterization
782 tests on morphological, thermal, mechanical and flammability performance (i.e. UL94, LOI,
Ac
783 cone calorimetry).

784
785 From these studies, it is generally reported that the incorporation of clays into polymer
786 matrices led to reduced burning rate with respect to neat polymers. The effect was attributed
787 to the ability of clay to form stable char on the surface of the burning nanocomposites. This
788 insulated the underlying polymer from heat transfer due to flames, thus lowering the rate of
789 volatilization (Wei, Bocchini and Camino, 2013). Furthermore, Wei, Bocchini and Camino
790 (2013) concluded that the combination of nanoclays and flame retardant did not exhibit
791 remarkable additional influence on fire behaviour of PLA nanocomposites except for
26
Page 26 of 110
792 improved resistance to self-sustained combustion. However, Ribeiro et al., (2009) and Si et
793 al., (2007) have concluded that the combination resulted to lower PHRR, average MLR and
794 HRR than those with only clay or the FRAs. This indicated some synergistic effect between
795 nanoclays and FRAs. Ribeiro et al., (2009) also reported that the modifications to natural
796 Brazilian MMT clay did not change their flame retardancy performance.
t
797
ip
798 Tai, Yeun, Song and Hu (2012) incorporated the organic nanoclay into polyphosphoramide
799 (PDEPD) by in-situ polycondensation to prepare flame retardant/clay nanocomposites. These
cr
800 were then introduced to both polystyrene (PS) and polyurethane (PU) by solvent blending
801 method. From the MCC tests, it was found that both PDEPD and mostly PDEPD/clay
us
802 nanocomposites FRAs improved the flammability performance of PS and PU matrices by
803 reducing both PHRR and THR. Moreover, the reduction in THR with the inclusion of
an
804 PDEPD was attributed to the enhancement of char residues after combustion thus leading to
805 less evolution of combustible fuel gases.
806
M
807 2.2.4.2 Carbon nanotubes
808
809 Carbon nanotubes (CNTs) are the most widely studied nanofibrous materials with respect to
d
810 polymer flame retardancy (Gao, Beyer & Yuana, 2005; Hapuarachchi & Peijs, 2010; Laoutid
te
811 et al. 2009; Ye, Wu & Qu, 2009).They may be synthesized in several ways such as arc
812 discharge, laser ablation and thermal or plasma enhanced chemical vapour growth deposition
p
813 (CVD). Direct arc discharge and laser ablation require the use of small quantities of a metal
ce
814 catalyst and very high temperatures. The CVD technique, on the other hand, enables the
815 synthesis of CNTs at lower temperatures but leaves significant amounts of catalysts residues
816 on the recovered sample. These nanotubes show exceptional properties that can be used in
Ac
817 many applications ranging from macroscopic material composites to nanodevices. They have
818 high aspect ratios and as a result percolate to form networks at very low loadings in a
819 polymer matrix. This leads to a substantial improvement in a number of properties such as
820 mechanical, rheological and flame retardancy (Laoutid et al. 2009).
821
822 There are two different types of carbon nanotubes, i.e. small diameter (1-2 nm) single walled
823 nanotubes (SWNTs) and large diameter (10-100 nm) multi walled nanotubes (MWNTs).
824 CNTs are an interesting alternative to the use of conventional flame retardants and nanoclays.
825 Their incorporation at low contents (< 3wt.%) has resulted in enhanced flammability for
27
Page 27 of 110
826 several polymers {PP, polystyrene (PS), ethylene vinyl acetate (EVA), polymethyl
827 methacrylate (PMMA), low density polyethylene (LDPE) and polyamide 6 (PA 6)}. Several
828 factors influence the flame retardant properties of polymeric material nanocomposites:
829 nanotube dispersion, nanotube loading rate, mean size of nanotubes and large aspect ratio.
830 Large aspect ratio can lead to the formation of an efficient and compact layer (Laoutid et al.
t
831 2009).
ip
832
833 The presence of CNTs may increase thermal conductivity of a polymer and thus increase the
cr
834 time to ignition (TTI) and peak heat release rate (PHRR) where MWNTs are used. Several
835 studies based on CNTs with nanoclays in different thermoplastic matrices were reported. Gao
us
836 et al. (2005), Hapuarachchi and Peijs (2010) and Ye et al. (2009) investigated the role of
837 MWNTs with clays (Hapuarachchi & Peijs, 2010; Ye et al., 2009) and magnesium hydroxide
an
838 (MH) (Gao et al., 2005) in the fire retardancy of PLA and EVA nanocomposites. In all these
839 studies, it was reported that the incorporation of MWNTs in the presence of other additives
840 resulted in a remarkable reduction in heat release rate (HRR), PHRR, mass loss rate (MLR)
M
841 as well as a prolonged combustion in the cone calorimetry test. Ye et al. (2009) concluded
842 that there was a synergistic effect which was driven by factors such as increased melt
843 viscosity, improved thermo oxidation stability and the formation of compact charred layers
d
844 due to MWNTs acting as heat barriers and insulation. Furthermore, Gao et al. (2005)
te
845 concluded that the addition of clay into a CNTs/EVA composite enhanced the formation of
846 graphitic carbon. Additionally, nanotubes reduced the surface cracks of chars to increase the
p
847 barrier resistance to the evolution of flammable volatiles and the oxygen ingress into the
ce
848 condensed phase.

849
850 Peeterbroeck et al., (2004, 2007) used MWNTs with EVA copolymers, in the presence of
Ac
851 commercial organoclays (Peeterbroeck et al., 2004) and high density polyethylene (HDPE)
852 coated-MWNTs (Peeterbroeck et al., 2007). In the latter study, the authors demonstrated the
853 significant effect of the HDPE coating on the mechanical properties of nanocomposites and
854 explained the flame retardant efficiency of MWNTs in EVA matrix. Furthermore, improved
855 flammability performance of coated MWNTs containing EVA nanocomposites was reported.
856 This followed the reduction in HRR and enhanced cohesion of the combustion residue, which
857 was attributed to high quality of dispersion of HDPE-coated nanotubes and the chemical
858 structure of the combustion products. In the former study (Peeterbroeck et al., 2004), it was
859 concluded that simultaneous addition of both modified clay and CNTs displayed a synergistic
28
Page 28 of 110
860 effect. The enhanced thermal and mechanical properties in the presence of nanofillers were
861 also reported.
862
863 When the synergistic effect of CNTs, MMTs and decabromodiphenyl oxide/tin oxide in
864 enhancing flame retardancy performance of PS was investigated, Lu and Wilkie (2010) found
t
865 that nanotubes were more efficient than clay in improving flame retardancy of materials.
ip
866 These CNTs are said to have promoted carbonization in the polystyrene matrix. On the other
867 hand, Isitman and Kaynak (2010) evaluated the potential synergistic flame retardancy action
cr
868 of filler nanoparticles (i.e. nanoclays and CNTs) combined with organophosphorus flame
869 retardant in PMMA. In this case, it is reported that nanoclays showed improved effect on fire
us
870 properties of intumescent nanocomposites compared to CNTs containing ones. This was
871 explained in terms of suppressed intumescent character of organophosphorus FRA exerted by
an
872 strong and continuous CNTs networks formed on the flaming surface during combustion.
873 Nanoclays on the other side are said to have physically reinforced and consolidated the
874 phosphate barriers without interfering with its intumescent character.
M
875
876 2.2.4.3 Graphene
877
d
878 Graphene is an emerging two dimensional material with unique mechanical, electrical and
te
879 thermal properties. It consists of monolayer of sp2-hybridized carbon atoms (carbon – carbon
880 bond length of ~ 142 pm) packed in a honeycomb lattice. Its current scientific research
p
881 interest results from marked enhancement in polymer properties at low filler contents. This is
ce
882 due to high aspect ratio of graphene platelets, homogenous dispersion of graphene platelets in
883 a polymer matrix, and the filler-polymer interactions at interface. Similar to other types of
884 nanofillers such as CNTs and MMTs, it is also used to impart flame retardancy character to
Ac
885 polymeric materials. This beneficial flame retardancy property may be attributed to the
886 physical barrier effect of layered graphene that slows down the release of volatile flammable
887 gases and protects the underlying material from further burning (Mittal, 2014; Premkumar &
888 Geckeler, 2012; Hong et al., 2014; Wang, Wei, Qiang & Liu, 2014).
889
890 Numerous works on graphene-based nanocomposites have been done with focus mainly on
891 various properties other than flammability. The graphene-based nanocomposites may be
892 manufactured in four main routes. These may be a) template synthesis, b) intercalation from
893 solution, c) in situ intercalative polymerization and d) melt intercalation. Mittal (2014)
29
Page 29 of 110
894 reviewed graphene materials in functional polymer nanocomposites, and has elaborated on
895 these fabrication methods. Premkumar and Geckeler (2012) looked at graphene-DNA hybrid
896 materials. Most studies on graphene nanocomposites mainly involved petroleum-based
897 polymer matrices such as EVA, PP, PVA, PMMA and epoxy (Wang, Wei, Qiang & Liu,
898 2014; Hong et al., 2014; Huang, Chen, Tang & Gao, 2012; Huang, Gao, Wang, Liang & Ge,
t
899 2012; Huang et al., 2012; Dittrich, Wartig, Hofmann, Mülhaupt & Schartel, 2013), whereas
ip
900 studied biopolymers included poly(D, L-lactic-co-glycolic acid), chitosan and cellulose
901 (Pandele et al., 2014; Yoon et al., 2011; Feng, Zhang, Shen, Yoshino & Feng, 2012; Ryu,
cr
902 Mahapatra, Yadav & Cho, 2013; Lee, Marroquin, Rhee, Park & Hui, 2013). Form these
903 studies, the flammability performance of graphene nanocomposites were based on petroleum
us
904 polymer matrices and so far non on biopolymer matrices.
905
an
906 Huang et al., (2012a, b, c) investigated the flame retardant properties of graphene containing
907 nanocomposites in EVA and PVA polymer matrices. In these studies, authors used graphene
908 alone (Huang et al., 2012a) and incorporated flame retardant additives such as melamine
M
909 polyphosphate (MMP) (Huang et al., 2012b) as well as an intumescent FR (i.e.
910 poly(piperazine spyrocyclic pentaerythrito bisphosphonate) (PPSPB) grafted onto the surface
911 of graphene oxide (Huang et al., 2012c). From all these studies, the presence of graphene and
d
912 other FRAs led to improved flammability character of the investigated nanocomposites. This
te
913 was indicated by increased TTI and reduction of values of PHRR, THR, ASEA and average
914 MLR (Huang et al., 2012a, b) compared to neat PVA. This was attributed to the condensed
p
915 phase flame retardancy through forming a compact, dense and uniform char during
ce
916 combustion (Huang et al., 2012a). Furthermore, the combination of MMP with graphene in
917 PVA achieved the LOI value of 29.6 vol.% and UL94 V-0 grade (Huang et al., 2012b).
918 Similarly, the graphene grafted PPSPB were reported to have enhanced the flammability
Ac
919 performance of EVA by reducing the PHRR of the nanocomposites by about 56% at 1 wt.%
920 filler content (Huang et al., 2012c).
921
922 Dittrich et al., (2013) used various carbon additives with different particle sizes and shape to
923 investigate their influence on both flammability and mechanical properties of isotactic PP.
924 Authors compared thermally reduced graphite oxide and multi-layer graphene with carbon
925 black, MWNTs and expanded graphite. The flammability properties of PP were mainly
926 enhanced in the presence of thermally reduced graphite and multi layer graphene which
30
Page 30 of 110
927 formed residue layers that protected the underlying polymer during combustion. These led to
928 a reduction PHRR up to 74% with respect to neat polymer.
929
930 2.2.4.4 Nano scale particulate additives
931
t
932 Nano scale particulate additives form another family of additives made up of nanoparticles of
ip
933 metal oxides, silica and polyhedral oligomeric silsesquioxane (POSS). They are distinguished
934 by their isometric dimensions.
cr
935
936 2.2.4.4.1 Silsesquioxane
us
937
938 Polyhedral oligomeric silsesquioxane (POSS) cluster is an inorganic silica like nanocage
an
939 (general formula RSiO3/2)n where 6 < n <18. The inorganic core of POSS is surrounded by
940 organic ligands (i.e. hydrogen, halogen, alkyl groups, organofunctional groups) covalently
941 bound to the Si atoms placed at the vertices of the polyhedral cage. A general concern about
M
942 POSS is the high level of interactions existing between clusters. This makes some POSS
943 immiscible with some monomers or polymers. Consequently, the nature of the organic
944 ligands of POSS clusters is an important element to choose, since it controls the behaviour of
d
945 clusters during processing and polymerization, and thus allows tailoring the desired
te
946 microstructure for the POSS hybrid polymer systems. POSS is given by methyl phenyl
947 polysilsesquioxane, aluminumisobutyl silsesquioxane (Al POSS) and zinc isobutyl
p
948 silsesquioxane (Zn POSS). They can play a role of metal dispersing agent, and it is possible
ce
949 to include a metal atom at one corner of the POSS nanocage structure. These inorganic
950 nanocages are also referred to as preceramic compounds (Franchini, Galy, Gérard, Tabuani &
951 Medici, 2009; Waddon & Coughlin, 2003).
Ac
952
953 There are two types of POSS that have been studied with respect to flame retardancy; those
954 that bear either i) eight identical R groups (R = methyl, phenyl, isobutyl or isooctyl), or ii)
955 seven R groups of the same nature and one functional R′ group (R′ = ester, silane, isocynate,
956 methacrylate, alcohol, epoxide or amine). This wide range of R and R′ groups allows for the
957 selective use of functionalized POSS according to the chemical nature of the polymer matrix.
958 The functionality of the R′ group can improve the compatibility between the dispersed
959 nanocages and the polymer matrix. It can also allow either chemical grafting of reactive
960 polymer chains or initiation of polymerization reactions from the POSS surface via the
31
Page 31 of 110
961 socalled “grafting from” technique (Franchini et al., 2009; Laoutid et al. 2009; Waddon &
962 Coughlin, 2003). Devaux, Rochery and Bourbigot (2002) used montmorillonite (MMT) clay
963 together with POSS to process polyurethane nanocomposites, and they concluded that the
964 nanoadditives appreciably reduced the harmful effects of fire. Additionally, the study showed
965 the importance of the choice of nanoadditives on the results of fire retardant behaviour with
t
966 two notable factors: the nature of the chemical groups grafted onto POSS and the conditions
ip
967 of the coating synthesis.
968
cr
969 The presence of POSS in polymers modifies both the viscosity and mechanical properties of
970 the molten polymer. It also affects the thermal stability and fire performance by reducing the
us
971 amount of heat released upon combustion. On combustion, POSS acts like a precursor
972 forming thermally stable ceramic materials at high temperatures. For example, Franchini et
an
973 al. (2009) showed that POSS nanoclusters resulted in the improvement of fire retardancy of
974 epoxy materials and the mechanism involved the formation of a rigid char structure during
975 combustion. Furthermore, He, Song, Hu and Zhou (2009) prepared a series of flame retardant
M
976 hybrids based on bisphenol A polycarbonate (PC), trisilanolphenylpolyhedral oligomeric
977 silsesquioxane (TPOSS) and oligomeric bisphenyl A bis(diphenyl phosphate) (BDP) by a
978 melt blending method.The group found enhanced thermal oxidative stability and fire
d
979 resistance of the char layer which built upon the surface of the burning polymer when both
te
980 BDP and TPOSS were introduced. A synergistic effect was established in the system
981 consisting of 2 wt.% TPOSS and 3 wt.% BDP.
p
982
ce
983 In their investigation where POSS and talc fillers were incorporated in vinyl ester resins and
984 tested for different properties including flammability, Glodek, Boyd, McAninch and LaScala
985 (2008) reported slightly improved fire retardancy and material property. There was a slight
Ac
986 increase in fire resistance of methacryl POSS relative to other fillers and this was attributed to
987 successful dispersion and reaction of this POSS into the polymer matrix. However, its overall
988 fire resistance performance was reported as poor relative to brominated FRAs used in the
989 study. Fina, Tabuani and Camino (2010) prepared PP/POSS blends using POSS with
990 different organic groups (methyl, vinyl or phenyl) by melt mixing method. Authors reported
991 improved performance in both thermal and combustion rate. This was said to be as a results
992 of formation of a ceramic superficial layer that protected the underlying material from
993 degradation. The conclusion made was that better results were obtained when vinyl-POSS
994 was used as seen from maximum HRR reduction and increased LOI value. In another study
32
Page 32 of 110
995 on the effect of flame retardance of isotactic PP/aminopropylisobutyl POSS composites,
996 Bouza et al., (2014) reported improved fire retardance as determined by LOI test. In this
997 study, authors incorporated maleic anhydrite grafted PP (MA-g-PP) coupling agent and such
998 composites led to remarkable increase in LOI values when 2% POSS and 10% MA-g-PP
999 were compounded with PP matrix. Furthermore, the presence of these additives in PP matrix
t
1000 gave composites with high thermal stability than neat matrix as reported from TGA test.
ip
1001
1002 When biopolymers such as poly(butylenes succinate) (PBS) (Wang et al., 2012) and PLA
cr
1003 (Fox et al., 2014) were used with POSS materials, improved materials properties were
1004 reported. Wang et al., (2012) used POSS and graphene as nanofillers to flame retard PBS
us
1005 prepared by melt blending. It was reported that the addition of graphene led to superior flame
1006 retardance to POSS. Authors concluded that the presence of both POSS and graphene
an
1007 improved the char yield with graphene incorporation into PBS leading to better thermo-
1008 oxidative resistance in char layer. In a latest study, PLA was extruded with intumescent FRAs
1009 based on APP, nanofibrillated cellulose fibre, POSS modified nanofibrillated cellulose fibre
M
1010 and PER by Fox et al., (2014). The authors found that the cross-linked network formed
1011 between cellulose, POSS and PLA produced composites with superior flame retardant,
1012 rheological and mechanical properties with respect to other intumescent formulations.
d
1013
te
1014 2.2.4.4.2 Metallic oxide particles

1015
p
1016 Metal oxide particles have been studied as reinforcing fillers for polymeric materials. These
ce
1017 particles may be nanometric titanium oxide (TiO2), ferric oxide (Fe2O3), aluminum oxide
1018 (Al2O3) or antimony oxide (Sb2O3) particles. Flammability performance of these metallic
1019 oxide nanoparticles is dependent upon filler content, particle size and surface area of the
Ac
1020 nanoparticles (Gallo, Braun, Schartel, Russo & Acierno, 2009; Gallo, Schartel, Acierno &
1021 Russo, 2011; Laachachi, Leroy, Cochez, Ferriol & Lopez-Cuesta, 2005, 2007; Laoutid et al.,
1022 2009; Lewin, 2011).
1023
1024 Laachachi et al. (2005, 2007) looked at the influence of different nanoparticles (Al2O3, TiO2
1025 and Fe2O3) in combination with organoclays (organomodified MMT) and phosphinate
1026 additives on the thermal stability and fire retardancy of poly(methyl methacrylate). In both
1027 studies, a synergistic effect on the thermal stability and fire performance of these systems was
1028 reported. This resulted in enhanced ignition times, reduced total heat, reduced smoke release
33
Page 33 of 110
1029 and a significant increase in the total burning period. The metal oxide particles seemed to
1030 promote carbonaceous layer/char formation. They also modified the heat transfer properties
1031 of the polymer nanocomposites due to their good thermal properties and large specific area.
1032 Depending on the system, the metal oxide particles may (Laachachi et al., 2005) or may not
1033 (Laachachi et al., 2007) improve the fire performance of the composites.
t
1034
ip
1035 Gallo et al. (2009, 2011) investigated the flame retardancy synergy between aluminium
1036 phosphinate and metal oxides for different polymers. In the first study (Gallo et al., 2009)
cr
1037 Al2O3 and TiO2 were used for poly(butylene terephthalate) PBT. In the second study (Gallo
1038 et al., 2011), they used Fe2O3 and Sb2O3 for a commercial poly(3-hydroxybutyrate-co-3-
us
1039 hydroxyvalerate)/poly(butylene adipate-co-terephthalate) PHBV/PBAT biodegradable blend
1040 system. They reported better fire retardancy which was ascribed to increased intermediate
an
1041 char formation. A synergistic effect due to the phosphorus and the nanofiller components was
1042 observed in the flame retardancy mechanism, where the phosphorus acted as flame inhibition
1043 in the gas phase, and the nanofiller promoted crosslinking in the solid phase (Gallo et al.,
M
1044 2009). In both studies a combination of metal oxides and aluminium phosphinate resulted in
1045 better classification in the UL94 test due to the combination of the different mechanisms.
1046
d
1047 Wang, Han and Ke (2006) prepared flame retardant nanocoatings of nanometer layer double
te
1048 hydroxides (nano-LDHs) and titanium oxide nanoparticles to ammonium polyphosphate-

1049 pentaerythritol-melamine intumescent FR system. Authors studied the improvement of
p
1050 nanoparticles in fire resistance and anti-ageing properties of the intumescent flame retarded
ce
1051 system. It was reported that the thermal decomposition of nano-LDHs promoted formation of
1052 the char by the IFR system, which was said to be intercalated nanostructure with mixed
1053 resultant metal oxides (Al2O3 and MgAl2O4). This intercalated structure was thought to have
Ac
1054 improved the anti-oxidation character of the char structure. It was further reported that
1055 inclusion of nano titanium oxide particles improved the anti-ageing of the IFR coated system.
1056 The conclusion made was that nanocoating has the good expanding effect and fire resistance
1057 property even after 500 hours accelerated ageing.
1058
1059 Shen, Chen and Li (2012) and Li et al., (2012) used PP to investigate the influences of metal
1060 oxides on flammability properties of nanocomposites. Lanthanum oxide in the presence of
1061 magnesium hydroxide were extruded with PP matrix and their flammability performance
1062 tested via LOI and microscale combustion calorimeter (Shen, Chen and Li, 2012). On the
34
Page 34 of 110
1063 other hand, Li et al., (2012) compounded the intumescent system based on APP and PER
1064 with antimony oxide by melt mixing method. LOI and UL94 were employed for flame
1065 resistance tests. In this study authors reported increased LOI values from 27.8 to 36.6 vol.%
1066 in the presence of antimony oxide. The FR system also recorded UL94 V 0 rating at the 2
1067 wt.% content of Sb2O3. This was attributed to the reaction of antimony oxide with APP to
t
1068 form crosslinked charred layers. Lowered mechanical properties were also reported in the
ip
1069 presence of a metal oxide due to poor compatibility between PP and Sb2O3. In the former
1070 study (Shen, Chen and Li, 2012), it was found that the presence of La2O3 could remarkably
cr
1071 improve the flame retardancy of magnesium hydroxide filled PP flame retarded composites.
1072 It was indicated by the obtained UL94 V-0 rating and reduced HRR, THR and HRC values of
us
1073 the PP/MH/ La2O3 composites. This was attributed to enhanced quality of condensed phase
1074 charred layers deposited on the surface of formed magnesium oxide particles through the
an
1075 participation of PP chains in char formation due to a catalytic effect of lanthanum oxide. The
1076 authors further proposed some flame retardancy mechanisms which may be obtained from the
1077 source.
M
1078
1079 In general, the incorporation of nanoparticles (organoclays, CNTs, or POSS) decreases
1080 polymer flammability through several mechanisms. Amongst others, limiting the fuel
d
1081 transfer, formation of protective layers (char and/or ceramic like materials) and prevention of
te
1082 dripping via reduced melt viscosity can be mentioned. These polymer nanocomposites still
1083 burn with little reduction in THR and TTI is generally not improved, which can even
p
1084 decrease for some nanocomposites. This may somehow necessitate the use of nanoparticles in
ce
1085 combination with other flame retardant agents for a synergistic effect.
1086
1087 2.2.4.5 Hybrid nanofillers
Ac
1088
1089 The hybrid materials refer to the class of materials whereby inorganic and organic
1090 components are mixed intimately at a nanometric or molecular scale. Hybrids may be either
1091 homogeneous systems of miscible organic and inorganic components or can be
1092 heterogeneous. The properties of the resultant material do not only depend on individual
1093 properties of the materials, but also on the scale of interaction between the two components
1094 that contributes noticeably to the properties of the resultant material. These materials have the
1095 potential to improve, amongst others, thermal, mechanical and photochemical stability
1096 (http://www.dstuns.iitm.ac.in/teaching-and-
35
Page 35 of 110
1097 presentations/teaching/undergraduate%20courses/vy305-molecular-architecture-and-
1098 evolution-of-functions/presentations/presentations-2007/seminar-1/P4.pdf).
1099
1100 A number of studies have been done on the use of hybrid materials in thermal, mechanical
1101 and flame resistance performance (Wang, Wei, Qian & Liu, 2014; Bonnet, Bounor-Legaré,
t
1102 Boisson, Camino & Cassagnau, 2012; Marras, Zuburtikudis & Panayiotou, 2007; Nurul &
ip
1103 Mariatti; 2013; Messori et al., 2003; Wang, Pang, Chen, Lin & Ning, 2013; Vasiljević et al.,
1104 2013). Different hybrid materials such as graphene, phosphorus, layered silicate, silane-PCL,
cr
1105 brucite-polyphosphate-amine based inorganic-organic materials. Messori et al., (2003)
1106 prepared organic-inorganic hybrid materials from tetraethoxysilane and α and α,ω-
us
1107 triethoxysilane terminated poly(ε-caprolactone) (PCL-Si) using sol-gel process. PMMA slabs
1108 were dip-coated with PCL-Si/silica hybrids and increased flame resistance was reported with
an
1109 respect to neat matrix. This was attributed to a preferential segregation of silica onto the outer
1110 surface of the nanocomposites. Bonnet et al., (2012) prepared EVA-based hybrid material
1111 containing silicon and phosphorus to improve flame retardancy. Authors found synergistic
M
1112 effect between silicon and phosphorus on the fire properties at 1.3 wt.% silicon and 1.4 wt.%
1113 of phosphorus loading. A reduction of 35% in PHRR measured in a cone calorimeter for
1114 EVA-hybrid materials compared to pure EVA. This was attributed to the formation of
d
1115 compact charred layer.

te
1116
1117 2.2.5 Mineral flame retardant
p
1118
ce
1119 Mineral FRs have been researched and reviewed by numerous investigators (Ahmad
1120 Ramazani, Rahimi, Frouchi & Radman, 2008; Cárdenas et al., 2008; Durin France, Ferry,
1121 Lopez-Cuesta & Crespy, 2000; Focke, Molefe, Labuschagne & Ramjee, 2009; Haurie et al.,
Ac
1122 2006, 2007; Hollingbery & Hull, 2010a, 2010b, 2012; Hull, Witkowski & Hollingbery, 2011;
1123 Laoutid et al., 2006, 2009; Morgan, Cogen, Opperman & Harris, 2007; Nachtigall, Miotto,
1124 Schneider, Mauler & Forte, 2006; Pawlowski, Schartel, Fichera & Jäger, 2010; Qui, Xie,
1125 Ding & Qu, 2003; Rothon & Hornsby, 1996; Sain, Park & Suhara, 2004; Tang, Zhou & Liu,
1126 2013; Witkowski, Stec & Hull, 2012). These inorganic fillers can influence the reaction of
1127 polymers including inert ones. They reduce the contact of combustible products, modifythe
1128 thermal conductivity and all its thermophysical properties, and change the viscosity of the
1129 resulting materials. These have indirect incidence on the fire performance of a polymer.
36
Page 36 of 110
1130 Some minerals (see Table 2) are specifically used as FRs due to their behaviour at high
1131 temperatures (Hollingbery & Hull, 2010a, 2010b; Laoutid et al., 2009).
1132
1133 The most commonly used mineral flame retardants are hydrocarbonates (Haurie et al., 2006,
1134 2007; Hollingbery & Hull, 2012; Hull et al., 2011; Laoutid et al., 2006, 2009), metal
t
1135 hydroxide (aluminum and magnesium) (Ahmad Ramazani et al., 2008; Cárdenas et al., 2008;
ip
1136 Durin France et al., 2000; Grexa & Lübke, 2001; Haurie et al., 2007; Hollingbery & Hull,
1137 2010a, 2010b; Laoutid et al., 2009; Nachtigall et al., 2006; Qui et al., 2003; Rothon &
cr
1138 Hornsby, 1996; Sain et al., 2004; Witkowski et al., 2012) and borates (Durin France et al.,
1139 2000; Grexa & Lübke, 2001; Laoutid et al., 2009; Pawlowski et al., 2010; Sain et al., 2004).
us
1140 Inorganic fillers have a physical flame retardant action. As the temperature of the system
1141 rises, fillers decompose endothermically and consequently absorb energy. Furthermore, they
an
1142 release non flammable molecules such as H2O and CO2. These molecules serve to dilute
1143 combustible gases and can also promote the formation of a protective ceramic or vitreous
1144 layer due to their release which leaves behind such a layer (Hollingbery & Hull, 2010a,
M
1145 2010b; Laoutid et al., 2006, 2009).
1146
1147
d
1148
te
1149 Table 2. Physical properties of potential fire retardant mineral fillers. Reprinted from
1150 Hull et al. (2011), Copyright 2011, with permission from Elsevier.
p
Filler Formula Tdecomp/ °C ∆Hdecomp/kJ g-1

ce
Aluminium hydroxide Al2O3·3H2O 180-200 1300

Magnesium hydroxide Mg(OH)2 300-320 1450
Calcium hydroxide Ca(OH)2 430-450 1150
Ac
Nesquehonite MgCO3·3H2O 70-100 1750

Hydromagnesite Mg5(CO3)4(OH)2·4H2O 220-240 1300
Huntite Mg3Ca(CO3)4 400 980
Ultracarb Hydromagnesite/Huntite 220-400 1172
Boehmite 60/40 AlO(OH) 340-350 560
1151
1152 2.2.5.1 Hydroxycarbonates
1153
37
Page 37 of 110
1154 All carbonates release CO2 at high temperatures, except for magnesium and calcium
1155 carbonates releasing it below 1000 °C. Magnesium carbonate seems to be the one releasing
1156 carbon dioxide at the lowest temperature of about 550 °C (Haurie et al., 2007). In comparison
1157 with other conventional flame retardants, hydrocarbonates are less widely used but remain an
1158 alternative to metal hydroxides. Natural magnesium carbonate (magnesite) and synthetic
t
1159 magnesium hydrocarbonate (hydromagnesite) release water, break down endothermically and
ip
1160 liberate CO2 at high temperature. The thermal decomposition of hydromagnesite
1161 or in air can be described as (Haurie et
cr
1162 al., 2006, 2007; Hollingbery & Hull, 2012; Hull et al., 2011; Laoutid et al., 2006, 2009):
1163
us
1164
1165 (800kJ/kg)
an
1166
1167 Hydromagnesite releases water and carbon dioxide over a wider temperature range than
1168 aluminum trihydroxide (ATH) and magnesium dihydroxide (MDH) (also called magnesium
M
1169 hydroxide, MH) (see section 2.2.5.2). It has been used as flame retardant in polypropylene
1170 (PP), ethylene vinyl acetate (EVA) (Haurie et al., 2006) and low density polyethylene
1171 (LDPE)/ethylene vinyl acetate (EVA) blends (Haurie et al., 2006, 2007). It releases both
d
1172 water and carbon dioxide between 200 and 550 °C in comparison with ATH (180 to 200 °C)
te
1173 and MDH (300 to 340 °C) suggesting that it may have similar or even better flame retardancy
1174 effectiveness than ATH and MDH (Laoutid et al., 2009).
p
1175
ce
1176 Some studies have been conducted on magnesium carbonate (Focke et al., 2009) and
1177 hydromagnesite (Haurie et al., 2006, 2007; Hollingbery & Hull, 2012; Hull et al., 2011;
1178 Laoutid et al., 2006). Haurie et al. (2006, 2007) investigated the flammability and thermal
Ac
1179 stability of hydromagnesite alone in polyethylene (Haurie et al., 2006) and combined with
1180 aluminum hydroxide, magnesium hydroxide and montmorillonite mixtures in
1181 polyethylene/ethylene vinyl acetate blends (Haurie et al., 2007). Laoutid et al. (2006)
1182 compared the flame retardancy of a combination of hydromagnesite/organomodified
1183 montmorillonite (MMT) with a magnesium hydroxide (MH and/or MDH)/MMT flame
1184 retardant system. In all these studies, improved fire resistance (i.e. reduced peak heat release
1185 rate, auto extinguishability, and increased time to ignition) was generally reported. The
38
Page 38 of 110
1186 conclusions made were, namely, reduction in mineral filler content as well as improved
1187 mechanical properties due to the presence of nanoclays.
1188
1189 2.2.5.2 Metal hydroxide
1190
t
1191 Metal hydroxides are the largest group of mineral fire retardants. They act as flame retardants
ip
1192 for polymers by releasing water vapour through endothermic decomposition and leave a
1193 thermally stable inorganic residue. This has to occur at temperatures higher than the polymer
cr
1194 processing temperature range and around the polymer decomposition temperature. Aluminum
1195 trihydroxide, Al(OH)3 (ATH) and magnesium dihydroxide, Mg(OH)2 (MDH) are the most
us
1196 commonly used metal hydroxides. They are both used as smoke suppressants and have been
1197 incorporated in wood products as flame retardants (Grexa & Lübke, 2001; Hollingbery &
an
1198 Hull, 2010a, 2010b; Laoutid et al., 2009).
1199
1200 The endothermic decomposition of ATH occurs between 180 and 200 °C, depending on
M
1201 particle size and physical form, leading to the release of water and formation of alumina:
1202 (1050 kJ/kg)
1203 The decomposition reaction of ATH has several effects on the combustion of a polymer,
d
1204 namely it absorbs 1050 kJ/kg of energy, and then cools down the polymer material, the
te
1205 formed solid alumina (Al2O3) provides a thermally insulating protective coating, and the
1206 released water vapour dilutes the combustible gases and forms a protective gas layer. The use
p
1207 of ATH lowers fire growth in cone calorimetry and markedly reduces smoke production.
ce
1208 However, the fire properties of ATH filled polymers are only of interest at high loading levels
1209 i.e. 60wt.%. Such high loadings have a negative effect on the mechanical properties of the
1210 composites. This limits the application of mineral flame retardants. Due to its low processing
Ac
1211 temperature, ATH is limited to polymers with low processing temperatures such as EVA and
1212 LDPE (Cárdenas et al., 2008; Haurie et al., 2007; Hollingbery & Hull, 2010a, 2010b; Laoutid
1213 et al., 2009; Witkowski et al., 2012).
1214
1215 The use of ATH as a flame retardant was explored in different studies (Ahmad Ramazani et
1216 al., 2008; Cárdenas et al., 2008; Haurie et al., 2007; Nachtigall et al., 2006; Witkowski et al.,
1217 2012) where it was used in combination with other additives. Haurie et al. (2007) used
1218 hydromagnesite, MDH, ATH and montmorillonite in LDPE/EVA blends, Cárdenas et al.
39
Page 39 of 110
1219 (2008) and Witkowski et al. (2012) investigated the influence of ATH (different particle sizes
1220 and surface treatments) and both ATH and MDH, respectively, on the fire retardant
1221 properties of EVA/nanoclay composites. As a way to minimize the negative effects of high
1222 loads of metallic hydroxides, Nachtigall et al. (2006) incorporated interfacial coupling agents
1223 for polypropylene (PP)/ATH composites. The effect of a combination of ATH and zinc
t
1224 borate on a PP matrix was investigated by Ahmad Ramazani et al. (2008). In all these
ip
1225 investigations, it was generally concluded that there is synergy between the ATH and other
1226 additives (i.e. nanoclays, MDH and zinc borate) resulting in improved fire retardancy and
cr
1227 mechanical properties.
1228
us
1229 Magnesium dihydroxide (MDH) acts the same way as ATH except that its endothermic
1230 decomposition occurs at temperatures above 300 °C. This makes MDH an interesting
an
1231 additive with respect to extrusion and injection moulding processes of some polymers
1232 (Laoutid et al., 2009; Rothon & Hornsby, 1996).
1233 (1300 kJ/kg)
M
1234
1235 Its flame retardant action is effective up to 400 °C. Beyond this point, the exothermic
1236 character of degradation predominates. On decomposition, MDH may have a catalytic effect
d
1237 on the carbonized residues produced by combustion. This leads to an after glow effect, which
te
1238 could be cancelled by incorporating additional additives to acquire effective barrier formation
1239 (Focke et al., 2009; Laoutid et al., 2009).
p
1240
ce
1241 Various polymer matrices such as PP (Sain et al., 2004), EVA (Durin France et al., 2000;
1242 Laoutid et al., 2006; Qui et al., 2003; Ye et al., 2009) and unsaturated polyester resins (Tang,
1243 H. et al., 2013) have been compounded with MDH filler and their flammability and
Ac
1244 mechanical properties were investigated. Sain et al. (2004) studied the flammability of
1245 sawdust and rice husk filled PP with magnesium hydroxide combined with boric acid and
1246 zinc borate as flame retardant systems. MDH (25 wt.%) lowered the burning rate (using a
1247 horizontal burning test) of the composites by 50% relative to the untreated ones. It was
1248 further reported that there was no flame resistance synergy observed between MDH and other
1249 additives. Grexa and Lübke (2001) investigated the effect of magnesium hydroxide (type A)
1250 on the flammability properties of wood particle boards.This was compared to combinations
1251 of monoammonium phosphate with ATH (type B) and monoammonium phosphate with boric
40
Page 40 of 110
1252 acid (type C). The group reported decreased peak values of HRR (using a cone calorimeter)
1253 as a function of MDH content (see Figure 2, where A1, A2 and A3 = 8, 15 and 24 wt.%,
1254 respectively) showing the possibilityof improving the overall fire performance of wood
1255 particleboard using this flame retardant.
1256
t
ip
cr
us
an
M
1257
1258 Figure 2. HRR as a function of time for untreated and FR treated particleboard with the
1259 use of magnesium hydroxide. Reprinted from Grexa and Lübke (2001),
d
1260 Copyright 2001, with permission from Elsevier.

1261
te
1262 MDH nanoparticles have also been considered as flame retardant agents (Qui et al., 2003).
1263 They can be obtained by several methods including a solgel technique followed by a
p
1264 hypercritical drying procedure, hydrothermal reaction using various precursors and solvents,
ce
1265 or precipitation of magnesium salts with alkaline solution. This last method allows for the
1266 control of nanoparticles morphology by fine tuning of experimental parameters such as the
Ac
1267 chemical nature of a base used as precipitant, type of counterion, temperature as well as
1268 hydrothermal treatment. The use of nanometric MDH led to good fire performance at lower
1269 loading levels (Laoutid et al., 2009). This was also shown by Qui et al. (2003) who prepared
1270 and characterized MDH nanoparticles as flame retardant for EVA nanocomposites. They
1271 attributed this to good dispersion of the nanoparticles resulting in the formation of more
1272 compact and cohesive char during combustion tests (i.e. limiting oxygen index, LOI).
1273
1274 2.2.5.3 Borates
1275
41
Page 41 of 110
1276 Borates are another family of inorganic additives with flame retardance properties. The most
1277 frequently used borate is zinc borate (2ZnO·3B2O3·3.5H2O). It undergoes endothermic
1278 decomposition (503 kJ/kg) between 290 and 450 °C and liberates water (H2O), boric acid
1279 (H3BO3) and boron oxide (B2O3). Boron oxide softens at 350 °C and flows above 500 °C,
1280 leading to the formation of a protective vitreous layer. In the case of polymers with oxygen
t
1281 atoms, the presence of boric acid causes dehydration, leading to the formation of a carbonized
ip
1282 layer. This layer protects the polymer from heat and oxygen thus reducing the amount of
1283 released combustible gases (Durin France et al., 2000; Grexa and Lübke, 2001; Laoutid et al.,
cr
1284 2009; Pawlowski et al., 2010; Sain et al., 2004).
1285
us
1286 3. Flammability testing techniques
1287
an
1288 Flammability of polymers can be characterized by the ignitability, flame spread rate and heat
1289 release. A number of small, intermediate and/or full scale flammability tests are used in
1290 industrial and/or academic laboratories. They are used for either screening materials during
M
1291 production or testing manufactured products. This section discusses commonly used
1292 flammability testing techniques such as cone calorimetry, pyrolysis combustion flow
1293 calorimetry (PCFC), limiting oxygen index (LOI), underwriters’ laboratories (UL 94), and
d
1294 Ohio state university (OSU) heat release rate (Carvel et al., 2011; Horrocks, 2011; Price et
te
1295 al., 2001).

1296
p
1297 3.1 Cone calorimetry

ce
1298
1299 Cone calorimetry is a technique used to quantify the flammability of materials by
1300 determining various flammability parameters. It was first reported on by the National Bureau
Ac
1301 of Standards (NBS), now known as the National Institute of Standards and Technology
1302 (NIST), in 1982. This came after several attempts to design a reliable bench scale engineering
1303 device for measuring heat release rate (HRR). Although there were such tools already built
1304 for this purpose in the late 1970’s and early 1980’s by NBS and other institutions, none was
1305 appropriate for normal engineering laboratory use. It was during this time when the concept
1306 of oxygen consumption was developing and becoming familiar. From this concept, the
1307 successful bench scale heat release rate (HRR) apparatus was developed and the method was
1308 termed cone calorimetry. There were numerous improvements made on the cone calorimeter
1309 since its introduction. However, its basic principle has remained unchanged. The greatest
42
Page 42 of 110
1310 changes were introduced in 1987 with the inclusion of systems for measuring smoke optically
1311 and soot yield gravimetrically. Most other changes involved parts redesign for ease of use
1312 and reliability of operation (Babrauskas, 1993; Lindholm, Brink & Hupa, 2009; Wichman,
1313 2003). Figure 3 shows a picture of a cone calorimeter apparatus.
1314
t
ip
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1315 an
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1316 Figure 3. Cone calorimeter apparatus (from the Council for Scientific and Industrial
1317 Research (CSIR) fire testing laboratory).
d

1319
te
1320 Cone calorimetry is one of the most effective medium sized fire behaviour tests used to study
1321 the rate of heat released by materials exposed to radiant heat flux. Its principle is based on the
p
1322 measurement of decreasing oxygen concentration in the combustion gases of the sample that
ce
1323 is subjected to a given heat flux (10 to 100 kW m-2). It has been standardized in the United
1324 States (ASTM E 1354) and now in an international standard (ISO 5660) (Carvel et al., 2011;
Ac
1325 Guillaume et al., 2012; Laoutid et al., 2009; Wichman, 2003).

1326
1327 Figure 4 shows an experimental schematic representation of a cone calorimeter. A sample of
1328 100 mm x 100 mm dimensions is horizontally (occasionally vertically) placed in a sample
1329 holder on a load cell for evaluation of the mass loss during the experiment. The sample is
1330 aluminum foil wrapped on the sides and at the bottom. It is put in a retainer frame over low
1331 density ceramic wool and the retainer frame is secured to the specimen holder. A conical
1332 radiant electrical heater uniformly irradiates the sample from above, and combustion is
1333 triggered by an electrical spark. The combustion gases that are produced pass through the
43
Page 43 of 110
1334 cone and are removed by means of an exhaust duct system with a centrifugal fan and an
1335 extraction hood. The centrifugal fan is situated in the combustion gas line to set the flow rate
1336 of combustion products. Along the combustion gas line there is a gas sampling ring
1337 positioned before the fan. The gas sampled in the ring is first passed through two filters to
1338 remove particles. It is then passed through a cold trap and a drying agent to remove possible
t
1339 water. Finally it reaches the gas analyzers. Between the gas sampling ring and the fan there is
ip
1340 also a smoke measurement system. This system determines the amount of smoke produced
1341 using a laser photometric beam (Carvel et al., 2011; Guillaume et al., 2012; Laoutid et al.,
cr
1342 2009; Lindholm et al., 2009; Wichman, 2003).
1343
us
an
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d
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1344
1345 Figure 4. Schematic representation of an experimental set-up in a cone calorimeter.
p
1346 Reprinted from Babrauskas and Peacock (1992), Copyright 1992, with
ce
1347 permission from Elsevier.

1348
1349 To perform the basic cone calorimeter experiments, only an oxygen analyser is required.
Ac
1350 Furthermore, to better understand the burning process and minimize the uncertainties in the
1351 results, additional analyzers are usually fitted. These may be CO and CO2 analyzers. To
1352 further analyse combustion products and gaseous species, a Fourier transform infrared (FTIR)
1353 spectrometer can be coupled through a heated line (Lindholm et al., 2009).
1354
1355 The measurements of gas flow and oxygen concentration are used to calculate the quantity of
1356 heat released per unit of time and surface area (heat release rate, HRR) expressed in kW m-2.
1357 Development of HRR over time i.e. the value of its peak maximum (PHRR) or HRR
1358 maximum is considered in order to assess the fire properties of materials. The calculation of
44
Page 44 of 110
1359 HRR is based on Huggett’s observation in a study of the estimation of HRR via oxygen
1360 consumption measurements (Huggett, 1980). Huggett observed that most organic materials
1361 release an amount of heat that is practically proportional to the amount of oxygen consumed
1362 while burning. The proportionality factor is constant from one material to another and is
1363 equal to13.1 kJ g-1 consumed oxygen, with an accuracy of approximately 5%. Integration of
t
1364 the heat release rate (HRR) versus time curve gives the total heat release (THR) expressed in
ip
1365 MJ m-2 (Carvel et al., 2011; Guillaume et al., 2012; Laoutid et al., 2009; Wichman, 2003).
1366
cr
1367 Cone calorimetry, in addition to the aforementioned parameters, also enables the
1368 characterization of time to ignition (TTI), time to flame out (TFO), mass loss rate, levels of
us
1369 oxygen, carbon monoxide and carbon dioxide, and total smoke released (TSR). Furthermore,
1370 it provides more detailed fire characteristics, with HRR being the most widely used parameter
an
1371 for evaluating the fire properties. Some conditions, such as ignition and flammability of
1372 weakly reacting materials, conditions of low or fluctuating oxygen concentration, and
1373 variable material thickness and composition, pose difficulty for proper examination of
M
1374 samples (Carvel et al., 2011; Guillaume et al., 2012; Laoutid et al., 2009;Wichman, 2003).
1375 However, cone calorimetry is regarded as the most versatile medium sized fire testing method
1376 ever invented.
d
1377
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1378 3.2 Pyrolysis combustion flow calorimetry (PCFC)

1379
p
1380 Pyrolysis combustion flow calorimetry (PCFC) is a fire test method for evaluating the
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1381 combustibility of milligram sized samples. It is also known as microscale combustion

1382 calorimetry (MCC). This was originally developed by the Federal Aviation Administration
1383 (FAA) in the United States. The intent was to identify inherently fire resistant polymers for
Ac
1384 use in commercial air flights. Later on the FAA adopted the method to screen new polymers
1385 for heat release rate in flaming combustion. Recently, PCFC has been used to assess the
1386 flammability of flame retarded polymers. It is now a standardized technique classified as
1387 ASTM D7309-07 (Lyon & Walters, 2002, 2004; Lyon, Walters & Stoliarov, 2007a; Morgan
1388 & Galaska, 2008; Morgan, Wolf, Guliants, Shiral Fernando & Lewis, 2009; Schartel,
1389 Pawlowski & Lyon, 2007).
1390
1391 PCFC simulates the burning of a polymer solid. It separately reproduces the solid state and
1392 gas phase processes of flaming combustion in a nonflaming test. This is achieved by
45
Page 45 of 110
1393 controlled pyrolysis of the sample in an inert gas stream followed by high temperature
1394 oxidation of the volatile pyrolysis products. The heat of combustion of the pyrolysis products
1395 is measured by the use of oxygen consumption calorimetry. This method combines the
1396 constant heating rate and flow characteristics of thermal analysis (i.e. thermogravimetry) with
1397 the ability to determine the heat of combustion typical of oxygen bomb calorimetry.
t
1398 Nonetheless, PCFC determines the heat release and heat release rate using an oxygen
ip
1399 consumption method. Consequently, PCFC is more of a fire calorimetry parallel rather than a
1400 thermal analysis (Lyon & Walters, 2004; Schartel et al., 2007).
cr
1401
1402 The PCFC technique attempts to improve upon laboratory pyrolysis combustion methods by
us
1403 providing a dynamic capability for solids without the need to measure mass loss rate during
1404 the test. It helps in measuring the maximum specific heat release rate Qmax (HRR, W g-1) at a
(THR, J g-1), and
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1405 heating rate β, the total amount of heat release for complete combustion
1406 the temperature at maximum pyrolysis rate Tmax (°C) of polymers using only milligram
1407 samples. For polymeric materials that thermally decompose to fuel gases and possibly
M
1408 forming char in a single step, the pyrolysis temperature interval ∆Tp is given by equation 1:
1409 (1)
1410 where Ea (J mol-1) is the global activation energy for pyrolysis, e is the natural number and R
d
1411 is the gas constant. These combustion parameters help define a heat release capacity ηc
te
1412 (HRC, J g-1 K-1) given by equation 2:

1413 (2)
p
1414
ce
1415 The heat release capacity is the maximum potential of the material to release combustion heat
1416 in a fire. From the above derivation, the heat release capacity(ηc) is a combination of material
1417 properties, consequently, is itself a material property as measured in PCFC (Lyon & Walters,
Ac
1418 2005; Lyon et al., 2007a, b; Schartel et al., 2007). According to Schartel et al. (2007) the use
1419 of HRC as a measure of fire risk is based on the assumption that the maximum specific heat
1420 release rate at the decomposition temperature reached at constant heating rate correlates with
1421 the mass loss rate during pyrolysis in a fire characterized by a transient temperature gradient.
1422
1423 The apparatus construction and calibration method are well described by Lyon and Walters
1424 (2002, 2004) and its schematic representation is shown in Figure 5a. PCFC is based on linear
1425 programmed heating of milligram samples in an inert atmosphere to separate the solid and
46
Page 46 of 110
1426 gas phase processes of flaming combustion as would normally be the case in a fire situation
1427 (Morgan et al., 2009).
1428
1429 The principles of this technique are as follows: A solid sample is subjected to heating at a
1430 constant rate (β) of temperature rise under an inert (N2) gas flow. The heating goes to a
t
1431 maximum temperature (Tmax) and the sample is held at this maximum temperature for
ip
1432 between 10 and 120 s in order to stimulate pyrolysis. The volatile pyrolysis products
1433 generated during the temperature rise are removed from the pyrolyser by the nitrogen purge
cr
1434 gas, and O2 gas is added to the pyrolyzate/nitrogen gas stream at the inlet to the combustor.
1435 Combustion products such as carbon dioxide, water, and acid gases that exit the combustor
us
1436 are removed by the scrubbers, and the dry nitrogen and the residual oxygen pass through the
1437 flow meter and oxygen analyser. Deconvolution of the oxygen consumption signal is
an
1438 performed numerically during the test and the heat release rate, heat release capacity, and
1439 total heat of combustion are calculated and displayed. To determine the residual mass of the
1440 sample, the quartz tube is weighed after the test. Figure 5b shows the experimental setup of
M
1441 the PCFC in comparison with the flaming combustion of a polymer. This figure illustrates
1442 how the condensed phase (pyrolysis) and gas phase (combustion) processes of flaming
1443 combustion are separately reproduced in a nonflaming combustion test using the flaming
d
1444 polymer combustion as a reference (Lyon et al., 2007b; Lyon & Walters, 2002, 2004, 2005;
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1445 Morgan et al., 2009; Schartel et al., 2007).

1446
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1447
47
Page 47 of 110
1448 Figure 5 (a, b).Schematic representation of pyrolysis combustion flow calorimetry (PCFC):
1449 (a) basic section of the apparatus. Reprinted from Morgan et al. (2009),
1451 (b) Experimental set-up of the PCFC (left) in comparison with the flaming
1452 combustion of a polymer (right). Reprinted from Schartel et al. (2007),
t
ip
1454
1455 The total heat of combustion of the solid, as opposed to just the pyrolysis gases, can be
cr
1456 measured by switching the purge gas from nitrogen to air after the temperature ramp, or by
1457 using air as the purge gas during the ramp and hold cycles. Thus, selective thermooxidative
us
1458 degradation of the solid or char can be accomplished and the oxygen consumption can be
1459 measured to determine the heat of complete combustion since any residual organic material
an
1460 will be oxidized in air at a maximum temperature (Tmax) (Lyon & Walters, 2004).
1461
1462 The pyrolysis combustion flow calorimetry method has some advantages. This technique
M
1463 requires small sample size of 5 to 50 mg, ideal for research work giving small product yields
1464 during synthesis. When a sample is reacted in an air atmosphere, it can separate oxide
1465 forming reactions from nitride forming reactions. PCFC has the capability of separately
d
1466 measuring the combustion of volatile and nonvolatile components (Lyon & Walters, 2004).
te
1467
1468 3.3 Limiting oxygen index (LOI)
p
1469
ce
1470 Limiting oxygen index (LOI) is the minimum concentration of oxygen in a mixture of oxygen
1471 and nitrogen that is needed to support the flaming combustion of a material. It is expressed in
1472 volume percent (vol%). It was first introduced in 1966 by Fenimore and Martin (Lyon et al.,
Ac
1473 2007a; White, 1979). It is used to indicate the relative flammability of materials. It is
1474 standardized in the United States (ASTM D 2863) and in France (NF T 51-071), as well as
1475 internationally (ISO 4589). The principle of the method is that a sample is placed vertically
1476 within a controlled atmosphere and its top inflamed with a burner. LOI, the minimum
1477 concentration of oxygen in a mixture of oxygen and nitrogen that either maintains flame
1478 combustion of a material for 3 minutes or consumes a length of 5 cm of a sample, is
1479 expressed as:
1480 (3)
48
Page 48 of 110
1481 where [O2] and [N2] are the concentrations of oxygen and nitrogen gases, respectively.
1482 According to ISO 4589, LOI is measured on specimen (dimensions: 80 x 10 x 4 mm)
1483 vertically placed at the centre of a glass chimney as illustrated in Figure 6. A mixture of gases
1484 flows upstream via this chimney and is homogenized by passing through layers of glass
1485 beads. After 30 s purge of the column, the top of a specimen is ignited like a candle
t
1486 (Kandola, 2012; Laoutid et al., 2009; Wichman, 2003).
ip
1487
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us
an
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1488
d
1489 Figure 6. Schematic representation of a limiting oxygen index (LOI) test setup.
te
1490 Reprinted from Laoutid et al. (2009), Copyright 2009, with permission from
1491 Elsevier.
p
1492
ce
1493 As air contains 21% of oxygen, materials with LOI values less than this are classified as
1494 combustible, but those with LOI greater than 21 are classed as self extinguishing since their
1495 combustion cannot be sustained at ambient temperature without an external energy
Ac
1496 contribution. It therefore means that high LOI value materials generally exhibit a better flame
1497 retardant property. This method remains one of the most important screening and quality
1498 control tools in the plastics industry to characterize both the ignitability and flammability
1499 resistance. However, LOI measurements are taken at room temperature and LOI values
1500 decrease as temperature increases. This means that self extinguishing cannot be considered a
1501 fast rule since materials with high LOI values at room temperature may burn without self
1502 extinguishing under intense fire conditions. It should be noted that melting and dripping of a
1503 polymer during the LOI test may cause a specimen to extinguish and thus give misleading
1504 high LOI values. In addition, LOI has a limitation as a test for nanocomposites in that
49
Page 49 of 110
1505 organomodified nanoclay reinforced polymer nanocomposites exhibit decreased LOI values
1506 due to an increased flame spread rate over the surface of the specimen, while inside the
1507 material nanoclays form a barrier layer that limits the propagation of fire (Chapple &
1508 Anandjiwala, 2010; Kandola, 2001; Laoutid et al., 2009; Wichman, 2003).
1509
t
1510 The advantages of LOI are that it provides a convenient, reproducible means of determining a
ip
1511 numerical measure of flammability. Furthermore, the test equipment is inexpensive and only
1512 a small sample size is required for testing (Nelson, 2001).
cr
1513
1514 3.4 UnderwritersLaboratories 94 (UL94)
us
1515
1516 UL 94 is a set of tests approved by Underwriters Laboratories Inc. as flame tests for plastics
an
1517 materials for parts in devices and appliances. It includes a range of tests such as small and
1518 large flame vertical (V) tests, horizontal (H) tests for bulk and foamed materials, as well as
1519 radiant panel flame spread test. The commonly used test is UL 94 V in terms of practice and
M
1520 usage. It measures ignitability and flame spread of vertical bulk materials exposed to small
1521 flame. It is equivalent to international standard IEC 60695-11-10 (Test method B) for small
1522 flames (50W) and ASTM D3801-10 (Laoutid et al., 2009; Patel, Hull & Moffatt, 2012;
d
1523 Wang, Y., Zhang, Chen & Zhang, 2010).

te
1524
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ce
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1525
1526 Figure 7. Schematic representation of UL 94 vertical test. Reprinted from Laoutid et al.
1527 (2009), Copyright 2009, with permission from Elsevier.
50
Page 50 of 110
1528
1529 As shown in Figure 7, the burner is adjusted to produce a blue flame with 20 mm high central
1530 cone and a power of 50W. The flame is applied to the bottom of a specimen with the top of
1531 the burner located approximately 10 mm from the bottom edge of the specimen. The flame is
1532 applied for 10 s and removed, and the time required for flaming combustion to cease (after
t
1533 flame time) is noted as t1. After flaming combustion has ceased, the flame is applied for
ip
1534 another 10 s and after flame t2 is noted together with afterglow time t3. The distance between
1535 the burner and specimen must remain constant during flame application. If some drops fall
cr
1536 from the specimen, the burner is tilted to a maximum angle of 45° and slightly removed from
1537 the edge of the specimen. During the test, the presence of burning drops and any ignition of a
us
1538 piece of cotton placed under the specimen must be noted. The standard specification is that at
1539 least 5 specimens must be tested. The classification is made via V-0, V-1 and V-2 rating and
an
1540 criteria as shown in Table 3(Laoutid et al., 2009; Patel et al., 2012; Wang, Y., et al., 2010).
1541
1542 Table 3. UL-94 V ratings and criteria. Reprinted from Patel et al. (2012), Copyright
M
1543 2011, with permission from John Wiley and Sons.
Sample classified to the following criteria V-0 V-1 V-2
After flame time for each individual specimen t1 or t2 ≤10 s ≤30 s ≤30 s
d
Total after flame for any set (t1 plus t2 for five specimens) ≤50 s ≤250 s ≤250 s
te
After flame/glow time for each specimen after second ≤30 s ≤60 s ≤60 s
application (t1 + t3)
p
After flame glow of any specimen up to clamp No No No

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Cotton indicator ignited by flaming drips No No Yes

1544 s stands for seconds
1545
Ac
1546 The UL 94 test is widely used both in industry and academic research centres. It is intended
1547 to meet industrial requirements as well as classify polymeric materials hierarchically. The
1548 information obtained remains limited due to its basic and unrefined character. For specimens
1549 that flow, the test seems less appropriate than for more cohesive materials (Laoutid et al.,
1550 2009; Patel et al., 2012; Wang, Y., et al., 2010).
1551
1552 3.5 Ohio State University heat release apparatus (OSU)
1553
51
Page 51 of 110
1554 The OSU is a technique developed to describe how a material burns. It is a quantitative
1555 method of analysis that was available in its basic form in the early 1970’s. The technique is
1556 used to measure the rate of heat release (RHR) of materials and products in a forced flaming
1557 combustion. Originally RHR is determined by measuring the temperature change (∆T) of a
1558 constant mass flow of air (ma) through the apparatus caused by the heat released from the
t
1559 burning sample. The change in enthalpy of the air is calculated using the usual relation:
ip
1560 (4)
1561 where cp is the heat capacity of air (Smith, 1996).
cr
1562
1563 The fundamental principles of the OSU heat release apparatus are outlined in the Federal
us
1564 Aviation Administration (FAA), FAR 25.853 (ASTM E906/E906M-10, 2010) and American
1565 Society of Testing and Materials (ASTM), ASTM E906
an
1566 (http://www.flightsimaviation.com/data/FARS/part_25-appF4.html ;
1567 http://www.astm.org/Standards/E906.htm ) test methods.This apparatus is used in two
1568 configurations A and B. Configuration A is used by FAA under the designation FAR 25.853
M
1569 as a regulatory tool in determining the fire properties of aircraft interior cabin materials. The
1570 FAA requirements are exclusively based on heat release. In order for a material to satisfy the
1571 requirements it must have an average maximum heat release of < 65 kW m-2, during 5
d
1572 minutes of the test and an average total heat release of < 65 kW min m-2 within the first 2 min
te
1573 of the test, when the incident heat flux is set at 35 kW m-2 (Hirschler, 2000;
1574 http://www.fire.tc.faa.gov/pdf/handbook/00-12_ch5-0909.pdf ). Configuration B, under the
p
1575 designation ASTM E906, is intended for use in research and development and not as a basis
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1576 for rating, regulatory, or code purposes. Figure 8 shows the OSU rate of heat release
1577 apparatus (http://www.fire-testing.com/astm-e-906-osu).
1578
Ac
1579 In the standard method (ASTM E906, configuration B), the OSU determines the rate of heat
1580 release (RHR) (also heat release rate, HRR) of a material from the sensible enthalpy
1581 (temperature) rise of the air. The specimen is injected into an environmental chamber through
1582 which a constant flow of air passes. The specimen’sorientation varies from vertical
1583 (configuration B) to horizontal (configuration A). The air flows past a 150 mm x 150 mm
1584 specimen with maximum thickness of 45 mm. The OSU monitors the temperature difference
1585 between the air entering and exiting the environmental chamber by a thermopile. The
1586 specimens of materials or products are exposed to different levels of radiant heat at incident
52
Page 52 of 110
1587 fluxes up to 100 kW mm-2. Combustion is initiated by piloted ignition. The combustion
1588 products leaving the chamber are monitored and the change in temperature (enthalpy) due to
1589 theseis used to calculate the rate of heat release(Hirschler, 2000;
1590 http://www.fire.tc.faa.gov/pdf/handbook/00-12_ch5-0909.pdf;http://www.fire-
1591 testing.com/astm-e-906-osu).
t
1592
ip
1593 Numerous modifications had been proposed to the OSU technique (Tran, 1988, 1990; Tran &
1594 White, 1992). This was because the standard thermal mode had some errors caused by the
cr
1595 heat losses that were not accounted for, as well as the fact that the mass flow rate is
1596 controlled (White & Dietenberger, 1999). Consequently the oxygen consumption mode was
us
1597 put in place in addition to the standard thermal mode within the OSU apparatus. For example,
1598 Tran and White (1992) modified OSU with the aim to improve its accuracy during the
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1599 investigation of the burning characteristics of wood. They used four ways in this regard: a)
1600 addition of oxygen consumption calorimetry, b) addition of an auxiliary heat flux meter, c)
1601 gas phase piloted ignition of the sample, and d) a mass loss determining system using an
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1602 injection shaft as a lever. According to Tran (1990), the common finding was that the HRR
1603 measurements obtained by the OSU standard thermal mode are lower than those obtained by
1604 the OSU oxygen consumption method in the same apparatus, despite some differences in the
d
1605 way gas samples are taken. The oxygen consumption mode is based on the fact that the
te
1606 quantity of net heat released by complete combustion per unit of oxygen consumed is almost
1607 constant over a wide range of materials (i.e. 13.1 kJ/g) (Huggett, 1980; Tran, 1988). It is
p
1608 through measuring the quantity of oxygen consumed that the amount of heat release is
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1609 calculated. The heat release rate (HRR) measured through OSU and cone calorimeter were
1610 investigated and compared in some studies (Filipczak, Crowley & Lyon, 2005; Tran, 1990).
1611 The general conclusion made by Tran (1990) was that there is some agreement of the HRR
Ac
1612 results from these two different test methods when a modified OSU was used. However, the
1613 HRR results from these two test methods did not agree in most cases according to Filipczak
1614 et al. (2005), who used single ply fibre glass reinforced epoxy thin composite materials.
1615
53
Page 53 of 110
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ip
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1616
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1617 Figure 8. Ohio State University heat release (OSU) apparatus. Reprinted from
1618 http://www.fire-testing.com/astm-e-906-osu , with permission from Fire
1619 Testing Technology Limited.
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1621
1622 The other modification is that of determining the smoke release rate. This is done by an
d
1623 optical method, with a white light source and a photo detector fitted above the exhaust stack
te
1624 close to the thermopile (Hirschler, 2000). Both heat and smoke release are measured from the
1625 moment the specimen is injected into a controlled exposure chamber. Measurements are
p
1626 continued during the period of ignition and to such a time that the test is terminated.
ce
1627
1628 Although the OSU heat release apparatus is a good tool for flammability testing, there are
1629 known limitations of this test method (Hirschler, 2000; ASTM E906/E906M-10, 2010):
Ac
1630 The heat and smoke release depend on several factors such as formation of surface
1631 char, formation of adherent ash, sample thickness, and method of mounting.
1632 Heat release values are a function of the exposed tested area of the specimen.
1633 The test method is restricted to the specified specimen size of materials, products or
1634 assemblies. In the case of products, the test specimen (i.e. prototype) is representative
1635 of the product in actual size.
1636 At very high specimen heat release rates, flaming above the stack is possible making
1637 the test invalid.
54
Page 54 of 110
1638 There is no established general relationship between heat release rate values obtained
1639 from horizontally and vertically oriented specimens. Specimens that melt and drip in a
1640 vertical position are tested horizontally.
1641 Vertical testing remains a problem for testing thermoplastic materials in the OSU.
1642 Moreover, the reflector used for horizontal testing leads to serious reproducibility
t
1643 errors in the heat flux input to the horizontal sample.
ip
1644
1645 Other analytical techniques including thermogravimetric analysis (TGA), differential thermal
cr
1646 analysis (DTA) and differential scanning calorimetry (DSC) are useful in broadening the
1647 understanding of the response of different materials under fire circumstances. Furthermore,
us
1648 TGA coupled with FTIR is also a useful tool for identifying gases being emitted during the
1649 thermal decomposition process. For example, TGA provides valuable information on char
an
1650 residue that remains after thermal degradation of a material, which helps clarify some flame
1651 retardancy mechanisms that are based on the formation of a protective char and/or vitreous
1652 layer by different materials (i.e. intumescent flame retardants). DTA aids at giving the
M
1653 amount of heat liberated or absorbed by materials during any physical transition or chemical
1654 reaction. Consequently, it is useful in measuring heat capacity, provides kinetic data, and
1655 gives transition temperatures. Similarly, DSC provides information on enthalpies of various
d
1656 transitions and chemical reactions (Rowell & Dietenberger, 2013).

te
1657
1658
p
1659 4. Flammability of biofibres and biocomposites

ce
1660
1661 The properties of biofibre (natural fibre) reinforced biocomposites have been reviewed by
1662 numerous authors. This section is divided into three subsections, namely, flammability
Ac
1663 studies on biofibres, biopolymers and biofibre reinforced biopolymer composites (Bourbigot
1664 & Fontaine, 2010; Chapple & Anandjiwala, 2010; Kandola, 2012; Kozlowski &Wladyka-
1665 Przybylak, 2008; Price et al., 2001).
1666
1667 4.1 Biofibres (natural fibres)
1668
1669 Biofibres are natural lignocellulosic composites composed of highly crystalline spirally
1670 wound cellulose fibrils embedded in an amorphous hemicellulose, lignin, pectin and wax
1671 matrix (Kandola, 2012). They have rounded and elongated structures with hollow cross
55
Page 55 of 110
1672 sections spread over the whole plant (Zavareze & Dias, 2012). Generally, their composition
1673 consists of cellulose, lignin, hemicellulose, pectin and wax. Depending on their origin, they
1674 may be classified as plant, animal, and minerals based. The minerals based fibres (e.g.
1675 asbestos) are scarcely used due to their negative effects on health. The examples of animal
1676 based fibres are wool, hair and silk. Table 4 gives the list of examples of important plant
t
1677 based natural fibres, which may be classified according to the anatomical origin such as stem,
ip
1678 leaf, wood and fruit. There is plenty of published literature on natural fibres and its
1679 composites based either on thermoplastics, thermosets or biopolymers as composites matrices
cr
1680 (Faruk et al., 2012; John & Thomas, 2008; Sahari & Sapuan, 2011; Satyanarayana et al.,
1681 2009; Zavareze & Dias, 2012).
us
1682
1683 Biofibres offer numerous advantages such as energy efficiency, low cost, low density, high
an
1684 toughness, appreciable specific strength and biodegradability. However, they are hydrophilic
1685 in nature and have poor fire resistance. These disadvantages limit their application in outdoor
1686 panels (i.e. construction) and in areas that pose fire hazard to humans (i.e. aerospace and
M
1687 marine) (Grexa, Poutch, Manikova, Martvonova, & Bartekova, 2003).
1688
1689 Biofibres are non-thermoplastic materials and their thermal degradation temperature is less
d
1690 than their glass transition (Tg) and/or melting (Tm) temperatures. When natural fibres are
te
1691 exposed to fire or a high intensity heat source, they are subject to thermal decomposition and
1692 combustion depending on prevailing conditions. Conditions such as direct contact with air
p
1693 and physical, chemical and microbiological stimuli associated with heat release can make the
ce
1694 combustion of natural fibres possible. In addition, the intensity of heat stimulus, oxygen
1695 concentration and circulation around the combustion area, as well as the intensity of the
1696 combustion process, influence the time to ignition (TTI) of natural fibres. The thermal
Ac
1697 degradation of plant fibres involves a number of processes: a) dehydration of adsorbed water
1698 molecules; b) depolymerisation and decarboxylation of cellulose chains with evolution of
1699 water to form dehydrocellulose; c) decomposition of formed dehydrocellulose to yield char
1700 and volatiles; d) formation of levoglucosan (an intermediate nonvolatile liquid product); and
1701 e) decomposition of the levoglucosan to yield lower molecular weight and highly flammable
1702 volatiles as well as nonflammable volatiles and gases, tar and char (Chapple & Anandjiwala,
1703 2010; Kandola, 2012).
1704
56
Page 56 of 110
1704
1705 Table 4. List of important biofibres. Reprinted from John and Thomas (2008),
Fibre source Species Origin
Abaca Musa textilis Leaf
Bagasse – Grass
t
Bamboo (>1250 species) Grass
ip
Banana Musa indica Leaf
Broom root Muhlenbergia macroura Root
Cantala Agave cantala Leaf
cr
Caroa Neoglaziovia variegata Leaf
China jute Abutilon theophrasti Stem
us
Coir Cocos nucifera Fruit
Cotton Gossypium sp. Seed
Curaua Ananas erectifolius Leaf
Date palm Phoenix Dactylifera Leaf
an
Flax Linum usitatissimum Stem
Hemp Cannabis sativa Stem
Henequen Agave fourcroydes Leaf
M
Isora Helicteres isora Stem
Istle Samuela carnerosana Leaf
Jute Corchorus capsularis Stem
d
Kapok Ceiba pentranda Fruit

Kenaf Hibiscus cannabinus Stem
te
Kudzu Pueraria thunbergiana Stem

Mauritius hemp Furcraea gigantea Leaf
Nettle Urtica dioica Stem
p
Oil palm Elaeis guineensis Fruit

ce
Piassava Attalea funifera Leaf

Pineapple Ananus comosus Leaf
Phormium Phormiumtenas Leaf
Roselle Hibiscus sabdariffa Stem
Ac
Ramie Boehmeria nivea Stem

Sansevieria (Bowstring hemp) Sansevieria Leaf
Sisal Agave sisilana Leaf
Sponge gourd Luffa cylinderica Fruit
Straw (Cereal) – Stalk
Sun hemp Crorolaria juncea Stem
Cadillo/urena Urena lobata Stem
Wood (>10,000 species) Stem
1707
57
Page 57 of 110
1708 These processes occur during the course of the three stages of heat action on natural fibres
1709 and natural polymers as detailed by Kozlowski and Wladyka-Przybylak (2001), i.e.
1710 preliminary flameless stage, followed by main flame stage and then the final flameless stage.
1711 Generally, these stages may be briefly described as follows:
1712 Preliminary stage involves dehydration (up to 105 °C) and release of liquid and
t
1713 volatiles, and further heating of natural fibre leads to their decomposition temperature. At this
ip
1714 stage, reactions are slow and endothermic. Above 105 °C, the fibre components begin to
1715 decompose with gaseous products being released within the temperature range of 150 to 200
cr
1716 °C. The bonds between natural fibre components become weak.
1717 The main flame stage includes ignition of thermal decomposition products, flame
us
1718 spread by combustible gases and increase in heat release and mass loss rates. This is an active
1719 process of decomposition occurring in the temperature range of 260 to 450 °C.
an
1720 The final flameless stage includes the slow burning of residue and the formation of
1721 ash from the remaining matter, which occurs above 500 °C.
1722
M
1723 The mechanism of thermal degradation of plant fibres may be similar from a
1724 thermogravimetric analysis point of view. However, the flammability behaviour of plant
1725 fibres is different. This is motivated by factors such as chemical composition, fine structure,
d
1726 degree of polymerization and fibrillar orientation. The decomposition of the major
te
1727 constituents (cellulose, hemicellulose and lignin) making up the natural fibre may be
1728 described as follows:
p
1729 Lignin: begins to decompose in the temperature range of 160 to 400 °C. At lower
ce
1730 temperatures, relatively weak bonds break, whereas at higher temperatures phenols result
1731 from cleavage of ether and carbon-carbon linkages. This results into more char than in the
1732 case of either cellulose or hemicellulose. Lower lignin content in natural fibre contributes to
Ac
1733 higher decomposition temperatures but lower resistance to oxidation which would be
1734 provided by the aromatic structure of lignin.
1735 Hemicellulose: decomposition of these low molecular weight polysaccharides begins
1736 at 180 °C releasing more incombustible gases and fewer tar substances. Released gases
1737 usually contain 70% of incombustible CO2 and about 30% of combustible CO. Depending on
1738 the availability of oxygen, subsequent reactions may be exothermic or endothermic. Between
1739 200 and 260 °C, exothermic reactions start and are characterized by increased emission of
1740 gaseous products of decomposition, release of tar substances and the appearance of local
58
Page 58 of 110
1741 ignition areas of hydrocarbons with low boiling points. No spontaneous ignition at these
1742 temperatures may occur, but under favourable conditions ignition can start from a pilot flame.
1743 Cellulose: decomposes in the temperature range of 260 to 350 °C, primarily yielding
1744 flammable volatiles and gases, noncombustible gases, tars as well as some char. The thermal
1745 degradation of cellulose can be catalysed in the presence of water, acids and oxygen.
t
1746 Consequently, natural fibres turn brown and a carbonaceous char (pyrophoric carbon) is
ip
1747 formed. The reaction below 260 °C is still low. High contents of cellulose are likely to
1748 increase flammability of a fibre whereas high contents of lignin are likely to reduce it
cr
1749 (Chapple & Anandjiwala, 2010; Kandola, 2012; Kozlowski and Wladyka-Przybylak, 2001).
1750
us
1751 The fine structure of the fibre also plays a role in influencing the flammability characteristics
1752 of a fibre. Fibres rich in cellulose have high levels of crystallinity. This results in high levels
an
1753 of levoglucosan during pyrolysis leading to increased flammability. Additionally, this
1754 increased level of crystallinity requires more activation energy (Ea) of the pyrolysis of
1755 cellulose to decompose the crystalline structure, consequently leading to higher ignition
M
1756 temperatures (Chapple & Anandjiwala, 2010; Lewin, 2005).
1757
1758 The degree of polymerization and fibrillar orientation also dictate the fibre flammability.
d
1759 Increased degree of polymerization and orientation results in decreased pyrolysis. Fibrillar
te
1760 orientation controls the quantity of oxygen that can penetrate into the fibre, thus the higher
1761 the orientation, the lower the permeability of the fibre to oxygen (Chapple & Anandjiwala,
p
1762 2010; Lewin, 2005). In their review on the flammability of natural fibre reinforced
ce
1763 composites and strategies for fire retardancy, Chapple and Anandjiwala (2010) made an
1764 important conclusion that, from a flammability perspective, natural fibres with low
1765 crystallinity, high degree of polymerization and high fibrillar orientation would be the best
Ac
1766 choice to use as reinforcement in composite materials.

1767
1768 The flammability properties of natural fibres were reported (Chai, Bickerton, Bhattacharyya
1769 & Das, 2012; Grexa & Lübke, 2001; Grexa et al., 2003; Hapuarachchi & Peijs, 2010; Jang et
1770 al., 2012; Kandola & Horrocks, 2000; Lazko et al., 2013; Reti et al., 2009; Sain et al., 2004),
1771 and mostly the biofibres were compounded with different polymer matrices [i.e. poly(lactic
1772 acid) (PLA), polypropylene (PP) and epoxy resin] in the presence of flame retardants. In
1773 some studies, fibres alone were treated with flame retardants and characterized. The different
1774 flame retardant additives used for lignocellulosic materials include ammonium salts of
59
Page 59 of 110
1775 phosphoric acid (i.e. melamine phosphate, ammonium polyphosphate), boric acid, zinc
1776 chloride, zinc borate, salts of sulphuric acid, vermiculite, magnesium hydroxide,
1777 aluminumhydroxide, expandable graphite and pentaerythritol (as the carbon source for
1778 intumescent systems) (Durin France et al., 2000; Grexa & Lübke, 2001; Grexa et al., 2003;
1779 Kandola & Horrocks, 2000; Lazko et al., 2013; Reti et al., 2009). The preparation of flame
t
1780 retardant treated natural fibres is achieved in different ways including a) impregnation of
ip
1781 fibres with a solution of the flame retardant, b) incorporation of the flame retardant into the
1782 adhesive system, c) surface treatment of the fibres, and d) mixing of the fibres with the flame
cr
1783 retardant before the addition of an adhesive (e.g. melamine urea formaldehyde condensate,
1784 pea protein) (Grexa & Lübke, 2001; Grexa et al., 2003; Lazko et al., 2013).
us
1785
1786 Grexa and Lübke (2001) and Grexa et al. (2003) reported on the flammability of
an
1787 lignocellulosic particleboard using a cone calorimeter. In both studies, samples were
1788 conditioned to equilibrium at 55% relative humidity (RH) and 23 °C prior to testing. In the
1789 first study (Grexa & Lübke, 2001), the authors looked at the effect of magnesium hydroxide
M
1790 loading and that of other flame retardants (i.e. monoammonium phosphate (MAP), aluminum
1791 hydroxide and boric acid), whereas in the second study (Grexa et al., 2003) they dealt with an
1792 intumescent system for wood based panels. The RHR (see Figure 2, section 2.2.5.2), average
d
1793 specific extinction area of smokeand the rate of smoke release (Figure 9) were generally
te
1794 improved with increasing amount of magnesium hydroxide flame retardant (type A) [where
1795 A1, A2 and A3 are 8, 15 and 24 wt.% respectively]. In addition to smoke production
p
1796 improvement, carbon monoxide yield was also improved due to this flame retardant (Grexa &
ce
1797 Lübke, 2001).

1798
1799
Ac
1800
1801
60
Page 60 of 110
t
ip
cr
us
1802
1803 Figure 9. Smoke production rate versus time for non-treated and magnesium hydroxide-
an
1804 treated particleboard. Reprinted from Grexa and Lübke (2001), Copyright
1805 2001, with permission from Elsevier.
1806
M
1807 Furthermore, when different flame retardant combinations [i.e. monoammonium phosphate
1808 (MAP) 17wt.% + aluminium hydroxide 8wt.% (type B), and MAP 20wt.% + boric acid
d
1809 5wt.% (type C)] were used and compared, the authors concluded that the combination of
1810 MAP/boric acid (type C) was the most effective system. As seen in Figure 10, the type C
te
1811 flame retardant system did not only lower the RHR, but also eliminated the second peak and
1812 shortened the time of burning with respect to other modifications including magnesium
p
1813 hydroxide. The mass loss was reduced for the flame retardant treated systems, especially type
ce
1814 C (i.e. from 72% to 17%), but the mass loss rate was almost the same for all the studied
1815 materials. In this study, the authors distinguished between the yield of CO and the production
1816 of CO, and they concluded that the stronger retardant effect may give better results on the
Ac
1817 total CO production than the weaker retardant effect, even though the CO yield per burned
1818 portion of the pure material increased (Grexa & Lübke, 2001).
1819
1820 In the second study (Grexa et al., 2003) ammonium phosphate and expandable graphite
1821 intumescent flame retardant systems formed a protective char layer on the surface of wood.
1822 Similar to the previous study (Grexa & Lübke, 2001), the RHR was reduced to about 55-66%
1823 of the untreated material. The time to ignition (TTI) remained unchanged with the presence
1824 of the flame retardant, and authors concluded that the flammable particles of wood on the
61
Page 61 of 110
1825 surface were not directly protected. The intumescent flame retardant system based on
1826 expandable graphite showed better flammability performance at low loadings than the
1827 phosphate based systems, which required high contents (i.e. 30 wt.%). This was explained in
1828 terms of the difference in the presence of the expanding charring foam layer on the pyrolysis
1829 surface. The other important aspect is that CO emissions increased for expandable graphite at
t
1830 the lowest loadings, and increased noticeably for the phosphate based system at 13 wt.% and
ip
1831 higher.
1832
cr
us
an
M
d
1833
te
1834 Figure 10. HRR versus time for untreated and flame retardant treated particle board with
1835 the use of different flame retardant combinations. Reprinted from Grexa and
p
1836 Lübke (2001), Copyright 2001, with permission from Elsevier.

1837
ce
1838 The flammability properties of flax fibres were investigated by Lazko et al. (2013). They
1839 used a wet process to prepare the flame retarded insulating agro materials made of flax short
Ac
1840 fibres with a pea protein binder. It was reported that the incorporation of different flame
1841 retardants [i.e. aluminum hydroxide (ATH), zinc borate (ZB), melamine phosphate (MMP)
1842 and melamine borate (MMB)] did not interfere with the expanded structure and the open
1843 porosity of the lignocellulosic matrix. This was shown by macroscopic and SEM results (see
1844 Figure 11). Two conclusions arose from these: a) the appropriate choice of process
1845 parameters allowed a coherent set of materials with comparable morphologies and densities,
1846 and b) the use of a pea protein binder permitted all flame retardants to be fixed firmly and
1847 permanently onto the flax fibre matrix. The presence of FRs lowered the flexural strength by
1848 50% and the flexural modulus by 65% (see Table 5), except for ATH, for which the
62
Page 62 of 110
1849 properties remained at the same levels as the reference. Different flax fibre flame retardant
1850 treatments led to lowered peak and total HRR (especially for ZB, MMP and MMB) relative
1851 to the untreated flax short fibres. Similar to studies by Grexa et al. (2003), the TTI remained
1852 unchanged including the resistance to ignition.
1853
t
1854 Table 5. Density and flexural properties of non FR treated flax short fibres with pea
ip
1855 protein binder (i.e. reference) and FR treated materials. Reprinted from Lazko
1856 et al. (2013), Copyright 2013, with permission from Elsevier.
cr
Composition Density [g/cm3] Flexural strength [MPa] Flexural modulus [MPa]
Reference 0.07 ± 0.01 0.34 ± 0.02 14.4 ± 2.5
us
ATH 20% 0.09 ± 0.01 0.39 ± 0.03 15.8 ± 6.6
ZB 20% 0.07 ± 0.01 0.18 ± 0.04 5.3 ± 1.9
MMP 20% 0.08 ± 0.01 0.21 ± 0.03 5.8 ± 2.6
MMB 20% 0.07 ± 0.01 0.15 ± 0.03 4.2 ± 1.4
an
1857
1858
M
d
p te
ce
Ac
63
Page 63 of 110
t
ip
cr
us
an
M
d
p te
ce
Ac
1859
1860 Figure 11. Macroscopic and SEM pictures (x200) of a) reference (untreated flax fibre),
1861 and flame retardant treated flax (fibre and pea protein binder) containing 20
1862 wt.% of b) ATH, c) ZB, d) MMP and e) MMB. Reprinted from Lazko et al.
64
Page 64 of 110
1865 In their study of sawdust and rice husk filled polypropylene (PP) composites, Sain et al.
1866 (2004) used magnesium hydroxide, boric acid and zinc borate as flame retardant agents. The
1867 composites were melt blended and then injection moulded in the presence of a maleated PP
1868 coupling agent. It was reported that magnesium hydroxide (i.e. 25 wt.%) effectively reduced
1869 the flammability of natural fibre/PP composites by 50% when tested using horizontal burning
t
1870 and LOI tests. The partial replacement of magnesium hydroxide with either boric acid or zinc
ip
1871 borate (i.e. 5 wt.%) did not show synergy, but rather the retarding effect of different flame
1872 retardants. A marginal decrease in the mechanical properties of flame retarded natural fibre
cr
1873 composites compared to non-flame retarded composites was reported. This was attributed to
1874 the poor compatibility of the flame retardants with the polymer. However, better mechanical
us
1875 properties were observed for these composites with respect to neat PP.
1876
an
1877 A large number of studies focused on the FR properties of natural fibre based fabrics (Abou-
1878 Okeil, El-Sawy & Abdel-Mohdy, 2013; Alongi & Malucelli, 2012; Alongi, Brancatelli &
1879 Rosace, 2012b; Alongi, Ciobanu & Malucelli 2011, 2012a; Alongi et al., 2013; Bosco et al.,
M
1880 2013; Chai et al., 2012; Didane, Giraud & Devaux, 2012; Flambard et al., 2005; Kandola &
1881 Horrocks, 2000; Laufer, Kirkland, Morgan & Grunlan, 2012; Nguyen, Chang, Condon,
1882 Uchimiya & Fortier, 2012; Šimkovic, 2012; Wang, L., Zhang, Yan, Peng & Fang, 2013;
d
1883 Yang, Wang, Lei, Fei & Xin, 2012;). Chai et al. (2012) used flax based fabrics reinforced
te
1884 epoxy resin and compared them with glass fibre reinforced epoxy composites of similar
1885 fabric architecture. These composite panels were prepared by a resin transfer moulding
p
1886 (RTM) process without any FR. The group reported, from cone calorimetry, horizontal and
ce
1887 vertical burning tests, that the flax fibre samples ignited earlier, released more heat overall,
1888 had an increased time to extinguish and increased smoke production rate (SPR) when
1889 compared to their glass fibre counterparts. This was attributed to a number of reasons,
Ac
1890 amongst others that flax fibres are themselves susceptible to ignition and combustion, that
1891 they provided additional fuel at a lower HRR, that fibres combusted exothermically, and that
1892 they burned more vigorously during combustion.
1893
1894 Additionally, flax fibre samples showed deformation during combustion while glass fibre
1895 samples kept their integrity. It was postulated that the bulging and delamination effect of the
1896 flax fibre composites (see Figure 12) may be due to internal or external forces applied to the
1897 fibres, causing buckling. The authors, therefore, suggested further investigations to
65
Page 65 of 110
1898 understand the mechanisms and behaviour that govern the combustion of natural fibre
1899 reinforced composites.
1900
t
ip
cr
us
1901
1902 Figure 12. Images of (a) flax twill weave in a cone calorimeter, and (b) a burnt flax
an
1903 unidirectional fabric sample. Reprinted from Chai et al. (2012), Copyright
1904 2012, with permission from Elsevier.
M
1906
1907 Kandola and Horrocks (2000) looked at the nonwoven cores of flame retardant
d
1908 cellulose/regenerated cellulose (viscose and cotton fibres) with intumescent melamine and
1909 phosphate based chemicals. They investigated the mass loss and thermal barrier properties of
te
1910 these systems. A large quantity of char formation was observed above 500 °C. This was
1911 resistant to oxidation and had better thermal insulative properties. The presence of
p
1912 intumescent FR led to increased activation energy (Ea) values for the full char development
ce
1913 stage of FR/cellulosic fibre composites, and reduced thermal conductivity values. According
1914 to the authors, this revealed the existence of an interaction between different FRs and the
Ac
1915 fibre substrate, and improved thermal barrier properties. Flambard et al. (2005) used wool,
1916 flax and blends made of poly(p-phenylenediamineterephthalamide) (PPTA) with wool in
1917 textile materials for use in public transportation (i.e. buses). They studied the flame
1918 retardancy properties of these materials. The group concluded that these natural fibres could
1919 be used to manufacture fabrics that are acceptable for use in seats for transportation when
1920 they are combined with a specific flame retardant treatment or in combination with high
1921 performance fibres (wool/PPTA). The advantages offered by these materials included good
1922 flammability and mechanical properties (abrasion and cutting resistance), dyeability and
66
Page 66 of 110
1923 ultraviolet (UV) resistance, biodegradability and no technological problems during
1924 manufacture.
1925
1926 In some studies,fabric materials were generally surface coated with either commercial or
1927 laboratory synthesized flame retardants (AbouOkeil et al., 2013; Didane et al., 2012; Laufer
t
1928 et al., 2012; Nguyen et al., 2012; Šimkovic, 2012; Wang, L. et al., 2013; Yang et al., 2012).
ip
1929
1930 Abou-Okeil et al. (2013), Nguyen et al. (2012) and Yang et al. (2012) developed
cr
1931 environmental friendly halogen free and formaldehyde free FRs which were subsequently
1932 applied onto cotton fabrics and evaluated for flammability performance. These were
us
1933 methacryloyloxyethylorthophosphorotetraethyl diamidate (MPD) (Abou-Okeil et al., 2013),
1934 novel halogen and formaldehyde free flame retardants (NeoFR) (Yang et al., 2012) and
an
1935 phosphorus-nitrogen bond (diethyl 4-methylpiperazin-1-ylphosphoramidate) (CN-3) (Nguyen
1936 et al., 2012) FR compounds. In the first two studies (Abou-Okeil et al., 2013; Yang et al.,
1937 2012), the performance of the novel FRs was compared with that of a commercial flame
M
1938 retardant (Pyrovatex), and it was concluded that the novel FRs were performing better in
1939 terms of flammability and durability than the latter. NeoFR was said to have played the role
1940 of an intumescence on the flame retarding mechanism of cotton. This was due to its ability to
d
1941 form char. Higher tensile strength and elongation were also reported (Yang et al., 2012).
te
1942 Similarly, better flame retardant properties were observed by Nguyen et al. (2012) when
1943 print-on and twill fabrics were treated with a CN-3 flame retardant. At certain loadings the
p
1944 char lengths of the FR treated fabrics were less than 50% of the original fabric with no after-
ce
1945 flame and after-glow times. The LOI values increased from 12 vol.% (print cloth) and 18
1946 vol.% (twill) to 28 vol.% and 29-31 vol.% respectively. In general, the improvement of
1947 flammability properties of cotton fabrics emphasized the role played by char formation for
Ac
1948 treated samples which prevented them from being completely burnt.
1949
1950 Extensive work on developing novel systems based on a sol-gel process for cotton based
1951 fabrics was done by Alongi and co-workers (Alongi et al., 2011, 2012a, b, 2013; Alongi &
1952 Malucelli, 2012; Bosco et al., 2013). These flame retardant finishing systems were developed
1953 in the presence of different FR compounds. The FRs were phosphorus based compounds
1954 (Alongi et al., 2011), metal alkoxide precursors (e.g. tetraethylorthosilicate, titanate,
1955 zirconate, and aluminium isopropylate) (Alongi et al., 2012a), polyhedral oligomeric
1956 silsesquioxane (POSS) and bohemite nanoparticles (Alongi et al., 2012b), and compounds
67
Page 67 of 110
1957 with smoke suppressant features (e.g. zinc oxide, zinc borate) or flame retardant properties
1958 (e.g. 9-oxa-10-phosphaphenanthrene10-oxide) (Alongi & Malucelli, 2012). The fabric
1959 exhibited improved flammability and thermooxidative stability. This was attributed to several
1960 factors including the homogeneous distribution and dispersion of FR additives on and in
1961 between the cotton fibres (Alongi et al., 2011), the morphology of the inorganic coatings on
t
1962 the fabric surface, the water content in the treated textiles (Alongi et al., 2012a) and the
ip
1963 ability of the nanoparticles to release water at high temperatures, forming a ceramic barrier
1964 that was able to delay the cellulose ignition and lower the heat release and corresponding rate
cr
1965 (Alongi et al., 2012b). The homogeneous distribution and fine dispersion of POSS at
1966 nanometric level (Alongi et al., 2012b) is said to have modified the degradation profile of
us
1967 cotton by playing a protective role on the thermo-oxidation of fabrics. During thermal
1968 decomposition in the presence of POSS nanoparticles, a carbonization mechanism was
an
1969 favoured and the final char residue increased which slowed down the overall thermo-
1970 oxidation kinetics and hence improved the properties. The TTI was increased and the HRR
1971 was reduced up to 40%. Based on LOI and cone calorimetry test results, nanoparticles show
M
1972 better performance in the flammability of cotton than the other flame retardant used. On the
1973 other hand, the major observation from the cone calorimetry tests was that in the presence of
1974 zinc based smoke suppressants, the release of CO and CO2 was remarkably reduced relative
d
1975 to fabrics treated with silica alone (Alongi & Malucelli, 2012). It was found that the
te
1976 combination of ZnO and silica showed a joint effect in reducing the release of these gases
1977 when compared to combinations of silica with phosphorus or boron based flame retardants.
p
1978
ce
1979 The current published work by Alongi and co workers looked at using whey protein (folded
1980 and unfolded structures) (Bosco et al., 2013) and deoxyribonucleic acid (DNA) powder from
1981 herring sperm (Alongi et al., 2013) on cotton fabrics. This was achieved by deposition of
Ac
1982 whey protein on cotton fabrics and impregnation whereby cotton fabrics were dipped in a
1983 DNA solution for some time, according to respective studies. The treated samples were
1984 assessed for their thermo-oxidative stability and flammability characteristics. It was found
1985 that the presence of protein coating (Bosco et al., 2013) significantly sensitized the cotton
1986 degradation, but led to very high final residues. These protein treated cotton materials were
1987 shown to have increased the total burning time as well as reducing the burning rate. The
1988 authors concluded that the system may represent a novel and promising eco-friendly finishing
1989 treatment for cellulosic substrates. Additionally, only a minimum of 10 wt.% DNA (Alongi et
1990 al., 2013) loading on cotton was necessary to reach the flame out of cotton when a methane
68
Page 68 of 110
1991 flame was applied, and that 19 wt.% DNA was able to show resistance to an irradiation heat
1992 flux of 35 kW m-2. In general, this cotton/DNA sample did not burn at increased loadings, but
1993 pyrolysed due to the presence of DNA molecules that absorbed heat and released inert gases.
1994 It was concluded that although these materials displayed promising flame retardant and
1995 suppressant properties, the design of DNA based FR needs some careful consideration and
t
1996 further investigation. This was due to the poor durability and resistance to washing treatments
ip
1997 of materials according to the ISO 6330 standard.
1998
cr
1999 4.2 Biopolymers
2000
us
2001 Biodegradable polymer matrices are those materials with an ability to decompose into
2002 biomass, carbon dioxide, inorganic compounds, methane or water due to enzymatic action by
an
2003 micro-organisms when disposed-off into landfills (Chapple & Anandjiwala, 2010; Jang et al.,
2004 2012; Kandola, 2012). The classification of biodegradable polymers is illustrated in Figure13.
2005 They are broadly classified as natural or synthetic depending on their origin. Furthermore,
M
2006 they are sub-classified into those from renewable resource, the chemically synthesized,
2007 microbial synthesized as well as blends systems (John & Thomas, 2008; Satyanarayana et al.,
2008 2009). The class of chemically synthesized biodegradable polymers may be further
d
2009 subdivided into those that are from biotechnology (i.e. polyacids, e.g. PLA) and the ones
te
2010 from petrochemical products (i.e. polycaprolactone, PCL, aliphatic and aliphaticaromatic
2011 polyesters, polyesteramides) (Chapple & Anandjiwala, 2010; Jang et al., 2012; John &
p
2012 Thomas, 2008; Kandola, 2012; Satyanarayana et al., 2009). These biopolymers are
ce
2013 hydrophilic polyesters that absorb moisture. They are characterized by higher cost and lower
2014 performance than conventional plastics. Their application is mainly in the packaging industry
2015 and other applications that need lower strength. Of these biopolymers, PLA is currently the
Ac
2016 most studied, both in blends and biocomposites reinforced with natural fibres (Frone, Berlioz,
2017 Chailan & Panaitescu, 2013; Gallo, Schartel, Acierno, Cimino & Russo, 2013; Sahari &
2018 Sapuan, 2011).
2019
2020 Different biopolymers have been used as matrices in the investigation of various composite
2021 materials. These were compounded with additives, fillers or reinforcements. The broader goal
2022 of this was to improve their performance compared to conventional polymeric materials, to
2023 lower the market cost of their final products and to broaden their range of applications to high
2024 performance polymer sectors (including aerospace, marine and electronics). The studied
69
Page 69 of 110
2025 biopolymers include poly(lactic acid) (PLA), polycaprolactone (PCL), starch, cellulose,
2026 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(butylene adipate-co-
2027 terephthalate) (PBAT), poly(trimethylene terephthalate) (PTT) and polyetherblockamide
2028 polymers. Different properties of biopolymers such as mechanical, thermal, biodegradability
2029 and flammability performance were studied (Cheng et al., 2012; Das, Ray, Chapple &
t
2030 Wesley Smith, 2013; Frone et al., 2013; Gallo et al., 2013; Tang, G., et al., 2012).
ip
2031
cr
us
an
M
d
2032
2033 Figure 13. Classification of biodegradable polymers and their nomenclature. Reprinted
te
2034 from Satyanarayana et al. (2009), Copyright 2009, with permission from
2035 Elsevier.
p
2036
ce
2037 A wide range of additives or reinforcements are used to fill biopolymers. The additives or
2038 reinforcements may be inorganic, organic, synthetic or natural in nature. These may include
2039 natural fibres (i.e. kenaf, flax, hemp, wool, cellulose, coconut fibre, rice husk and kraft
Ac
2040 lignin), clays, silica, metal oxides and hydroxides, phosphate compounds and graphite. The
2041 preparation of reinforced biopolymer composites and/or blends is achieved through different
2042 methods. They include melt blending, extrusion, compression moulding and injection
2043 moulding. Of all the investigated properties of the filled biopolymer composites,
2044 flammability performance is of recent research interest (Das et al., 2013; Ke et al., 2010;
2045 Tang, G., et al., 2012; Zhan, Song, Nie & Hu, 2009; Zhu et al., 2011).
2046
70
Page 70 of 110
2047 Flame retardant treated PLA composites have been investigated more than those of other
2048 biopolymers (Das et al., 2013; Ke et al., 2010; Tang, G., et al., 2012; Zhan, Song, Nie & Hu,
2049 2009; Zhu et al., 2011). Ke et al. (2010), Zhan et al. (2009) and Zhu et al. (2011) prepared
2050 PLA/flame retardant composites by a melt blending/mixing method. In these studies,
2051 ammonium polyphosphate (APP) (Ke et al., 2010; Zhu et al., 2011), hyperbranched
t
2052 polyamine charring agent (HPCA) (Ke et al., 2010), expandable graphite (EG) (Zhu et al.,
ip
2053 2011) and spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine (SPDPM)
2054 (Zhan et al., 2009) were used to formulate different flame retarded systems with PLA. Both
cr
2055 HPCA and SPDPM were synthesized and characterized by the authors before incorporation
2056 into the PLA composites. Techniques that include UL94, LOI, TGA, MCC (PCFC), SEM
us
2057 and cone calorimetry were employed, amongst others, for various tests on the composites.
2058
an
2059 All these studies reported that the intumescent flame retardant (IFR)/PLA showed improved
2060 flame retardancy and anti-dripping performance. It was found that different combinations of
2061 APP/HPCA (3:2) at 30 wt.% (Ke et al., 2010), APP/EG (1:3) at 15 wt.% (Zhu et al., 2011)
M
2062 and SPDPM at 25 wt.% (Zhan et al., 2009) exhibited LOI values of 36.5 (Ke et al., 2010; Zhu
2063 et al., 2011) and 38 (Zhan et al., 2009) vol.%, as well as UL94 V0 rating (see Table 6).
2064 Additionally, Zhu et al. (2011) indicated that APP/EG (1:3) showed better performance than
d
2065 APP and EG alone. As shown in Figure 14 for specimens after an LOI test, the presence of
te
2066 different IFR additives led to the formation of charred layers. Pure PLA does not form any
2067 char and decomposes almost completely.
p
2068
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71
Page 71 of 110
2068
t
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2069
us
2070 Figure 14. Photographs of PLA specimens after LOI tests. Reprinted from Zhu et al.
an
2073
2074 Table 6. Composition of the samples and the flame retardancy of the composites.
2075 Reprinted from Ke et al. (2010), Copyright 2010, with permission from
M
2076 Elsevier.
t1 + t2a LOI UL-94 Flaming
Sample PLA APP HPCA
(s) vol.% rating dripping
d
PLA-1 100 – – – 21 Fail Yes

PLA-2 70 30 – 10 + 5 33 V-2 Yes
te
PLA-3 70 20 10 0+1 34 V-0 No

PLA-4 70 18 12 0+1 36.5 V-0 No
PLA-5 70 15 15 0+2 28 V-0 No
p
PLA-6 70 12 18 0 + 13 27.5 V-1 No

PLA-7 70 10 20 1 + 14 26.5 V-1 No
ce
PLA-8 70 – 30 – 22 Fail Yes

PLA-9 75 15 10 0 +1 28.5 V-0 No
PLA-10 80 12 8 0+1 26.8 V-0 No
9
Ac
PLA-11 85 6 0+1 26.2 V-0 No

PLA-12 90 6 4 0 +3 25.2 V-2 Yes
a
2077 t1: the burning time after first ignition, t2: the burning time after second ignition.
2078
2079 This phenomenon of charred layer formation is further emphasized by the char residue as
2080 seen from TGA results (see Figure 15). Furthermore, both the cone calorimetry and
2081 microscale combustion calorimetry results were indicative of the improved fire retardancy of
2082 PLA in the presence of FR agents. This was concluded from the reduction in time to ignition
2083 (TTI), heat release rate (HRR), peak HRR, average HRR, total heat release (THR) and mass
2084 loss rate (MLR) (Ke et al., 2010; Zhu et al., 2011) (see Table 7), as well as reduction in heat
72
Page 72 of 110
2085 release capacity (ηc) (HRC), total heat release (hc) and the temperature at maximum pyrolysis
2086 rate (Tmax) (Zhan et al., 2009) (see Figure 16). From all the studies, the key conclusion made
2087 by the authors is based on the efficiency and synergistic effect between different intumescent
2088 flame retardant agents. This effect led to the formation of an intumescent protective charred
2089 layer and a change in the degradation process of PLA as concluded by Zhan et al. (2009). On
t
2090 the other hand, Ke et al. (2010) made the conclusion that PLA/APP/HPCA can form a char
ip
2091 layer containing a P – O – C structure. This layer may have possibly hindered the transfer of
2092 heat and combustible gas resulting in good flame retardancy without melt dripping.
cr
2093
2094 Table 7. Part data recorded in cone calorimeter experiments. Reprinted from Ke et al.
us
Sample TTI Av-HRR PHRR TTPH Av-MLR THR
(s) (kW/m2) (kW/m2) (s) (g/s) (MJ/m2)
an
PLA 60 161 272 203 0.098 65.1
PLA-2 81 125 228 146 0.072 48.6
PLA-4 65 65 153 98 0.038 35.6
M
2096
d
p te
ce
Ac
2097
2098 Figure 15. TGA curves of PLA, APP/HPCA, PLA/APP/HPCA, PLA/APP/HPCA
2099 (Calculation). Reprinted from Ke et al. (2010), Copyright 2010, with
2101
2102 Zhu et al. (2011) proposed a possible flame retardancy mechanism of PLA/APP/EG
2103 composites in which the synergism between APP and EG is explained. Figure 17 illustrates
2104 the phenomenon. This is explained in that EG expands and migrates with the flow of
73
Page 73 of 110
2105 PLA/APP. This is followed by the decomposition of APP which produces polyphosphoric
2106 and ultraphosphoric acids. These compounds catalyse PLA to form char residue. During the
2107 decomposition of EG and APP, incombustible gases such as SO2, CO2, NH3, and H2O are
2108 released, which diluted the fuels that originate from the degradation fragments. The flow of
2109 PLA/APP degradation products (i.e. polyphosphate) provides adhesion between the graphite
t
2110 flakes, consequently leading to continuous, dense and sealed char layers. It is these layers that
ip
2111 inhibit the further degradation of PLA, APP and EG, and slow down the volatilization of
2112 polyphosphoric and ultraphosphoric acids at high temperatures.
cr
2113
us
an
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d
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2114
p
2115 Figure 16. The HRR curves of PLA and its composites at 1 K/s heating rate. Reprinted
2116 from Zhan et al. (2009), Copyright 2009, with permission from Elsevier.
ce

2118
Ac
74
Page 74 of 110
t
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2119
2120 Figure 17. Possible flame retardant mechanism of PLA/APP/EG composite. Reprinted
2121 from Zhu et al. (2011), Copyright 2011, with permission from Elsevier.
d
2122
te
2123 In another study, the flame retarded biopolymers containing aluminium based compounds,
2124 melamine (MA) and organoclays were investigated for their thermal, mechanical and
p
2125 flammability performances. These biocomposites were prepared by melt compounding and
ce
2126 extrusion methods. The matrices used were PLA (Cheng et al., 2012; Das et al., 2013; Tang,
2127 G., et al., 2012) and polyetherblockamide (PEBAX) (Hoffendahl, Fontaine & Bourbigot,
2128 2013) biopolymers. In all these studies, it was reported that the incorporation of flame
Ac
2129 retardant additives such as ammonium hypophosphite (AHP) at 30 wt.% (Tang, G., et al.,
2130 2012), boehmite alumina at 5 wt.% (Das et al., 2013), ATH and organoclay at 50 wt.% and 5
2131 wt.% respectively (Cheng et al., 2012), and a maximum loading of 30 wt.% MA and 6 wt.%
2132 organoclay (Hoffendahl et al., 2013) promoted carbonization of the biopolymers. This was
2133 supported by the increased char residues of the composites as seen in TGA studies (Figure
2134 18). An additional contribution to carbonization due to the presence of organoclays was also
2135 reported (Cheng et al., 2012; Hoffendahl et al., 2013). Consequently, this contributed to
2136 improved fire resistance performance of filled biopolymers as reported from LOI, UL94,
2137 cone calorimetry and MCC tests used in these studies.
75
Page 75 of 110
2138
t
ip
cr
2139
us
2140 Figure 18. TGA and DTG curves of PLA and FR-PLA composites under nitrogen
2141 condition. Reprinted from Tang, G., et al. (2012), Copyright 2012, with
2142 permission from American Chemical Society.
an
2144
M
2145 According to Cheng et al. (2012), the addition of organoclay into a PLA/ATH system led to
2146 further thermo-oxidative stability, and the presence of both organoclay and ATH increased
2147 the degradation activation energy of the composites. The authors proposed that during the
d
2148 UL94 test, both the layered silicates and a high content of ATH in PLA were integrated to
te
2149 form a compact insulator on the burning surface, thus lowering the melt dripping. It was
2150 further reported that at high loadings of the conventional flame retardant ATH (i.e. 50 wt.%),
p
2151 the PLA composites were brittle, but improved with the addition of organoclay. On the other
2152 hand, after a series of tests based on solid state nuclear magnetic resonance (NMR) (13C and
ce
27
2153 Al) and TGA-FTIR, Hoffendahl et al. (2013) established the possible flame retardancy
2154 mechanisms of PEBAX/MA with and without organoclay. They concluded that MA acted by
Ac
2155 a gas phase mechanism through different routes including fuel dilution, a cooling effect due
2156 to endothermic processes, and the formation of free radicals that interacted with the flame.
2157 The incorporation of organoclay into PEBAX/MA resulted in the formation of a char layer,
2158 adding a condensed phase mechanism to the flame retardancy mechanisms.
2159
2160 The mechanical properties of these flame retarded PLA biocomposites were also reported.
2161 Tang, G. et al. (2012) reported a decreased tensile strength and elongation at break with the
2162 incorporation of ammonium hypophosphite (AHP) from 10 to 30 wt.% (Figure 19). This
2163 reduction was attributed to the rigid nature of the AHP particles, especially on the elongation
76
Page 76 of 110
2164 at break. On the other hand, Das et al. (2013) reported improved mechanical properties of the
2165 PLA/Boehmite alumina (BAl) (with a maximum loading of 5 wt.%) composites as seen from
2166 Table 8. This observation was explained as being due to an optimum uniform dispersion of
2167 Bal in the PLA matrix, good filler/matrix interaction and the high aspect ratio of the filler.
2168 Consequently, this led to increased rigidity and effective stress transfer between the matrix
t
2169 and the filler. The increased rigidity was further emphasized in the dynamic mechanical
ip
2170 analysis (DMA) results where storage modulus increased inconsistently with BAl loading.
2171 The explanation was that the high D content of the neat PLA made it less rigid and
cr
2172 inconsistently increased the modulus.
2173
us
an
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d
te
2174
p
2175 Figure 19. Effect of AHP loading on the mechanical properties of FR/PLA composites.
ce
2176 Reprinted from Tang, G. et al. (2012), Copyright 2012, with permission from
2177 American Chemical Society.
Ac
2179
2180
2181
2182
2183
2184
2185
2186
2187
2188
2189
2190
77
Page 77 of 110
2191 Table 8. Mechanical properties of the PLA/BAl composites. Reprinted from Das et al.
2192 (2013), Copyright 2013, with permission from American Chemical Society.
Sample Tensile Standard Tensile Standard Elongation Standard
identification strength deviation modulus deviation at break deviation
(MPa) (GPa) (%)
PLA BAl 0 74.4 3.2 3.0 0.2 6.3 0.2
t
PLA BAl 1 84.4 2.6 3.3 0.06 5.5 0.1
ip
PLA BAl 2 97.5 5.3 3.2 0.09 5.4 0.7
PLA BAl 3 116.4 7.8 3.1 0.1 6.1 0.5
PLA BAl 4 113.4 4.4 3.4 0.04 5.2 0.3
cr
PLA BAl 5 107.9 8.2 3.3 0.1 4.8 0.2
2193
us
2194 Hapuarachchi and Peijs (2010) developed a flame retarded system based on PLA,
2195 multiwalled nanotubes (MWNTs), sepiolite organoclays and hemp fibres. These were
an
2196 prepared by an extrusion followed by film stacking method in the case of hemp fibre
2197 reinforced biocomposites. The separate introduction of MWNTs and sepiolite nanoclays
2198 resulted in decreased onset temperatures of degradation and thermal stabilityof the PLA. It
M
2199 was attributed to a percolation threshold causing a network of MWNTs that acted as a
2200 conducting pathway causing early onset of decomposition. The addition of sepiolite
2201 nanoclays resulted in a catalytic effect on the pyrolysis of PLA. The flame retarded
d
2202 biocomposites exhibited improved flammability performance with a reduction of 58% in

te
2203 PHRR. This was attributed to the presence of nanofillers that increased the melt viscosity of
2204 the system and eliminatedthe bubbling of neat PLA.
p
2205
ce
2206 PLA based materials were used in developing flame resistant housings for notebook
2207 computers as reported by Kimura and Horikoshi (2005). Flame retarded PLA biocomposites
2208 were prepared by an extrusion method with the incorporation of different flame retardants
Ac
2209 including aromatic silicon resin, polydimethylsiloxane and aluminum hydroxide, amongst
2210 others. Due to the low rigidity of PLA, the authors used several resin additives (e.g.
2211 polystyrene, polyethylene and polypropylene) to improve its physical properties. The
2212 developed PLA based materials showed optimal physical and flammability properties that
2213 qualified them for the purpose.
2214
2215 In an attempt to address the environmental concerns, Feng, Su and Zhu (2011) investigated
2216 the use of β cyclodextrin (β CD) as carbon agent in an intumescent flame retardant (IFR)
2217 system based on PLA/APP/melamine (MA). This β CD is a bio product mainly from starch.
78
Page 78 of 110
2218 It contains many hydroxyl groups that aid at forming char during burning. It is said to
2219 decompose in one major step in an inert atmosphere leaving a char that is thermally stable
2220 and decomposes at a low rate at high temperatures. The gaseous products such as CO2, CO
2221 and H2O are released during its decomposition. The IFR complex system was prepared by
2222 mechanical grinding, whereas the IFR/PLA composites were melt blended and then hot/melt
t
2223 pressed.
ip
2224
2225 The authors reported that the combination of β CD/APP resulted in more char formation due
cr
2226 to the presence of APP. Both β CD and APP contributed to the release of gaseous products
2227 such as NH3 and H2O from APP in addition to those mentioned in the case of β CD.
us
2228 Furthermore, phosphoric and polyphosphoric acids were also formed as products from APP
2229 degradation. Melamine (MA) was reported to promote β CD char formation too. On heating,
an
2230 both intramolecular and intermolecular dehydration were involved in β CD degradation. The
2231 char formation during decomposition of β CD followed several complex pathways and is
2232 elaborated by the authors. In the case of IFR/PLA composites, it was concluded that β CD is
M
2233 an efficient green carbon agent when coupled with APP and MA at appropriate weight ratios.
2234 This was due to improved LOI values and UL94 rating tests. However, it was noted that MA
2235 containing systems formed unstable char and had some degradation effect on PLA due to the
d
2236 basic NH3 it produced during burning.

te
2237
2238 Gallos, Fontaine and Bourbigot (2013) investigated the effect of an IFR from APP, MA and
p
2239 nanoclays on poly L, D lactide (PDLLA). The stereocomplexed PLA was synthesised by
ce
2240 reactive extrusion in a two step polymerization of L lactide and D lactide to yield PDLLA
2241 multiblocks, and then the IFR system was incorporated to form the PDLLA/IFR
2242 nanocomposites. The group reported improved flame retardancy as observed from cone
Ac
2243 calorimetry test results, namely a decrease of 83% in the HRR peak for nanocomposites
2244 relative to neat PDLLA. A THR of 2 MJ m-2 was also reported for the nanocomposites and
2245 related to a 95% drop with respect to the matrix (i.e.THR of 45 MJ m-2). Consequently, the
2246 authors suggested the mechanism of flame retardancy to be the decomposition of APP into
2247 acids that reacted with melamine and PLA. Such a reaction led to the formation of protective
2248 intumescent char. Additionally, APP reacted with nanoclays to produce alumino phosphates,
2249 which limited the formation of large cracks at the surface of the coating and provided an
2250 efficient protection.
2251
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Page 79 of 110
2252 Similar to Feng et al. (2011),Wang, X. et al. (2011) reported on the flame retardancy and
2253 thermal degradation of PLA/starch biocomposites where starch was used as the carbonizing
2254 agent. Starch is a polyol that is inexpensive, biocompatible, biodegradable and renewable,
2255 and could be utilized as a natural carbon source. In this study, microencapsulated ammonium
2256 polyphosphate (MCAPP) and melamine (MA) were used to formulate a MCAPP/MA/starch
t
2257 IFR system. The group reported improved flammability of the PLA based biocomposites with
ip
2258 an LOI value of 41.0 vol.% and a UL94 V0 rating when 30 wt.% IFR was incorporated. This
2259 was related to the effectiveness of starch as a carbonizing agent. In the MCC tests,
cr
2260 biocomposites exhibited reduced PHRR and THR. This was explained as being due to IFR
2261 catalysing the degradation of PLA with the release of less flammable gaseous products.
us
2262 Improved char yields and thermal stability from TGA tests were also reported, and the char
2263 was said to be made up of pyrophosphoric acid and/or polyphosphate compounds. It was due
an
2264 to this formed char layer that the inner polymer degradation was retarded and PLA fire
2265 resistance was improved.
2266
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2267 Recently, Lin et al. (2013) synthesized flame retardant poly(1,2-propanediol-2-carboxyethyl
2268 phenyl phosphinates) (PCPP) and developed PLA based blends by melt blending. It was
2269 reported, using DMA and scanning electron microscopy (SEM) results, that PCPP/PLA
d
2270 blends were immiscible with LOI values higher than 26 vol.% as well as at a UL94 V0 rating
te
2271 as low as 3 wt.% PCPP loading. The presence of PCPP was found to have simultaneously
2272 enhanced both the rheology (i.e. reducing PLA brittleness and improving processability) and
p
2273 mechanical properties of the PLA based blends. Finally, from both the morphology of the
ce
2274 residual material and phosphorus content measurements, it was concluded that both
2275 condensed phase and gas phase flame retardant mechanisms existed during burning.
2276
Ac
2277 4.3 Biofibre reinforced biopolymer composites

2278
2279 This section deals with flammability studies of composites made of biopolymer matrices
2280 reinforced with biofibres. Various additives/agents may be incorporated in biocomposites
2281 which may include coupling, processing, dispersion and fire retardant agents. It is the latter
2282 that forms the focus point of this study (Chapple & Anandjiwala, 2010; John & Thomas,
2283 2008; Kandola, 2012; Tang, G., et al., 2012; Zavareze & Dias, 2012).
2284
80
Page 80 of 110
2285 FR additives, as discussed earlier, have the ability to alter the flammability character of the
2286 composite material. The properties, including flammability, of the biocomposites are
2287 governed by various factors such as a) the structure of the composite, b) adhesion between
2288 matrix and reinforcement, c) type of natural fibre and d) type of biodegradable polymer
2289 matrix (Chapple & Anandjiwala, 2010; John & Thomas, 2008; Kandola, 2012; Tang, G., et
t
2290 al., 2012; Zavareze & Dias, 2012).
ip
2291
2292 Several studies were carried out for natural fibre reinforced biopolymer composites and their
cr
2293 thermal, morphological, mechanical and flame retardancy properties were reported (Biswal,
2294 Mohanty & Nayak, 2012; Fox, Lee, Citro & Novy, 2012; Gallo et al., 2013; Hapuarachchi
us
2295 &Peijs, 2010; Jang et al., 2012). Gallo et al. (2013) investigated the performance of a multi
2296 component laminate composite based on a biodegradable commercial blend E-PHBV
an
2297 reinforced with kenaf fibres. The E-PHBV consists of poly(3-hydroxybutyrate-co-3-
2298 hydroxyvalerate) (PHBV) and poly(butylene adipate-co-terephthalate) (PBAT). Furthermore,
2299 a phosphate based additive and a metal oxide (Sb2O3) were incorporated to formulate the
M
2300 flame retarded biocomposites. The biocomposites were prepared by an extrusion method
2301 followed by compression moulding. Their laminate structure and thickness were as shown in
2302 Figure 20.
d
2303
p te
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2304
2305 Figure 20. Structure (a) and laminate thickness (b) of the investigated materials.
2306 Reprinted from Gallo et al. (2013), Copyright 2013, with permission from
2307 Elsevier.
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Page 81 of 110
2309
2310 Table 9. Mechanical properties.Reprinted from Gallo et al. (2013), Copyright 2013,
2311 with permission from Elsevier.
Flexural strength (σf) Flexural modulus (Ef) R (KJ m−2)
(MPa) (MPa)
t
E-PHBV 7.5 ± 0.4 233 ± 3 4.3 ± 0.7
ip
Layer 1 7.0 ± 0.2 215 ± 5 2.5 ± 0.4
Layer 2 19.8 ± 1.1 804 ± 26 6.8 ± 0.8
cr
Lam 1:1 10.7 ± 0.3 450 ± 35 4.8 ± 0.4
Lam 1:6 13.4 ± 1.5 488 ± 5 6.1 ± 1.1
us
2312
2313 This multi component structure approach was reported as a successful way to balance the
2314 mechanical and fire retardancy performance in biopolymer composites. It was reported that
an
2315 the presence of both the flame retardant and antimony oxide nanoparticles did not
2316 significantly change the flexural properties of the matrix, but reduced its resilience in
2317 comparison to the blend. On the other hand, addition of kenaf fibres was reported to have
M
2318 improved all the mechanical parameters of the matrix (see Table 9). The different ratios of
2319 used samples (E-PHBV/Kenaf/AlPi/Sb2O3) were: 100/0/0/0 (E-PHBV), 90/0/8/2 (Layer 1),
d
2320 70/30/0/0 (Layer 2), Layer 1/layer 2 (Lam 1:1), Layer 2/layer 1 (Lam 1:6).
2321
te
2322
p
ce
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Page 82 of 110
t
ip
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2323
2324 Figure 21. Heat release rate for E-PHBV (solid line), Layer 1 (open circles), Layer 2
2325 (solid triangles) and laminate structures (a); fire residue after cone calorimeter
d
2326 test for E-PHBV (b.1), barrier formation during burning (Lam 1:1) (b.2) and
te
2327 fire residue for Lam 1:6 (b.3); total heat evolved (c). Reprinted from Gallo et
2328 al. (2013), Copyright 2013, with permission from Elsevier.
p
2329
ce
2330 A reduction in the PHRR, HRR, and fire spread indices from the cone calorimetry test were
2331 reported as shown in Figure 21. This was explained as being due to a combination of both gas
2332 and condensed phase mechanisms from phosphorus and natural fibre. The kenaf fibres were
Ac
2333 said to have contributed by promoting the formation of an additional stable char layer during
2334 combustion. It is reported that kenaf fibres achieved this through intermolecular crosslinking
2335 and by inducing oxidation of phosphorus in the solid phase. Consequently, this prevented
2336 heat and flammable volatiles from penetrating the flame zone.
2337
2338 The char residue obtained after cone calorimetry tests were studied by SEM as seen in Figure
2339 22, and the relationship between the microstructure of the residue and the flame retardancy
2340 mechanism was established. It was concluded that the dense, porous structure in the residue
2341 proved that hydroxyl rich kenaf fibres acted as a carbonization agent by forming a network of
83
Page 83 of 110
2342 holes and cavities that affected the release of pyrolysis gases. However, the authors noted that
2343 there is a need to refine the coupling between the skin and core layer for improved interaction
2344 at the interphase.
2345
t
ip
cr
us
an
M
d
p te
ce
Ac
84
Page 84 of 110
2345
t
ip
cr
us
an
M
d
p te
2346
ce
2347 Figure 22. SEM micrograph of Layer 2 (a–c) and Lam 1:6 (d–f) at different
2348 magnifications. Reprinted from Gallo et al. (2013), Copyright 2013, with
Ac
2350
2351 In the study discussed previously, Hapuarachchi and Peijs (2010) reinforced the flame
2352 retarded ternary system based on PLA/MWNTs/organoclays with nonwoven needle punched
2353 hemp fibre mat (800g m-2). The authors reported that these hemp fibres reduced the HRR
2354 relative to pure PLA, but increased the THR. It was attributed to natural fibres causing the
2355 composites to burn for longer. The flame retardant effect of hemp fibres was thought to be
2356 due to fibres charring and protecting the underlying polymer.
2357
85
Page 85 of 110
2358 Furthermore, it was reported that introducing hemp fibres lowered the HRR when compared
2359 to the non reinforced ternary system. In general, the authors proposed that the main flame
2360 retardant mechanism was due to silicate char surface layer that acted as a barrier for heat and
2361 mass transportation. The group concluded by suggesting that the use of short fibre
2362 compounds may be more suitable for these composites. This was to avoid thick layered
t
2363 structures that delaminated during cone calorimetry tests and exposed the underlying
ip
2364 materials.
2365
cr
2366 Similar results were reported by Biswal et al. (2012) where banana fibre was used to
2367 reinforce polypropylene nanoclay composites in the presence of a maleic anhydride grafted
us
2368 polypropylene (MA-g-PP) compatibilizer. The nanocomposites were prepared by melt
2369 intercalation and the fibre reinforced nanocomposites by melt blending, followed by
an
2370 compression moulding. The group reported that both the tensile and flexural strengths
2371 showed a linear increase as a function of clay content. This was explained as being due to the
2372 insertion of the polymer chains inside the silicate clay layers, which led to an increase in the
M
2373 surface area of interaction between the clay and the polymer matrix. Furthermore, MA-g-PP
2374 facilitated expansion of the gallery space of the nanoclay by the inclusion of polar groups to
2375 intercalate between the clay layers through hydrogen bonding with the oxygen groups of the
d
2376 tetrahedral clay. No considerable increase in the impact strength was observed and this was
te
2377 due to the presence of clay agglomerates resulting in non uniform dispersion within the
2378 polymer matrix. It was concluded that the better system was based on PP/clay/MA-g-PP
p
2379 (92/3/5 w/w), and it was termed optimized polypropylene (OPP).

ce
2380
2381 As far as the flammability properties of these nanocomposites are concerned (Table 10), the
2382 incorporation of nanoclay showed a remarkable reduction in the HRR. This was attributed to
Ac
2383 i) nanoclay changing the degradation path of the polymer matrix, thus acting as a barrier by
2384 creating a roundabout path for migration, and ii) the change in thermal properties or an
2385 increase in the radiation absorptivity due to the high aspect ratio of the nanoclay. The group
2386 reported that the compatibilized banana fibre/PP/clay nanocomposites indicated a variation in
2387 reaction to fire parameters and exhibited an earlier ignition time relative to neat PP. However,
2388 the combustion process proceeded at lower HRR and mass loss rate (MLR) due to improved
2389 interfacial adhesion, but increased as a function of fibre in the nanocomposites. This was
2390 attributed to the typical characteristics of lignocellulosic fibres. Higher thermal stability was
2391 also reported and it was attributed to the presence of nanoclays. Finally, it was concluded that
86
Page 86 of 110
2392 the banana fibre had some nucleating ability on the PP during crystallization which was due
2393 to strong interaction between the polymer matrix, fibres and nanoclays.
2394
2395 Table 10. Cone calorimetric parameters for the PP, OPP and banana fibre-PP (BRPP)
2396 nanocomposites. Reprinted from Biswal et al. (2012), Copyright 2012, with
t
2397 permission from John Wiley and Sons.
ip
Description PP OPP BRPP-10 BRPP-20 BRPP-30
Time to ignition (s) 30 36 28 27 26
cr
Time of flameout (s) 561 855 719 648 615
Total heat release (MJ/m2) 100.5 107.3 121.7 137.4 141.5
Mass lost (g) 30.8 31 32.5 32.2 32.6
us
HRR (kW/m2) 2498.2 748.3 926.4 1136.77 1256.2
Total smoke release (m2/m2) 1298.8 1164.5 1581.9 1746.5 1612.7
SEA (m2/kg) 445.87 519.61 304.1 322.24 360.42
an
2398
2399 Jang et al. (2012) looked at the mechanical and flammability performance of plasma treated
2400 (without any FR) coconut fibre reinforced PLA composites prepared by the comingled yarn
M
2401 method. The mechanical properties were determined and flammability tests were carried out
2402 using the LOI method. It was reported that the tensile strength and Young’s modulus
d
2403 increased with the introduction of the natural fibres, but no improvement was observed for
2404 the elongation at break. The group reported that although there was no obvious distinction
te
2405 between the LOI values for the coconut fibres/PLA composites, they were above 20 vol.%,
2406 indicating a non flammability character.
p
2407
ce
2408 Fox et al. (2013) investigated the flame retarding properties of PLA using POSS modified
2409 nanofibrillated cellulose as a carbon source in IFR systems. Improved flammability was
2410 reported for both the APP/cellulose and the APP/PER (pentaerythritol) systems. POSS
Ac
2411 modified cellulose showed an additional benefit by slightly lowering the PHRR and reducing
2412 the smoke. Furthermore, the use of POSS modified cellulose in IFRs proved effective at
2413 lowering flammability while simultaneously inhibiting APP induced PLA degradation,
2414 increased thermal oxidative resistance and increased composite stiffness.
2415
2416 Recently the researchers at CSIR have been involved in a project in collaboration with
2417 AIRBUS focussing on the development of natural fibre reinforced thermoset panels for use in
2418 aircraft. The research work involved the development of aqueous based flame retardant
87
Page 87 of 110
2419 treatments for flax fabric to ensure that the composite panels comply with Federal Aviation
2420 Airworthiness (FAA) regulations. In addition to primary flame retardant, the composite
2421 contained non fibrous natural silicate fire resistant material as well. The composite material
2422 was reported to exhibit superior flammability, smoke and toxicity properties for the
2423 aforementioned purpose (Anandjiwala et al., 2013).
t
2424
ip
2425 5. Summary
2426
cr
2427 The flammability of biofibre (natural fibre) reinforced biopolymer composites as well as that
2428 of the biopolymer blends was reviewed in this work. Different flame retardants ranging from
us
2429 phosphorus, halogen, silicon, nanometric particles and minerals were discussed. Their
2430 different flame retarding mechanisms, advantages and uses, disadvantages and limitations
an
2431 were elaborated on. The fire testing techniques such as cone calorimetry, pyrolysis
2432 combustion flow calorimetry, limiting oxygen index, UL94 and Ohio State University rate of
2433 heat release apparatus were also discussed. From this work, it could be seen that not only
M
2434 these testing technologies are needed to help define and come up with flame retardancy
2435 mechanisms, but other methods do play a role too. These may include burning tests,
2436 horizontal and vertical, thermal and thermomechanical methods of analysis (i.e. TGA, DSC),
d
2437 microscopic methods [i.e. SEM, transmission electron microscopy (TEM)], spectroscopic
te
2438 methods [i.e. FTIR and X ray diffraction (XRD)] and TGA-FTIR coupled systems.
2439
p
2440 Based on the reviewed work, a number of conclusions on the flammability of biofibre
ce
2441 (natural fibre), biopolymers and biofibre reinforced biopolymer composites can be made:
2442 Natural fibres (NFs) alone are a source of fuel. Thus, they are highly flammable,
2443 susceptible to ignition and combustion, combust exothermically and are burned
Ac
2444 vigorously during combustion.

2445 The range of studied NFs from the flammability perspective is narrow since thus far it
2446 includes wood (saw dust, particle board), flax, rice husk, regenerated cellulose
2447 (viscose), wool and mainly cotton fabric materials. There is therefore a need to
2448 investigate other often used NFs including bamboo, coir, hemp, jute, kenaf, ramie and
2449 sisal.
2450 In general, the treatment of NF with various FR compounds does indeed result in
2451 improved flame resistance.
88
Page 88 of 110
2452 The flammability of biofibres is mainly dependent on their immediate environment:
2453 the nature of the polymer matrix and other FRs present, the presence or absence of
2454 coupling agents and the method of manufacturing natural fibre reinforced
2455 biocomposites. The main flammability mechanism favoured by FR treatment of NFs
2456 is carbonization followed by increased char formation.
t
2457 Depending on the system, the mechanical properties may improve or show marginal
ip
2458 decrease due to treatment.
2459 Current research has mainly focused on PLA as the preferred biopolymer matrix for
cr
2460 the development of biofibre reinforced biocomposites. As a result, there is a need to
2461 begin exploring the use of other biopolymers {e.g.polycaprolactone(PCL), poly(3-
us
2462 hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(tetraethylene terephthalate)
2463 PTT, poly(ether ether ketone) (PEEK), polybutylene succinate (PBS)} in this field.
an
2464 The current interest in using biobased materials such as nanoclays, β CD, pea binder,
2465 starch, whey protein and DNA as participants in developing flame retardant systems
2466 (FRs) could lead to discoveries of “all green”FRs that may aid to addressing the
M
2467 environmental concerns. However, the important point on such systems may be two
2468 phased: the successful development of “all green” FRs on one hand, and the
2469 performance and fulfilment of the required standards for the market on the other. This
d
2470 poses a challenge to the scientific arena on fire retardancy.

te
2471 Finally, further studies need to be conducted to develop flame retarded biofibre
2472 reinforced biopolymer composite systems that simultaneously possess good
p
2473 flammability, thermal, mechanical, morphological and thermo mechanical properties

ce
2474 for practical engineering applications.

2475
2476 6. Acknowledgements
Ac
2477
2478 The authors would like to acknowledge the financial support by the National Research
2479 Foundation (NRF) and Professional Development Programme (PDP). Acknowledgements are
2480 further extended to the colleagues for their undivided attention and support.
2481
2482 7. References
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te

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2666 with synthetic hydromagnesite/aluminium hydroxide/montmorillonite and magnesium
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te

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3099 structured brucite@polyphosphate@amine hybrid system for enhanced flame retardant
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3102 Vasiljević, J., Hadžić, S., Jerman, I., Černe, L., Tomšič, B., Medved, J., Godec, M., Orel, B.,
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3105 Stability, 98, 2602 – 2608.

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3106 http://dx.doi.org/10.1016/j.polymedegradstab.2013.09.020
3107 Marras, S. I., Zuburtikudis, I., & Panayiotou, C.(2007). Nanostructure vs. microstructure:
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3109 silicate hybrids. European Polymer Journal, 43, 2191 – 2206.

3110 DOI:10.1016/j.eurpolymj.2007.03.013
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3112 and physical properties of polypropylene composites. Polymer Bulletin, 70, 871 – 884.
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108
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3182
3183 List of Tables
3184
3185 Table 1. Examples of components of intumescent systems.Reprinted from Bourbigot
3186 and Duquesne (2007), Copyright 2007, with permission from Royal Society of
3187 Chemistry.
t
ip
3188 Table 2. Physical properties of potential fire retardant mineral fillers.Reprinted from
3189 Hull et al. (2011), Copyright 2011, with permission from Elsevier.
cr
3190 Table 3. UL-94 V ratings and criteria.Reprinted from Patel et al. (2012), Copyright
3191 2011, with permission from John Wiley and Sons.
us
3192 Table 4. List of important biofibres.Reprinted from John and Thomas (2008),
3194 Table 5. Density and flexural properties of non FR treated flax short fibres with pea
an
3195 protein binder (i.e. reference) and FR treated materials. Reprinted from Lazko
3196 et al. (2013), Copyright 2013, with permission from Elsevier.
M
3197 Table 6. Composition of the samples and the flame retardancy of the
3198 composites.Reprinted from Ke et al. (2010), Copyright 2010, with permission
3199 from Elsevier.
d
3200 Table 7. Part data recorded in cone calorimeter experiments. Reprinted from Ke et al.
te

3202 Table 8. Mechanical properties of the PLA/BAl composites.Reprinted from Das et al.
p
3203 (2013), Copyright 2013, with permission from American Chemical Society.
3204 Table 9. Mechanical properties.Reprinted from Gallo et al. (2013), Copyright 2013,
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3205 with permission from Elsevier.

3206 Table 10. Cone calorimetric parameters for the PP, OPP, and banana fibre-PP (BRPP)
Ac
3207 nanocomposites.Reprinted from Biswal et al. (2012), Copyright 2012, with

3208 permission from John Wiley and Sons.
3209
112
Page 109 of 110
3209 Highlights
3210 Discusses types of flame retardants and their mechanisms in biocomposites
3211 Covers the principles and methodology of various flammability testing techniques
3212 Reviews literature on flammability of biofibres, biopolymers and their biocomposites
3213 Successful use of flame retardants on biopolymers like PBS, PCL and PHBV still need to be
3214 explored.
3215
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Title: Review on flammability of biofibres and biocomposites

Author: Mfiso E. Mngomezulu Maya J. John Valencia Jacobs

Received date: 6-11-2013

16 Mfiso E. Mngomezulu: MMngomezulu1@csir.co.za, Tel. numbers: +27(0)415083241

17 Maya J. John*: MJohn@csir.co.za

18 Valencia Jacobs: VJacobs@csir.co.za, Tel. numbers: +27(0)415083229

19 Adriaan S. Luyt: LuytAS@qwa.ufs.ac.za, Tel. numbers: +27(0)587185314

22 * Author for correspondence:

24 Telephone numbers: +27(0)41 508 3292

69 2.2.3 Silicon based flame retardants 21

72 2.2.4 Nano-metric particles 23

74 2.2.4.2 Carbon nanotubes 25

76 2.2.4.4 Nano scale particulate additives 27

137 HRC Heat release capacity (ηc)

138 IFR Intumescent flame retardant

140 LDPE Low density polyethylene

144 MPD methacryloyloxyethylorthophosphorotetraethyl diamidate

171 PBDE Polybromodiphenyl ether

172 PHRR Peak heat release rate

175 RAs Reactive additives

178 SPDPM Spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine

330 2.1 Mode of action of flame retardants

Product of reaction of ammonia

542 2.2.2 Halogen based flame retardants

709 with two nanometric dimensions.

711 (POSS), spherical silica nanoparticles; three nanometric dimensions.

749 retardancy mechanisms in polymer/silicate layered nanocomposites may be the formation of

783 cone calorimetry).

848 condensed phase.

1014 2.2.4.4.2 Metallic oxide particles

1048 hydroxides (nano-LDHs) and titanium oxide nanoparticles to ammonium polyphosphate-

1115 compact charred layer.

Filler Formula Tdecomp/ °C ∆Hdecomp/kJ g-1

Aluminium hydroxide Al2O3·3H2O 180-200 1300

Nesquehonite MgCO3·3H2O 70-100 1750

1260 Copyright 2001, with permission from Elsevier.

1295 al., 2001).

1297 3.1 Cone calorimetry

1318 (Intended for colour on the Web and black-and-white in print)

1325 Guillaume et al., 2012; Laoutid et al., 2009; Wichman, 2003).

1347 permission from Elsevier.

1378 3.2 Pyrolysis combustion flow calorimetry (PCFC)

1381 combustibility of milligram sized samples. It is also known as microscale combustion

1412 (HRC, J g-1 K-1) given by equation 2:

1445 Morgan et al., 2009; Schartel et al., 2007).

1523 Wang, Y., Zhang, Chen & Zhang, 2010).

After flame glow of any specimen up to clamp No No No

Cotton indicator ignited by flaming drips No No Yes

1656 transitions and chemical reactions (Rowell & Dietenberger, 2013).

1659 4. Flammability of biofibres and biocomposites

Kapok Ceiba pentranda Fruit

Kudzu Pueraria thunbergiana Stem

Oil palm Elaeis guineensis Fruit

Piassava Attalea funifera Leaf

Ramie Boehmeria nivea Stem

1766 choice to use as reinforcement in composite materials.

1797 Lübke, 2001).

1836 Lübke (2001), Copyright 2001, with permission from Elsevier.

PLA-1 100 – – – 21 Fail Yes

PLA-3 70 20 10 0+1 34 V-0 No

PLA-6 70 12 18 0 + 13 27.5 V-1 No

PLA-8 70 – 30 – 22 Fail Yes

PLA-11 85 6 0+1 26.2 V-0 No