Accepted Manuscript

Effect of fire-retardant ceram powder on the properties of phenolic-based GFRP

composites

Wahid Ferdous, Tuan Duc Ngo, Kate T.Q. Nguyen, Abdallah Ghazlan, Priyan Mendis,
Allan Manalo

PII: S1359-8368(18)31316-7
DOI: 10.1016/j.compositesb.2018.09.032
Reference: JCOMB 6002

To appear in: Composites Part B

Received Date: 28 April 2018

Revised Date: 15 September 2018
Accepted Date: 15 September 2018

Please cite this article as: Ferdous W, Ngo TD, Nguyen KTQ, Ghazlan A, Mendis P, Manalo A, Effect of
fire-retardant ceram powder on the properties of phenolic-based GFRP composites, Composites Part B
(2018), doi: https://doi.org/10.1016/j.compositesb.2018.09.032.

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 ACCEPTED MANUSCRIPT
1 RESEARCH PAPER
2
3
4 Effect of fire-retardant ceram powder on the properties of phenolic-based
5 GFRP composites
6 (Title contains 12 words)
7
8
9

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Running headline: Effect of fire-retardant ceram powder on the properties of phenolic-based GFRP composites
10 (78 characters)
11
12 by

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13
14 Wahid Ferdous*1, Tuan Duc Ngo*2, Kate T. Q. Nguyen1, Abdallah Ghazlan1, Priyan
15 Mendis2 and Allan Manalo3

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16
1
17 Research Fellow, The University of Melbourne, Department of Infrastructure Engineering,
18 Parkville, VIC 3010, Australia.
2
19 Professor, Structural Engineering, The University of Melbourne, Department of

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20 Infrastructure Engineering, Parkville, VIC 3010, Australia.
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21 Associate Professor, University of Southern Queensland, Centre for Future Materials
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22 (CFM), School of Civil Engineering and Surveying, Toowoomba, QLD 4350, Australia.
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24
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25 Submitted to
26 Composites Part B: Engineering
27
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28 *Corresponding Authors:
29
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30
31 Tuan Duc Ngo (PhD, MEngSc, BEng)
32 Professor in Civil Engineering,
33 Research Director, ARC Centre for Advanced Manufacturing of
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34 Prefabricated Housing
35 Department of Infrastructure Engineering,
36 The University of Melbourne,
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37 Parkville, VIC 3010, Australia.

38 E-mail: dtngo@unimelb.edu.au
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39
40 Manuscript summary:
41 Total pages 26 (including 1-page cover)
42 Number of figures 9
43 Number of tables 6
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45
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46 Effect of fire-retardant ceram powder on the properties of phenolic-based
47 GFRP composites
48
49 Wahid Ferdous1, Tuan Duc Ngo2, Kate T. Q. Nguyen1, Abdallah Ghazlan1, Priyan
50 Mendis2 and Allan Manalo3
51
1
52 Research Fellow, The University of Melbourne, Department of Infrastructure Engineering,
53 Parkville, VIC 3010, Australia.

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2
54 Professor, The University of Melbourne, Department of Infrastructure Engineering,
55 Parkville, VIC 3010, Australia.
3
56 Associate Professor, University of Southern Queensland, Centre for Future Materials

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57 (CFM), School of Civil Engineering and Surveying, Toowoomba, QLD 4350, Australia.
58 Email: wahid.ferdous@unimelb.edu.au; dtngo@unimelb.edu.au; kate.nguyen@unimelb.edu.au;
59 abdallah.ghazlan@unimelb.edu.au; pamendis@unimelb.edu.au; allan.manalo@usq.edu.au

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60

61 Abstract

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62 This paper investigated the effect of ceram powder on the properties of composite laminates
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63 based on glass fibres and phenolic resin. The amount of ceram in the polymer matrix was

64 varied between 30% and 50% of the weight of resin. The density, void ratio, tensile strength,
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65 interlaminar shear strength, bond strength, bending modulus and glass transition temperature
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66 were studied, and the effect of ceram on these properties was assessed. A systemic decision-
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67 making strategy is applied to evaluate the optimal amount of ceram in the polymer matrix.

68 Results showed that while the increase of ceram decreased the strength properties of the
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69 composite laminates, the bulk density and bending modulus increased. Moreover, the glass

70 transition temperature increased by 32°C with the addition of 50% (by weight of resin) ceram
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71 powder. The strategic decision-making approach suggested that a good balance of physical,
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72 mechanical, and thermos-mechanical properties can be achieved when ceram is added at a

73 fraction of 50% of the weight of resin, and this amount is considered as optimal for designing

74 laminated fibre composites.

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76 Keywords: Laminated composites; phenolic resin; ceram powder; properties; optimal design

77

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78 1. Introduction

79 Composite sandwich panels have been the subject of active research in replacing

80 conventional materials (such as concrete, aluminium and steel) for prefabricated building

81 façades due to their high strength-to-weight ratio, excellent durability, corrosion free

82 properties, good insulation, strong bonding and rapid offsite construction facilities [1-6]. The

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83 sandwich systems are fabricated by attaching two thin laminated composite skins to a thick

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84 lightweight core that recently attracted attention in civil construction [7, 8]. When applied as

85 a building façade, the skins are exposed to the environment including fire and elevated

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86 temperature, which limit the use of organic materials in construction [9]. Recent incidents

87 and consequences of fire in London Grenfell Tower, Dubai Torch Tower, Lacrosse Building

88
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at Melbourne and others are becoming a matter of great concern for design engineers. A
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89 report has been published that linked the rapid spread of fire to combustible construction
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90 materials [10]. Traditional fibre reinforced polymer (FRP) composites have relatively poor

91 fire performance [11]. Therefore, the composite skins need to be modified to meet the fire
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92 requirements of building codes before their widespread application in modular construction.

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93 One approach in improving fire performance of polymer composites is by

94 incorporating fire retardant filler as a constituent to the matrix [12, 13]. Several fire-retardant
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95 fillers are available in the market and the most common types are Alumina Trihydrate
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96 (Al(OH)3), also known as ATH, and Magnesium Hydroxide (Mg(OH)2), known as MDH [13-
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97 16]. Instead of traditional fire retardant fillers, this study used Ceram Polymerik powder

98 because of its greater design flexibility, lower smoke development, higher resistance against

99 moisture, better thermal and electrical stabilities and cost effectiveness compared to existing

100 systems [17, 18]. Phenolic resin [19] was also chosen due to its superior flame resistance and

101 low cost [9] over traditional resin systems such as polyesters [20], vinyl ester [21] and epoxy

102 [22]. Recent studies by Manalo et al. [23] suggested that sandwich beams with glass FRP

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103 (GFRP) skins and phenolic core can retain more than 80% of their mechanical properties at

104 80oC. While some studies showed that the mechanical properties of composites may degrade,

105 the addition of fire retardant filler can greatly improve their fire resistance [12, 24]. For

106 example, the bending strength of an epoxy-based polymer matrix was reduced with the

107 addition of ATH fillers but increased its glass transition temperature by 5oC [25]. For

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108 composite laminates, the mechanical properties cannot be sacrificed significantly for meeting

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109 fire requirements. Therefore, the present study focused on investigating the properties of

110 phenolic-based laminated GFRP composites with the addition of ceram powder and

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111 determining the optimal volume of ceram powder to achieve a balance in mechanical

112 properties.

113
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Different percentages of ceram powder were added to the matrix of the laminated
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114 composites during the fabrication. The mechanical properties of these composites were then
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115 evaluated including tensile, interlaminar shear, bond and bending properties. The effect of

116 ceram powder on the glass transition temperature of laminates was also investigated. Finally,
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117 the optimal volume of ceram was determined using a structured technique based on the
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118 experimental results. The outcome of this study will contribute scientific knowledge for

119 designing laminated composites for with optimal mechanical and fire resistance performance.
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120
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121 2. Experimental program

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122 2.1. Materials

123 The materials employed in this investigation were fabrics, resin and filler.

124 2.1.1. GFRP Fabrics

125 The glass fibre reinforced fabrics were composed of three plies of reinforcement in a stacking

126 sequence of [0/-45/+45]. The bonded fabrics strictly control fibre alignment, allowing for

127 stronger, stiffer and lightweight laminates; and improve surface quality while minimising the

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128 formation of resin-rich pockets. The stacking sequence allows flexibility in engineering

129 laminated composites for specific strength requirements using different fibre orientations.

130 2.1.2. Phenolic Resin

131 In this study, GP 486G34 Phenolic impregnating resin was used as a binder of fibreglass mat.

132 The liquid amber resin was formulated by phenol and formaldehyde, which have a specific

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133 gravity of 1.24. To enhance the polymerisation reaction within a practical time period, the

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134 resin was mixed with hardener. The liquid brown hardener (GP 4826C Hardener) with a

135 specific gravity of 1.41 was formulated by phosphoric, arylsulphonic and sulphuric acid.

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136 UrePac+1008 with specific gravity of 1.14 was also introduced in the resin system to

137 maintain the pH and improve the workability of the polymer matrix. The resin and hardener

138
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were supplied by Pacific Urethanes Pty Ltd, Australia.
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139
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140 2.1.3. Fire-retardant Filler

141 The filler material used in this study is Ceram Polymerik FM-3H, which is a development
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142 grade of ceramifying additives in powder form. This powder, when added to the resin, creates
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143 a ceramic shell in fibre reinforced composites once activated by high temperature (from

144 350 °C to 800 °C or higher) under fire conditions [26]. The off-white colour ceram powder
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145 has a specific gravity of 1.80 and is also effective in reducing overall weight, resisting
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146 moisture, and controlling smoke development. This material was supplied by Ceram
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147 Polymerik Pty Ltd, Australia.

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149 2.2. Specimen preparation

150 The laminated composite specimens were fabricated by three layers of fabrics with a stacking

151 sequence of [0/-45/+45/+45/-45/90/+45/-45/0], which were bonded with a phenolic polymer

152 matrix. The longitudinal (0°), transverse (90°) and diagonal (±45°) fibres provide a balance of

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153 strength and stiffness in all directions. Polymer matrices were produced with different mixing

154 ratios of resin, hardener, urepac and ceram. The liquid resin, hardener and urepac were mixed

155 together before adding the ceram powder. In all mixtures, the fractions of the hardener and

156 urepac were 20% and 10% of the weight of phenolic resin, respectively, while the ceram was

157 added at 0%, 30%, 40% and 50% of the resin weight, thereby producing four different

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158 matrices named C0, C30, C40 and C50, respectively. These percentages of filler were based

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159 on the previous study by Ferdous et al. [25] wherein they found that epoxy-based polymer

160 resin with 30% to 50% of fillers will produce a matrix with reasonable properties.

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161 Furthermore, the addition of ceram over 50% by weight did not produce a workable polymer

162 matrix. The laminated composite without Ceram (C0) is considered as a reference specimen

163
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for comparing the performance of the C30, C40 and C50 samples.
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164 After hand laminating the GFRP laminates (nominal dimensions of 375 mm × 375
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165 mm × 2.5 mm), they were placed in an oven for heat curing. In the oven, the laminates were

166 positioned between two plain aluminium sheets and non-stick hot plate liner to facilitate a
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167 smooth non-stick surface. Each specimen was then loaded with a 20 kg plate to compress it
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168 during heating. The oven was preheated at 95°C and each specimen was subjected to three

169 different temperatures, namely 95°C, 115°C and 165°C. The total curing time was
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170 approximately 100 minutes, which consisted of the following phases: starting with an initial
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171 temperature of 95°C for 20 mins; increasing the temperature from 95°C to 115°C over 10
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172 minutes; settling at a temperature of 115°C for 20 minutes; again increasing the temperature

173 from 115°C to 165°C over 20 minutes; and finally heating the sample at 165°C for the final

174 30 minutes. This curing regime was implemented to minimise pitting on the composites

175 surface caused by gas release. When heated at 165°C, the surface colour of the specimen C0

176 turned into light orange while the other samples with ceram (C30, C40 and C50) turned into

177 light yellow as shown in Fig. 1.

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(a) C0 (b) C30 (c) C40 (d) C50

178 Fig. 1: Changes of colour with the increase of ceram in the laminated composites.

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179

2.3. Mechanical testing

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180

181 The tensile, interlaminar shear, bond and bending properties of laminated composites with

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182 different ceram volumes were evaluated following the relevant ASTM standards. The tests

183 were conducted at room temperature under displacement controlled conditions at a rate of 1

184
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to 2 mm/min [27] using a 100 kN MTS testing machine. Five specimens were tested for each
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185 specimen type to account for statistical variation and to achieve reliable results. The load and

186 corresponding displacements were directly recorded by the instruments and the failure
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187 behaviour was observed during the testing. The specimens’ length (L), width (W) and
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188 thickness (T) and the test standards followed are provided in Table 1.
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189 Table 1: Specimen details and test standards

Type of test Nominal dimensions No. of samples Test standard Ref.

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(L×W×T)

Tensile 250 mm × 25 mm × 2.5 mm 5 ASTM [27]

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D3039
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Short beam shear 15 mm × 5 mm × 2.5 mm 5 ASTM [28]

D2344

Lap shear Each leg 100 × 25 × 2.5 mm 5 ASTM [29]

D5868

Bending 80 mm × 25 mm × 2.5 mm 5 ASTM D790 [30]

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DMA 55 mm × 10 mm × 2.5 mm 2 ASTM [31]

D4065

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191 2.4 Dynamic Mechanical Analysis (DMA)

192 The thermomechanical behavior of the composite laminates was investigated under the

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193 dynamic mechanical analysis (DMA) with a NETZCH 242 E Artemis according to the

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194 ASTM D4065 [31] testing standard. Two samples from each laminate type were prepared

195 with a nominal thickness of 2.5 mm, width of 10 mm, and length of 55 mm. These laminates

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196 were then loaded in a dual-cantilever setup at a frequency of 1 Hz from room temperature to

197 180°C at a heating rate of 3°C/min. The storage modulus (E’) was recorded and plotted

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against temperature. The glass transition temperature (Tg) of the laminates was then measured
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199 based on the onset of the storage modulus curve.
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200

201 3. Results and discussion

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202 3.1. Density and void content

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203 The bulk density and void content of the laminated composites containing ceram powder was

204 measured prior as they can have influence on the performance of composites. Fig. 2(a) shows
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205 the theoretical and measured density with the percentage of voids. The bulk density was
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206 measured by the weight per unit volume and calculated theoretically using Eq. (1). The
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207 volume of void content is measured by Eq. (2).

208 = 100 ( + + + + ) (1)

209 = 100( − )⁄ (2)

210 In Eq. (1) and Eq. (2): and are the theoretical and measured density of the laminates;

211 , , , and are the percentage weights of resin, hardener, urepac, ceram and fibre

212 in the laminates respectively; , , , and are the densities of these constituents; and

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213 is the percentage void content. It is interesting to observe that the theoretical density is

214 increasing with an increase of ceram while the measured bulk density is decreasing. The

215 theoretical density obtained for C0, C30, C40 and C50 laminates are 1.777, 1.790, 1.792 and

216 1.795 g/cm3, respectively, while the corresponding measured densities are 1.705, 1.695,

217 1.659 and 1.581 g/cm3. This opposite trend between theoretical and measured densities can

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218 be attributed to the formation of voids in the polymer matrix. The formation of voids is a

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219 common phenomenon that is unavoidable in composite materials, which is caused by the

220 mixing and consolidation of two or more discrete material components [32]. Fig. 2(a) shows

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221 that the void percentage is at 4%, 5.3%, 7.4% and 11.9% for C0, C30, C40 and C50 samples,

222 respectively. This range of voids is similar to that of other laminated fabric composites, e.g.

223
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between 5.09% to 11.2% according to the findings of Jeong’s [33] study. The increase of
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224 ceram reduced the flowability of the matrix, thereby increasing the void content. This finding
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225 is further supported by the microscopic images as presented in Figs. 2(b) to 2(e). The optical

226 microscope captured the voids at the surface and it can be seen that more and larger voids
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227 were formed with the increase of ceram powder.

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2.2 18
Theoretical density
Measured density 15
Density, (g/cm3)
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% Void
1.8 12
% Void

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1.4 6
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1 0
C0 C30 C40 C50
% Ceram in composites

(a) Density and void formation with ceram

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(b) void in C0 (c) void in C30

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(d) void in C40 (e) void in C50

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228 Fig. 2: Effect of ceram on density

229
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230 3.2. Tensile properties

231 The failure modes of the tensile specimen in the longitudinal and transverse directions are
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232 shown in Fig. 3(a) and 3(b), respectively. In the longitudinal direction, all of the specimens
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233 failed due to tensile failure of the glass fibres within the gauge length with no observed slip

234 or failure in the anchorage zone. However, delamination was observed for C50 specimen as

235 shown in Fig. 3(a). This delamination can be due to the existence of large voids in this

236 specimen. The delamination observed for C50 in the longitudinal direction is also reflected in

237 the stress-strain behaviour shown in Fig. 3(c). As can be seen from the figure, the stress in the

238 laminates dropped when delamination occurred at a strain of around 1% and stress of 80 MPa

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239 but continued to carry load until rupture of the longitudinal fibres. Similarly, a slight decrease

240 in stiffness was observed at the same level of strain for all longitudinal (Fig. 3c) and

241 transverse (Fig. 3d) specimens. This decrease in stiffness was due to the formation of cracks

242 in the matrix. The nonlinearity could also be from the progressive interfacial bond failure of

243 +45o and 90o GFRP layers as was also suggested by Manalo et al. [34] these fibres are not

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244 continuous throughout the length of the specimens. The nonlinear stress-strain behaviour

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245 became more obvious with the increase of ceram due to the increase in voids as highlighted

246 in the previous section.

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247 Figs. 3(c) and 3(d) indicates that the increase of ceram reduced the tensile strength of

248 the laminates. The ultimate tensile strength of C0, C30, C40 and C50 specimens are 267, 247,

249
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245 and 225 MPa in the longitudinal direction or a reduction of strength by 7.5%, 8.2% and
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250 15.7%, respectively. On the other hand, the tensile strength in the transverse direction is 168,
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251 142, 132 and 125 MPa for C0, C30, C40 and C50 specimens, respectively or a decrease of

252 15.5%, 21.4% and 25.6% for the samples with a ceram content of 30%, 40% and 50%,
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253 respectively. This reduction of strength was due to the increased amount and size of voids in
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254 the laminates. These defects tend to open in tension loading and continue to grow

255 significantly with increased loading therefore giving a lower stiffness and overall strength.
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256 This behaviour was also observed by Haj-Ali and Kilic [35] for their composite materials.
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257
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(a) failure in the longitudinal direction (b) failure in the transverse direction

300 200
C0 C0
Tensile stress (MPa)

Tensile stress (MPa)

250 C30 C30
C40 150 C40
200 C50 C50
150 100
100

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50
50
0 0

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0 2 4 6 0 2 4 6
Tensile strain (%) Tensile strain (%)

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(c) stress-strain at longitudinal direction (d) stress-strain at transverse direction

258 Fig. 3: Effect of ceram on tensile properties

259
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260 3.3. Interlaminar shear strength
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261 The interlaminar shear strength is an important characteristic to evaluate the integrity of the

262 fiber-resin interface in laminated composites [36]. When the transverse shear stress of a
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263 laminated composite exceeds the interlaminar shear strength (ILSS), delamination failure will
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264 occur between the fibre layers. From the experimental results, it was observed that all

265 specimens failed along the length at the mid-plane (Fig. 4a). Fig. 4(b) illustrates the load
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266 displacement behaviour of GFRP laminates with different ceram content. It can be seen that
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267 the load displacement in ILSS are almost same for all specimens up to a load of 50kN. After
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268 this load level, the load-displacement curve for laminates with ceram powder began to behave

269 differently. This was due to the initiation of failure in these laminates, resulting in lower ILSS

270 compared to C0. The ILSS is determined from the ultimate load (P) and cross-sectional area

271 (A) relationship (ILSS = 0.75P/A) according to ASTM D2344 [28]. Fig. 4(c) illustrates the

272 ILSS for samples with different percentages of ceram. The ILSS decreased from 14 MPa to

273 10.7, 9.4 and 5.7 MPa with the increase of ceram by 30%, 40% and 50%, respectively. The

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274 decrease of ILSS with the increase of ceram can be attributed to the decrease of resin content

275 and the formation of voids on which the bond properties of the matrix are primarily

276 dependant. Moreover, the decreasing ILSS for laminates with increasing percentage of ceram

277 can be explained by the failure behaviour. Fig. 5 showed the fracture surface observed under

278 a microscope. As can be noticed from the figures, the fracture surface for C0 (Fig 5a) was

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279 rougher than other laminates (Figs. 5b to 5d) and became smoother with the increase

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280 percentage with ceram. Fig. 5(d) showed C50 had the smoothest fracture surface among the

281 laminates, which explained the lowest ILSS for this sample.

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(a) failure under short beam shear test

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250 16

200
Shear load (N)

12
ILSS (MPa)
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150
8
100 C0
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C30 4
50 C40
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C50
0 0
0 0.5 1 1.5 C0 C30 C40 C50
Displacement (mm) % Ceram in composites

(b) load-displacement behaviour (c) interlaminar shear strength

282 Fig. 4: Effect of ceram on interlaminar shear properties

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(a) C0 (b) C30

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(c) C40 (d) C50
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283 Fig. 5: Failure of laminates in interlaminar shear

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284

3.4. Bond strength

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285

286 The lap shear test was performed to further understand the effectiveness of the ceram powder
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287 in bonding fibres. Fig. 6(a) shows the bond failure under the lap shear test. In all specimens,

288 failure was observed due to adhesion. The load-displacement relationship illustrated in Fig
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289 6(b) indicates that the increase of ceram in the matrix reduces the ultimate failure load. The
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290 bond strength (Fig. 6c) obtained for C0, C30, C40 and C50 specimens are 10.1, 7.8, 7.2 and

291 5.1 MPa indicating a reduction of bond strength by 23%, 29% and 50% when ceram is added

292 at 30%, 40% and 50%, respectively. This is mainly due to the decrease in adhesion of the

293 matrix with the increase of ceram. Compared to the short beam test, the measured bond

294 strength from the lap shear test was 39%, 37%, 31% and 12% lower for C0, C30, C40 and

295 C50 specimens, respectively. This is because of the different loading mechanisms wherein in

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296 the lap shear method, the failure plane was loaded in shear simultaneously with tension while

297 the short beam method measures the almost pure shear of the laminates.

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(a) failure under lap shear test

16 12
C0

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Bond strength (MPa)
C30 10
Bond load (kN)

12 C40
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8
C50
8 6
4
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4
2
0 0
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0 0.25 0.5 0.75 1 C0 C30 C40 C50

Displacement (mm) % Ceram in composites
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(b) load-displacement behaviour (c) bond strength

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298 Fig. 6: Effect of ceram on bond properties

299
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300 3.5. Bending properties

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301 Failure of the specimen under three-point bending is shown in Fig. 7(a). It was observed that

302 the specimens with ceram under bending load failed prematurely due to delamination. This

303 can be explained by the reduced ILSS shear strength of laminates as discussed in the previous

304 section. Fig. 7(b) illustrates the load-displacement relationship for C0, C30, C40 and C50

305 specimens under three-point bending while Fig. 7(c) illustrates a plot of the bending modulus

306 with respect to different ceram contents. The bending modulus (E = PL3/48δI) was

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307 determined from the initial slope of the load-displacement curve (P/δ). It can be seen from

308 Fig. 7(b) that the bending strength of the laminates decreased with the increase of ceram

309 while the bending modulus (slope) increased with the addition of ceram. As mentioned

310 previously, the specimens failed due to delamination and the failure load is not representative

311 of the ultimate bending capacity for ceram-based laminates. The bending modulus on the

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312 other hand obtained for C0, C30, C40 and C50 specimens are 18.6, 21.9, 24.2 and 25.5 GPa,

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313 respectively, which indicated that the bending modulus increases by 18%, 30% and 37% with

314 the addition of 30%, 40% and 50% of ceram, respectively. The increase of bending modulus

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315 with the increase of ceram can be attributed to the partial replacement of low modulus resin

316 by high modulus ceram in the polymer matrix.

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(a) failure under bending

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700 30
Bending modulus (GPa)

C0
600 25
C30
Bending load (N)

500 C40 20
400 C50
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15
300
10
200
100 5
0 0
0 2 4 6 8 C0 C30 C40 C50
Displacement (mm) % Ceram in composites

(b) load-displacement behaviour (c) bending modulus

317 Fig. 7: Effect of ceram on bending properties

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318 3.6. Glass transition temperature

319 Fig. 8 shows the composite laminates after the test as well as the DMA plots. Fig. 8(b) shows

320 an almost constant storage modulus (E’) was observed for sample C0 from 30oC up to around

321 75oC. This indicates that the molecular chain mobility of the phenolic resin did not change,

322 since the temperature was below Tg. On the other hand, the samples C30, C40 and C50

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323 retained most of their storage modulus up to a temperature of 90oC. This result suggests that

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324 the addition of the ceram powder made the mechanical properties of composite laminates

325 stable at elevated temperature. A rapid decrease in E’ was then observed at a temperature

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326 higher than 90oC. This behavior indicates the transition of the matrix from a glassy to a

327 leathery state. Under these conditions, the breakdown of secondary molecular bonds started

328
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leading to a decrease in mechanical properties.
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329 At the onset of the storage modulus curves, Tg values of almost 86oC, 97oC, 103oC, and

118oC were recorded for the samples C0, C30, C40, and C50, respectively. For composite
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330

331 laminates without ceram powder (sample C0), an almost similar Tg values was measured by
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332 Manalo et al. [23] for the phenolic based composite laminates. Similarly, the Tg values
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333 measured from the peak of the tan delta curve, which is approximately 10-15% higher than

334 the Tg measured from storage modulus plot [37], are reported in Table 2, based on standard
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335 practices and recommendations in ASTM D4065 [31]. The laminates with ceram powder
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336 consistently showed a higher Tg than that without ceram (C0). The increase in Tg of
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337 composite laminates with ceram powder can be due to the high temperature resistance of this

338 material which helped stabilizes the properties of the phenolic based resin. Garrido et al. [38]

339 suggested a maximum usable temperature (service temperature) of 20oC lower than the Tg of

340 the materials can be specified for civil engineering applications, which corresponds to more

341 than 80oC for all laminates. Thus, the results from this study suggested that the phenolic-

342 based composite laminates can fulfill the requirements for civil infrastructure exposed to an

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343 in-service elevated temperature of at least 65oC. With the addition of ceram powder,

344 phenolic-based composite laminates can be used in applications subjected to an elevated

345 temperature for up to 95oC.

6000

Storage modulus, (MPa)

103°C
5500

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118°C
97°C
86°C
5000

RI
C0
4500 C30
C40

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C50
4000
0 50 100 150 200
Temperature (°C)

(a) test setup

U (b) storage modulus plots
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346 Fig. 8: DMA test of laminated composites
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347 Table 2. Tg of composite laminates with ceram filler measured from different plots.
348
Specimen Glass transition temperature, Tg (oC)
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Storage modulus Tan delta

C0 86 101
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C30 97 109
C40 103 116
C50 118 131
349
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350
351 4. Design of optimal ceram volume
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352 An optimal volume of ceram is the amount added to the matrix which produces composite
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353 laminates with physical and mechanical properties that can satisfy the performance

354 requirements for a particular application. The results of the experimental investigations

355 revealed that the addition of ceram powder from 30% to 50% can satisfy the minimum

356 performance requirements of building façades of at least 100 MPa tensile strength (obtained

357 225 – 247 MPa), 10 GPa bending modulus (obtained 21.9 – 25.5 GPa), 1.35 g/cm3 density

358 (obtained 1.581 – 1.695 g/cm3) and 65°C glass transition temperature (obtained 97 – 118oC)

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359 [39]. However, it is noted that the increase of ceram powder decreased some important

360 properties whilst improving others. The addition of ceram reduced tensile, interlaminar shear

361 and bond strengths, and produced larger voids in the matrix. On the other hand, the bending

362 modulus, glass transition temperature and density improved with the increase of ceram. The

363 lower bending stiffness of composites is a major problem compared with traditional

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364 construction materials such as timber, concrete and steel. The addition of ceram powder

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365 increase the glass transition temperature that help the laminated composites to sustain higher

366 temperature. The reduction of density with the increase of ceram improves composites by

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367 lowering the structural weight. Therefore, higher bending modulus, higher glass transition

368 temperature and lower density have been considered as positive attributes. Moreover, resin is

369
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the most expensive component in polymer matrix composites. Therefore, the partial
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370 replacement of resin by the low cost ceram will reduce the overall cost of composites. This
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371 gives rise to the following question: what percentage of ceram content (out of 30%, 40% and

372 50%) is the most suitable whilst considering the positive and negative attributes compared
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373 with others? To solve this complex problem and to determine the optimal amount of ceram,
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374 this study applied the analytic hierarchy process.

375
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376 4.1. Analytic Hierarchy Process (AHP)

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377 The Analytic Hierarchy Process (AHP) is a strategic decision-making method based on
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378 mathematics and psychology. This method derives the ratio scales from paired comparisons

379 and the relative importance of each attribute can be expressed by the AHP fundamental scale

380 proposed by Saaty and Vargas [40]. One advantage of this method is its ability to check and

381 reduce inconsistencies in judgement, with a magnitude up to 10% generally acceptable. The

382 fundamental scale 1, 3, 5, 7 and 9 signifies the verbal judgments as ‘equal importance’,

383 ‘moderate importance’, ‘strong importance’, ‘very strong importance’ and ‘extreme

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384 importance’, respectively, while 2, 4, 6 and 8 represent intermediate behaviours. A relative

385 importance matrix can be formulated for attributes, where the relative importance of

386 attribute i with respect to attribute j is presented by aij. All the diagonal entries are equal to 1

387 in the -order square matrix as a strong attribute always needs to be compared with weight

388 scale 1 for a weak attribute. Eq. (3) expresses a typical relative importance matrix =

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389 [ ]"×" which has reciprocal properties where = 1⁄ and "" = 1.

%% ⋯ %"

RI
=$ ⋮ ⋱ ⋮ *
1/ ⋯
390 (3)
%" ""

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391 The relative weights of the attributes or the priority matrix is the normalised Eigenvector of

392 matrix . The Eigenvector of matrix can be determined either manually or by Matlab and

393
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then be normalised by dividing the sum of all its elements that can be expressed by Eq. (4).
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-./
∗
= ∑1
.23 -./
394 (4)
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395 In Eq. (4), is an element of the Eigenvector.

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396 The Consistency Ratio (CR) needs to be checked to ensure consistent relative weights among

the attributes. The values are generally considered inconsistent in a pair-wise comparison
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397

398 when 45 ≥ 0.1 and need to be revised. The CR can be expressed by Eq. (5).

89
45 = :9
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399 (5)

400 In Eq. (5), CI is the Consistency Index that can be expressed by Eq. (6). The average values
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401 of Random Index (RI) with respect to are given in Table 3 [40].
AC

<=>? @"
402 4; = "@%
(6)

403 In Eq. (6), A -B is the Eigenvalue, and is the number of comparisons.

404 Table 3: Average values of RI

1 2 3 4 5 6 7 8 9 10

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5; 0 0 0.52 0.89 1.11 1.25 1.35 1.40 1.45 1.49

405

406 The hierarchy of the analysis is divided into criteria and alternatives. The main drivers of

407 criteria are density, void content, tensile strength, ILSS, bond strength, bending modulus,

408 glass transition temperature and cost. Each of these criteria has three alternatives (C30, C40

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409 and C50).

RI
410

411 4.1.1. Relative intensities of criteria

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412 The main drivers for selecting the optimal mix is the criteria because a small change in

413 intensity in this stage has a significant effect on the final output. The design requirements

414
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depend on the priorities of the properties. Three main challenges of composites are their low
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415 fire performance, high cost and low stiffness properties. Therefore, this study provided high
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416 importance on glass transition temperature, cost and bending modulus. The tensile strength,

417 bond strength and interlaminar shear strength are given almost equal priority as they all
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418 represent the strength of the composites and give moderate importance over void content and
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419 density. Thus, the highest priority was given to the glass transition temperature followed by

420 the cost, bending modulus, ILSS, bond strength, tensile strength, void and density. The
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421 relative importance and intensities of the properties in criteria are provided in Table 4.
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422 Table 4: Pairwise comparison of criteria

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Criteria Importance Intensity Criteria Importance Intensity

A B A B

Tensile Modulus B 3 ILSS Density A 4

Tensile ILSS B 1 ILSS Void A 4

Tensile Bond B 1 ILSS Tg B 5

Tensile Density A 4 ILSS Cost B 3

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Tensile Void A 4 Bond Density A 4

Tensile Tg B 5 Bond Void A 4

Tensile Cost B 3 Bond Tg B 5

Modulus ILSS A 3 Bond Cost B 3

Modulus Bond A 3 Density Void B 1

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Modulus Density A 6 Density Tg B 8

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Modulus Void A 6 Density Cost B 6

Modulus Tg B 3 Void Tg B 8

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Modulus Cost A 1 Void Cost B 6

ILSS Bond A 1 Tg Cost A 3

423
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424 4.1.2. Relative intensities of alternatives
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425 The relative weightings of the alternative composite laminates (i.e., C30, C40 and C50) are

426 calculated based on their performances obtained in this study. As previously mentioned, some
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427 of the properties were found to be good for C30 while others were good for C50. The
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428 percentage improvement or reduction of performance with respect to the control specimen

429 (i.e., C0) is tabulated in Table 5. The increase of ceram reduces the cost of the matrix and the
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430 percentage improvement is calculated based on the consideration that resin is 8 times more
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431 expensive than ceram. The intensity of the weak specimen is given 1 in pairwise comparison
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432 for a particular property and increased proportionally for the strong one. For example, when

433 comparing normalised relative intensities between C30 and C40, the intensity of the density

434 attribute for C40 is 2.5 (i.e., 2.9/1.2) relative to 1.0 (i.e., 1.2/1.2) for C30. Using this concept,

435 the normalised relative intensities of the alternatives are determined and provided in Table 5.

436 Table 5: Change of performance with respect to C0 and normalised relative intensities

Properties % Improvement (+ve) or Normalised relative intensities

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reduction (-ve) C30 vs C40 C30 vs C50 C40 vs C50

C30 C40 C50 C30 C40 C30 C50 C40 C50

Density 1.2 2.9 7.6 1 2.50 1 6.50 1 2.60

Void -32.5 -85.0 -197.5 2.62 1 6.08 1 2.32 1

Tensile strength -7.5 -8.2 -15.7 1.10 1 2.10 1 1.91 1

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Bond strength -22.9 -28.9 -49.6 1.26 1 2.16 1 1.72 1

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ILSS -23.6 -32.9 -59.3 1.39 1 2.52 1 1.80 1

Bending modulus 17.7 30.1 37.1 1 1.70 1 2.09 1 1.23

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Cost 25.0 36.0 43.0 1 1.44 1 1.72 1 1.19

Tg 12.8 19.8 37.2 1.00 1.55 1.00 2.91 1.00 1.88

437
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438 4.1.3. Determination of priorities for laminates
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439 The priorities of the alternatives with respect to the criteria and those of the criteria with

440 respect to the goal are calculated and presented in Fig. 9. The global priority of GFRP
D

441 laminates containing different amounts of ceram is determined by multiplying its

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442 corresponding local priorities and summing them as expressed in Eq. (7).

443 Global priority = ∑ [Priority alternative × Priority criteria] (7)

C EP
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444

445 Fig. 9: Local priorities of the laminates

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446 Table 6: Global priorities of the laminates

Samples Density Void Tensile Bond ILSS Modulus Cost Tg Total

C30 0.0026 0.0168 0.0319 0.0337 0.0360 0.0374 0.0429 0.0664 0.268

C40 0.0065 0.0064 0.0290 0.0268 0.0258 0.0633 0.0620 0.1028 0.323

C50 0.0169 0.0027 0.0152 0.0156 0.0143 0.0780 0.0739 0.1934 0.410

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447

448 Based on the comparative importance of each attribute with respect to the goal, Table 6

RI
449 presents the global priorities of each laminate and the optimal one out of the three alternatives

SC
450 are determined. It is apparent from Table 6 that the highest global priority is obtained for C50

451 specimen (global priority 41%) compared with C30 (26.8%) and C40 (32.3%). This result

452

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suggests that the addition of 50% ceram in the polymer matrix can balance the attributes (i.e.,
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453 density, void content, tensile strength, ILSS, bond strength, bending modulus, cost and glass

454 transition temperature) of GFRP laminates in the best possible way.

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455
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456 5. Conclusions
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457 This paper investigated the behaviour of GFRP laminated composites with a fire retardant

458 ceram powder employed as a filler in the polymer matrix. The effect of ceram powder on the
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459 density, void content, tensile strength, interlaminar shear strength, bond strength, bending

460 modulus and glass transition temperature were examined. A strategic decision-making
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461 method is applied to determine the optimal volume of ceram in the polymer matrix. The
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462 nature of the failure, load carrying capacity and stiffness behaviour were systematically

463 investigated from which the following conclusions are drawn:

464 • The addition of ceram powder in the polymer matrix resulted in a reduction in the

465 bulk density of laminated composites. However, this led to the formation of more and

466 bigger voids.

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467 • The addition of ceram up to 50% by weight of the resin resulted in only a 15% and 25%

468 reduction in tensile strength in the longitudinal and transverse direction, respectively

469 of the composite laminates. This reduction in tensile strength was due to the

470 delamination of the composite layers before fibre rupture.

471 • The interlaminar shear strength and bond strength of composite laminates was

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472 significantly affected with the addition of ceram powder. Up to 60% reduction in

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473 interlaminar shear strength and 50% reduction in bond strength was observed for

474 composite laminates with 50% ceram powder. Moreover, this resulted in a smoother

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475 fracture surface compared to the composite laminates without the ceram powder.

476 • The addition of 50% ceram powder improved the bending modulus by 37%. However,

477
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this led to the composite laminates failing prematurely due to delamination.
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478 • The glass transition temperature of the phenolic-based composite laminates increased
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479 by 32oC (from 86oC to 118oC) with the addition of 50% ceram powder. This suggests

480 that the phenolic-based composite laminates can be used for civil infrastructure
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481 exposed to an in-service elevated temperature of up to 95oC.

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482 • The amount of ceram in the polymer matrix is found to be optimal when it is added by

483 50% to the weight of resin. This amount of ceram can provide a good balance among
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484 the physical, mechanical and thermo-mechanical properties.

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485 An in-depth investigation on the effect of fire-retardant ceram powder on the fire
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486 performance of laminated composites is currently being conducted and has shown promising

487 results. The results of this work are currently being analysed and the significant findings will

488 be published in the near future.

489

490 Acknowledgements

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491 This project was funded through the ARC Training Centre for Advanced Manufacturing of
492 Prefabricated Housing (ARC-CAMP.H) at the University of Melbourne. The technical
493 assistance from Ms Jinghan Lu during specimen testing is highly acknowledged.
494
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