1 Alkali treatment of hemp fibres for the

2 production of aligned hemp fibre mats for

3 composite reinforcement
4 Sunny, Tom*; Pickering, Kim L; Lim, Shen Hin

5 School of Engineering, The University of Waikato, Gate 8, Hillcrest Road,

6 Hamilton, 3240, New Zealand
7 *Correspondence to: Email: [email protected]

8 Abstract

9 The main objective of this study was to produce aligned hemp fibre mats from high strength hemp
10 fibres using dynamic sheet forming (DSF). Alkali treatment of hemp fibre was carried out at
11 ambient and high temperature to separate fibres. Single fibre tensile testing was used to assess the
12 tensile properties of the fibres. It was found that the highest tensile properties were exhibited by
13 high temperature treated fibre, whereas the tensile properties exhibited by ambient temperature
14 treated fibre were lower than for untreated fibre. It was also found that fibre granulated after high
15 temperature treatment, was better separated than that granulated before high temperature
16 treatment. This well-separated fibre could successfully be formed into mats using DSF. The
17 orientation of the formed mat was analysed using ImageJ (NIH, USA) software by which the
18 potential of DSF to produce aligned hemp fibre mat was supported. The mechanical performance
19 of composite reinforced by these aligned hemp fibre mats were assessed.

20 Keywords: Dynamic sheet forming (DSF); Alkali treatment; Aligned fibre mats;
21 Hemp fibre

22 1. Introduction
23 A major area of recent technological development has been that of natural plant fibre composites

24 (NPFCs). Generally, NPFCs consist of plant fibres as reinforcement in a polymer matrix. Natural

25 plant fibres (NPFs) have undergone increased industrial uptake because of their favourable

26 characteristics such as lower density, higher specific strength and stiffness, lower cost, and with

27 lower associated hazards during manufacture (Pickering 2008, Kabir, Wang et al. 2012, Kabir,

28 Wang et al. 2013, Pickering, Efendy et al. 2015). Hemp fibres are attractive reinforcements for

29 NPFCs as they exhibit high tensile strength ranging between 550-1110 MPa (Beckermann and

30 Pickering 2008, Pickering, Efendy et al. 2015). Hemp fibres are also more environmentally

31 friendly than most fibres since they can be grown without pesticides and herbicides.

1
32 The main reasons that limit NPFCs in industry are moisture absorption, lower strength and greater

33 variability of properties compared to synthetic fibre composites (Pickering, Efendy et al. 2015).

34 Previous research has shown that chemical treatments of reinforcing fibres can help to overcome

35 these limitations (Mwaikambo and Ansell 2002, Li, Tabil et al. 2007, John and Anandjiwala 2008,

36 Kabir, Wang et al. 2012, Pickering, Efendy et al. 2015). Among the different chemical treatments,

37 alkali treatment with sodium hydroxide (NaOH) is the most widely used. This treatment removes

38 fibre constituents such as pectin, hemicellulose, lignin and waxes from NPFs bringing about fibre

39 separation and can enhance fibre properties (Beckermann and Pickering 2008, Islam, Pickering et

40 al. 2011, Pickering, Efendy et al. 2015). Modest treatments have been seen to bring about

41 increased cellulose crystallinity, which is considered to be due to the removal of the

42 aforementioned materials, whereas harsher treatments have been shown to convert crystalline

43 cellulose to amorphous cellulose and possibly resulted in chain scission (Sawpan, Pickering et al.

44 2011, Kabir, Wang et al. 2012). These alkali treatments have been carried out by different

45 researchers with varying process parameters including at ambient temperatures (AT) as well as at

46 high temperatures (HT) (Mwaikambo and Ansell 2002, Beckermann and Pickering 2008, Islam,

47 Pickering et al. 2010, Islam, Pickering et al. 2011, Sawpan, Pickering et al. 2011, Kabir, Wang et

48 al. 2012, Kabir, Wang et al. 2013, Efendy and Pickering 2014). Ambient temperature treatments

49 have many advantages such as simplicity, low cost and they can be easily carried out in large

50 volumes compared to HT treatment. However, there is limited information available on the effect

51 of alkali treatment temperature (high temperature versus ambient temperature) on the tensile

52 properties of individual hemp fibres. Also, where the tensile properties are given, these values are

53 based on variable testing regimes including: fibre bundles as opposed to single fibres and

54 unspecified gauge lengths (Beckermann 2007). Therefore, direct comparison is needed between

55 high temperature and ambient temperature treatment to inform which is best.

56 To encourage uptake of NPFCs, convenient forms of NPFs that could be used as alternatives to

57 synthetic fibre mats in standard moulding operations would be helpful. Dynamic sheet forming

58 (DSF) is a method that can be used to produce preferentially aligned short NPF mats (Sunny,

59 Pickering et al. 2017). Previous studies have demonstrated that these mats can be incorporated into

60 polymer matrices to produce composites, which exhibited higher tensile strength as well as

61 Young’s modulus compared to randomly oriented fibre mats composites (Pickering and Efendy

62 2016, Pickering and Le 2016, Sunny, Pickering et al. 2017). Prior to DSF, good fibre separation is
2
63 needed. Alkali treated hemp and harakeke fibres have been reported as used for the production of

64 DSF mats, (Le and Pickering 2015, Pickering, Efendy et al. 2015, Ghazali and Efendy 2016) but

65 the tensile strengths of these treated fibres were reduced compared to raw fibre due to the

66 weakening of structural components (Islam 2008, Ghazali and Efendy 2016, Le 2016, Pickering

67 and Efendy 2016). Therefore, further research is needed to develop processing parameters to

68 improve fibre separation without reduction in tensile properties of fibres prior to DSF. In the

69 current research, the alkali treatments used are modifications of selected alkali treatments from the

70 literature that report improved tensile strength for NPFs (Beckermann and Pickering 2008,

71 Oushabi, Sair et al. 2017). The data obtained for the tensile strengths of the hemp fibres were

72 statistically analysed using Weibull statistics.

73 2. Experimental

74 2.1 Materials

75 Industrial hemp fibre was obtained from Moffett Orchards Ltd., New Zealand. The bast fibres

76 were hand separated from the stalks. The chemicals used for the experiments were sodium

77 hydroxide (NaOH) and sodium sulphite (Na2SO3) supplied by Sigma Aldrich. Polypropylene (PP)

78 random copolymer SKRX3600 supplied by Clariant (New Zealand) Limited, with a melt index of

79 18 g/10min and a density of 0.9 g/cm3, was used as the matrix. The coupling agent used was A-C

80 950P maleic anhydride polypropylene (MAPP) supplied by Honeywell International Inc., USA

81 2.2 Methods

82 2.2.1 Alkali treatment

83 High temperature (HT) and ambient temperature (AT) alkali fibre treatments were carried out on

84 pre-dried hand separated hemp fibres. For ambient temperature treatment, fibres were granulated

85 using an 8 mm mesh in a laboratory scale Castin granulator and then immersed in 5wt% sodium

86 hydroxide (NaOH) solution in a glass beaker as shown in Fig. 1a, for one (AT/one hour) or two

87 hours (AT/ two hours) with a fibre to solution ratio of 1:8. The temperature inside and outside the

88 beaker was measured using a thermometer. The measured room temperature was between 20.5 °C

89 and 22 °C, whereas the temperature inside the beaker ranged from 30.5 °C at the start of the

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 90 treatment to 24 °C at the end of the treatment. For high temperature treatment, fibre and a solution

91 of 5wt% NaOH and 2wt% Na2SO3 with a fibre to solution ratio of 1:8 were placed in stainless

92 steel canisters (SSCs) Fig. 1b. These canisters were then positioned inside a laboratory scale pulp

93 digester controlled by a proportional-integral-derivative (PID) system as displayed in Fig. 1b,

94 which was set to operate with a time-temperature profile as shown in Fig. 2. Granulation was

95 either conducted before or after treatment. The fibres were washed after the treatments for about

96 15 minutes in clean water, before being dried in an oven at 80 °C for 48 h.

a b

97
98 Fig. 1. (a) Set up used for the AT treatment (b) SSC and PID system used for the HT treatment.

99
100 Fig. 2. Time-temperature profile used for the HT treatment.

101 2.2.2 Single fibre tensile testing

102 The ASTM D 3379-75: Standard Test Method for Tensile Strength and Young’s Modulus for

103 High-Modulus Single-Filament Materials (ASTM 1986) was followed to determine the tensile

104 strength and Young’s modulus of untreated (UT), AT/one hour treated, granulated before HT

105 treated and granulated after HT treated hemp fibres. The untreated fibres were soaked in water for

4
106 around 10 days to remove dirt from the fibre surface. Two-millimetre thick cardboard was used for

107 mounting tabs with a gauge length of two millimetres as schematically represented in Fig. 3.

108 Selected single fibres were adhered to the mounting tabs by the application of polyvinyl acetate

109 (PVA) glue.

110

111 Fig. 3. Schematic representation of a mounting tab used for tensile testing of single fibres.

112 For the measurement of single fibre diameter, optical images were captured of single fibres as

113 shown in Fig. 4, by means of an Olympus BX60F5 optical microscope fitted with a Nikon camera.

114 The diameter was measured at five different points along each fibre (as hemp fibres have variable

115 diameters across their length) and average values were used for the calculations.

116

117 Fig. 4. Single hemp fibre as observed under optical microscope: (a) UT, (b) AT/one hour, (c)
118 granulated before HT and (d) granulated after HT treated hemp fibres.
5
119 The single fibres were then tensile tested using an Instron-4204 universal testing machine after

120 burning off the supporting sides using a hot wire cutter. The test was carried out at a rate of 0.5

121 mm/min with a 10 N-load cell. Thirty samples were tested for each treatment and system

122 compliance was determined experimentally to obtain Young’s moduli according to the procedure

123 described in ASTM D 3379-75. For this, mounting tabs with gauge lengths of 5, 10 and 15 mm

124 were also prepared.

125 The Weibull distribution is commonly used to analyse the strength variation for natural fibres

126 (Biagiotti, Puglia et al. 2004, Pickering, Beckermann et al. 2007, Zafeiropoulos and Baillie 2007,

127 Efendy and Pickering 2014). Here, the rearranged two-parameter Weibull cumulative distribution

128 expression (Biagiotti, Puglia et al. 2004, Pickering, Beckermann et al. 2007), as shown below was

129 used to analyse data obtained for different single fibre testing statistically.

130 lnln (1/(1-Pf ) = wlnσ – wlnσo + lnL (1)

131 where w is the Weibull modulus (shape parameter) and σ0 characteristic strength (scale parameter).

132 These parameters are important as they describe the variability of the fibre failure strength

133 (Zafeiropoulos and Baillie 2007). A Weibull plot of lnln (1/(1-Pf) versus lnσ provides a straight

134 line with gradient w and intercept σo at lnln (1/(1-Pf) = 0.

135 2.2.3 Scanning electron microscopy (SEM) of hemp fibre surfaces

136 A Hitachi S-4100 SEM was used to obtain micrographs of fibres. Carbon tapes were employed to

137 mount the samples on aluminium stubs and were then sputter coated with platinum to make them

138 conductive.

139 2.2.4 Wide angle X-ray diffraction (WAXD)

140 To assess fibre crystallinity, a Philips X’Pert diffractometer fitted with a ceramic X-ray diffraction

141 tube was used. For the measurements, the fibres were chopped and pressed into a disk using a

142 cylindrical steel mould. The scanning range was between 5 o and 45o by employing CuKα radiation

143 (λ=1.54 nm) with a voltage and current of 45 mV and 40 mA respectively. Crystallinity index (Ic )

144 of the fibres was calculated using the Segal method (Segal, Creely et al. 1959):

145 IC = (I22.7 - I18.3/I22.7) X 100 (2)

6
146 where I200 is the maximum intensity of the (200) lattice diffraction peak at a 2θ angle of between

147 22o and 23o, and Iam is the minimum intensity of diffraction at an angle 2θ between 18 o and 19o

148 representing amorphous materials (Pickering, Beckermann et al. 2007, French 2014).

149 2.2.5 Fourier transform infrared spectroscopy (FTIR)

150 An FTIR Digilab FTS-40 was used to obtain infrared spectra of untreated, AT/one hour treated

151 and granulated after HT treated hemp fibres. Hemp fibre samples were ground to fine powder

152 using a Retsch MM400 ball mill. The ground powder for each sample was then mixed and

153 compressed with KBr (potassium bromide) using a hydraulic press by applying 8 tonnes/cm2

154 pressure to prepare corresponding sample disc for FTIR analysis.

155 2.2.6 Thermal analysis

156 Thermal gravimetric analysis (TGA) of untreated, AT/one hour treated and granulated after HT

157 treated hemp fibres was carried out using a PerkinElmer simultaneous thermal analyser STA 800.

158 Data were obtained at a rate of 10 °C/min with a heating range of 40 °C to 500 °C and a static

159 airflow at 20 ml/min.

160 2.2.7 Fibre mat assessment

161 The OrientationJ plugin of ImageJ was used to assess the orientation of fibres in fibre mats.

162 Availability and ease of use make ImageJ attractive (Abràmoff, Magalhães et al. 2004, Schneider,

163 Rasband et al. 2012). The principles behind this analysis tool are available in the literature

164 (Rezakhaniha, Agianniotis et al. 2012, Gesellchen, Bernassau et al. 2014, Shah, Vollrath et al.

165 2015, Püspöki, Storath et al. 2016, Sunny, Pickering et al. 2018). OrientationJ can provide a fibre

166 orientation distribution profile based on the orientation of fibres within a mat analysed. The peak

167 of the profile indicates the predominant orientation of fibres within the mat.

168 Additionally, with the calculation of majority of the orientation of fibres in an image, this program

169 also calculates a ‘coherency factor’ to that orientation (Lewis 2016). This factor is calculated based

170 on the amount of pixels that are in line in a particular direction and is bounded between 0 and 1;

171 with 0 and 1 indicating isotropic and anisotropic orientations, respectively (Palmieri, Lucchetti et

172 al. 2015). Twenty-five images, each of aligned and random mats were used for the analysis. All

7
173 the macroscopic images (Fig. 5 a and 5b) were taken using a Wild M3B stereomicroscope attached

174 with Nikon Digital DS-SMc camera.

175

176 Fig. 5. Macroscopic images of (a) aligned short hemp fibre mat (b) random aligned mat.

177 2.2.8 Fibre mat production

178 Aligned fibre mats (Fig. 6a) were produced using a dynamic sheet former (Fig. 6b) built by Canpa,

179 Canada. To produce fibre mats, fibre suspension (approx. 5g in 10 litres of water) was made. This

180 suspension was then pumped by the dynamic sheet former through a reciprocating nozzle onto a

181 rotating drum covered with a wire mesh which acts as a cushion for the deposited fibre (Pickering,

182 Efendy et al. 2015). The alignment of the fibres is in accordance with the nozzle and rotation of

183 the drum. A total of 45g of fibre was used for production of each mat. For the production of fibre

184 mats using DSF, well separated fibre is required to avoid blocks mainly in the flow hoses through

185 which the fibre suspension is discharged onto the rotating drum from the suspension tank.

186 Randomly aligned fibre mat was also produced by pouring fibre suspension (10g in 10 litres) onto

187 a screen with fine holes through which the water drained. The formed mat was partially drained

188 with paper towels by hand pressing. Finally, both aligned and random mats were oven dried at

189 80 °C for 48 hours.

190

8
191

192 Fig. 6. (a) Aligned short hemp fibre mat (b) dynamic sheet former.

193 2.2.9 Production of composites and testing

194 A sheet die attached to a ThermoPrism TSE-16-TC twin-screw extruder was used to produce

195 PP/MAPP (100/7.14) sheets. In order to produce composites (except neat PP), the PP/MAPP

196 sheets and the fibre mats were weighed and arranged in stacks between two Teflon sheets before

197 inserting into a mould. The details of the mould used are available in the literature (Pickering and

198 Efendy 2016). The stacking arrangements used for the production of various composites are listed

199 in Table 1. The stacks were heated and pressed in a hot press same as that of neat PP samples (at

200 170 °C for 5 minutes at 1 MPa). Since the fibre mats are easily distorted, the production process

201 should be carried out carefully. Before the application of pressure, it was ensured that the sheets

202 were fully melted such that the matrix material consolidates sufficiently with the fibre mats.

203 Procedures detailed in ASTM D 638-03; Standard Test Method for Tensile Properties of Plastics

204 was followed for testing the specimens. An Instron-4204 tensile testing machine fitted with a 5 kN

205 load cell, operated at a constant rate of 1mm/min was used for the testing. For the measurement of

206 strain, an Instron 2630-112 extensometer with a gauge length 50 mm was attached to the central

207 part of the test specimen. Before testing, all the samples were conditioned at 23 °C ± 3 °C and

9
208 50 % ± 5% relative humidity for at least 48 hours. A total of five samples were tested from each

209 batch.

210 Table 1: Stacking arrangements used for the production of composites.

Number of Number of Fibre wt.% Stack arrangements from
Samples
PP* sheets fibre mats (approx.) bottom to top of the mould

Neat PP 4 0 0 PP/PP/PP/PP

1PP*/1MAT/1PP*/
HM-15 P#-HM-15 4 3 15
1MAT/1PP*/1MAT/ 1PP*

211 Note: PP*- PP/MAPP, P#- fibres loaded perpendicular to the DSF rotation direction

212 3. Results and discussion

213 3.1 Tensile properties of fibres

214 Hemp fibres have a complex layered structure, containing primary and secondary cell walls. These

215 cell walls consist of many layers of helically wound cellulose microfibrils. The main factors that

216 determine the mechanical properties of different plant fibres are cellulose content, microfibrillar

217 angle, defects and treatments. (Bledzki and Gassan 1999).

218 Table 2: Mechanical properties of hemp samples

Fibre Diameter Average Tensile Young's Modulus
Hemp Samples Maximum Load (N)
(µm) Strength (MPa) (GPa)

UT 30.25 (10.6) 0.299 (0.14) 517 (355) 7.4 (4.7)

AT/one hour 29.87 (6.7) 0.296 (0.18) 436 (236) 6.4 (2.73)

Granulated before
21.38 (4.3) 0.252(0.08) 781 (428) 12.04 (4.4)
HT

Granulated after HT 22.38 (5.8) 0.2784(0.13) 833 (577) 12.32 (7.3)

219 *Standard deviations are shown in parentheses

220 Table 2 displays the diameters, maximum load and mechanical properties of untreated and treated

221 fibres obtained in this work. As can be seen, the HT alkali treatment (granulated before and after

222 HT) resulted in more fibre diameter reduction compared to the AT treatment. It has been found

223 that reduction in fibre diameter is due to removal of hemicellulose and lignin (Taha, Steuernagel et

224 al. 2007, John and Anandjiwala 2008, Kabir, Wang et al. 2012, Kabir, Wang et al. 2013).

225 Although no specific studies were carried out to measure the hemicellulose or lignin content in this

226 work, it has been reported elsewhere that hemicellulose breakdown occurs easily in a high

10
227 temperature environment than at low temperature and the addition of Na2SO3 assists NaOH in the

228 removal of lignin (Beckermann 2007). It was found that HT treatment removed sufficient

229 hemicellulose and lignin from the fibres to give good fibre separation, whereas similar separation

230 was not observed for the fibres with AT treatment.

231 From the tabulated results, it can be seen that the HT alkali treated fibre exhibited higher average

232 tensile strength and Young’s modulus compared to UT and AT alkali treated fibres, whereas the

233 average tensile strength and Young’s modulus exhibited by the AT alkali treated fibre were lower

234 than for UT fibre. This suggests that the resulting structures of the treated fibres depend on the

235 alkali treatment used. The increase in average tensile strength for HT alkali treated fibre compared

236 to UT fibre is thought to be due to the removal of weak components (non-strengthening

237 components) evidenced by the fibre diameter reduction after the treatment. The removal of weak

238 components from the fibre cell walls can lead to close packing of cellulose chains and possibly a

239 decrease in the microfibrillar angle. This close compaction could have enhanced the adhesions

240 between cellulose microfibrils, thereby provided better tensile properties for HT treated fibres

241 towards the loading direction compared to UT treated fibres (Efendy and Pickering 2014). As can

242 be seen in Table 2, although the diameter of AT alkali treated fibre reduced after the treatment

243 compared to UT fibre, the tensile properties of the fibre were reduced even below that of UT fibre.

244 The decrease in tensile properties associated with the fibre is thought to be due to the degradation

245 of the crystalline cellulose chains in the microfibrils or bonding between cellulose microfibrils as

246 affected by the AT treatment (Roy, Chakraborty et al. 2012, Efendy and Pickering 2014).

247 A Student’s t-test was carried out for comparing HT alkali treated fibres with different granulation

248 sequence and it was found that the sequence of granulation had no significant effect on tensile

249 properties of the fibres. Weibull modulus, Weibull characteristic strength and experimental

250 average tensile strength are displayed in Table 3. As expected, the characteristic strength has the

251 same trend as that of average tensile strength. The Weibull modulus for the fibres varied from 1.47

252 to 2.05. These values are comparable with those reported in the literature for cellulosic fibres

253 (Pickering, Beckermann et al. 2007, Ghazali and Efendy 2016).

254 Table 3: Comparison of Weibull parameters with experimental tensile strength for hemp samples
Characteristic Strength Average Tensile
Hemp Samples Weibull Modulus, w
(MPa), σ0 Strength (MPa)

11
 UT 1.68 576 517

AT/one hour 1.92 478 436

Granulated before HT 2.05 869 781

Granulated after HT 1.47 928 833

255 3.2 Crystallinity index (Ic)

256

257 Fig. 7. X-ray diffraction curves for untreated, atmospheric temperature treated and high
258 temperature treated fibres.

259 Crystallinity index indicates the degree of crystallinity (Mwaikambo and Ansell 2002, Ouajai and

260 Shanks 2005). The X-ray diffraction profiles (curves) of UT, AT/one hour, AT/two hours and

261 granulated after HT treated hemp fibres are shown in Fig. 7. The Ic values were calculated from

262 maximum and minimum intensity crystallographic peaks for each profile which are around 2θ =

263 22.7 o and 2θ = 18.3 o respectively and are displayed in Table 4.

264 Table 4: Crystallinity index for hemp samples

Hemp Samples Crystallinity Index (Ic)

UT 64.87

AT/ One Hour 71.16

AT/ Two Hours 61.68

Granulated after HT 80.65

265

266 As can be seen in Table 4, alkali treatments improved the Ic values except for AT/two hours. The

267 higher Ic value of HT alkali treated fibre compared to the UT fibre would be expected due to the

268 removal of non-crystalline materials and possibly better packing of cellulose chains within the

12
269 fibre (Beckermann 2007). Although the Ic value of AT/one hour alkali treated fibres was higher

270 compared to UT fibre, as discussed earlier the tensile strength of this fibre was lower than that of

271 UT fibre. This suggests that chain scission could have overridden the influence of increased

272 crystallinity (Islam, Pickering et al. 2010, Islam, Pickering et al. 2011, Sawpan, Pickering et al.

273 2011, Ghazali and Efendy 2016). It has been reported elsewhere that the degradation rate of

274 cellulose in alkali is influenced by fibrillar morphology; a more ordered physical structure impedes

275 degradation (Knill and Kennedy 2003). This supports the production of better-packed cellulose

276 chains with HT treatment which would have impeded the diffusion of alkali reducing cellulose

277 degradation compared to AT alkali treated fibres.

278 3.3 Infrared spectroscopic analysis

279 Peaks (Fig. 8) in the regions 1730-1740 cm-1 and 1200-1300cm-1 indicate the hemicellulose and

280 lignin components through the presence of C=O linkages (Abraham, Deepa et al. 2011, Chen, Yu

281 et al. 2011). Peaks at 1737 cm-1, 1252 cm-1 and 1201 cm-1 for the UT fibres, became smaller for

282 the AT alkali treated fibres and were not visible for HT alkali treated fibres. Reduction of peak

283 heights supports that alkali treatment removed hemicellulose and lignin, with more removal

284 occurring in HT alkali treated fibres compared to AT alkali treated fibres (Olsson and Salmén

285 2004, Li and Pickering 2008, Peng, Ren et al. 2009, Abraham, Deepa et al. 2011, Islam, Pickering

286 et al. 2011, Kabir, Wang et al. 2013). Similarly, the smaller peaks in the range between 1280 cm-1

287 and 1330 cm-1 for HT alkali treated fibre compared to AT alkali treated and UT fibres further

288 support that HT treatment removes more hemicellulose than AT alkali treated fibres (Taha,

289 Steuernagel et al. 2007). The intensity of peaks between 1630 cm-1 and 1650 cm-1 slightly

290 increased after alkali treatment, which may be due to water molecules formed by the reactions

291 between sodium hydroxide and cellulosic hydroxyl groups (Le Troedec, Sedan et al. 2008).

13
292

293 Fig. 8. The FTIR spectra of untreated, AT/one hour treated, and granulated after HT treated fibres.

294 3.4 Thermal gravimetric analysis (TGA)

295 Typically, for NPFs, there are three main stages of degradation where most of the weight loss

296 occurs: 50-100 °C due to evaporation of moisture in the fibres, 200-350 °C due to hemicellulose

297 decomposition and 300-500 °C mainly due to degradation of lignin and cellulose (Sun, Tomkinson

298 et al. 2000, Dahiya and Rana 2004, Methacanon, Weerawatsophon et al. 2010).

299
300 Fig. 9. TGA thermograms for UT, AT/one hour treated, and granulated after HT treated fibres.

14
301
302 Fig. 10. Weight loss summary for different samples.

303 Figures 9 and 10 (Fig. 9 and Fig. 10) show the TGA thermograms and weight loss summary for

304 UT fibres, AT and HT alkali treated fibres. From Fig. 10, it can be seen that the initial 10 %

305 weight loss occurred only at 297 °C and 329 °C for the AT and HT alkali treated fibres

306 respectively compared to 288 °C for UT fibres supporting the overall improved thermal stability of

307 the fibres. The improved thermal stability of the fibres is likely to be due to thermally unstable

308 components (hemicellulose and pectin) being removed from the fibres due to alkali treatment

309 (Beckermann 2007), with more removal occurring with HT alkali treatment compared to AT

310 treated fibres as supported by FTIR analysis. As the temperature further increased above 360 °C,

311 the weight loss was lower for UT fibres compared to treated fibres, which may be due to a stable

312 lignocellulose complex formed at higher temperatures that prevented this lignin-rich fibre from

313 further weight loss above 360 °C (Islam 2008). Also, at higher temperatures, it was found that the

314 weight percentage loss was higher for HT alkali treated fibres compared to AT alkali treated fibres

315 (Fig. 10). This higher weight percentage loss for HT alkali treated fibres above 360 °C supports

316 that the greater removal of lignin from the fibre was by HT alkali treatment compared to AT alkali

317 treatment (Beckermann 2007, Ghazali and Efendy 2016). This greater removal was further

318 supported by the higher amount of residue obtained after the TGA analysis for AT treated fibres

319 compared to the HT treated fibres (Beg 2007).

15
320 3.5 SEM microscopy of hemp fibre

321
322 Fig. 11. SEM images of hemp fibre surfaces (a) UT fibre (b) AT/one hour alkali treated fibre (c)
323 granulated before HT alkali treated fibre (d) granulated after HT alkali treated fibre.

324 Fig. 11 shows the SEM micrographs of hemp fibre. As can be seen in Fig. 11a, the UT fibres are

325 mostly bundle form; substances known to include lignin, pectin, hemicellulose and other non-

326 strengthening components are localised on their surfaces (Ghazali and Efendy 2016). Alkali

327 treated hemp fibres appeared to have undergone some degree of fibre separation known to occur

328 due to the removal of some of these components (Fig. 11b, 11c and 11d). However, it was found

329 that the AT treatment resulted in very little separation of fibres compared to the HT alkali

330 treatment (Fig. 11b). It was also found that the fibres granulated after HT alkali treatment were

331 better separated compared to the fibres granulated before HT alkali treatment, which is evident

332 from Fig. 11d compared to Fig. 11c.

333 3.6 Fibre mat assessment

334 It was found that only fibres granulated after HT alkali treatment were sufficiently separated to

335 successfully be used in a dynamic sheet former to form short hemp fibre mats (Fig. 5a and Fig.

16
336 6a). Fig. 12 shows the fibre orientation distribution profiles obtained for the mats analysed using

337 OrientationJ (ImageJ). As can be seen for the random mats, there appeared only a relatively small

338 broad peak (almost a flat curve). In contrast, there appeared a sharp predominant peak for the mats

339 produced using DSF around 0 ° (± 5 °), i.e. the preferred orientation direction. The coherency

340 factors generated by the OrientationJ program for the DSF mats and random mats were 0.23 (±

341 0.028) and 0.11 (0.038), respectively. The predominant peak and higher coherency factor for the

342 DSF mats compared to the broad peak and lower coherency factor for the random mats support the

343 potential of dynamic sheet former to produce aligned short hemp fibre mats.

344

345 Fig. 12. Fibre orientation distribution profiles obtained by OrientationJ.

346 3.7 Evaluation of composites

347
348 Fig. 13. Typical stress-strain curves for polypropylene reinforced with 15 wt% hemp fibre loaded
349 parallel and perpendicular to the DSF rotation (main fibre orientation) direction.

17
350 Composites were tested parallel and perpendicular to the main fibre orientation direction (DSF

351 rotation direction). Fig. 13 shows the stress versus strain curves for the composites with fibre

352 content of 15 wt% along with that of neat PP for comparison purposes. Neat PP extended in a

353 ductile manner to high strain without fail, whereas the incorporation of fibres caused PP to fail in

354 almost a brittle manner without much noticeable yielding.

a b

355

356 Fig. 14. Graph representing (a) tensile strength and (b) Young’s modulus for the hemp composites
357 tested parallel and perpendicular to the DSF rotation direction.

358 Tensile properties for neat PP along with composites are presented in Fig. 14. The maximum

359 tensile strength and Young’s modulus of the composite were approximately 59 and 120 % higher

360 than for neat PP. From the results, it can be seen that composite tested parallel to the main fibre

361 orientation direction exhibited higher tensile properties compared to the composite tested

362 perpendicular to the main fibre orientation direction. This further supports the potential of DSF to

363 produce aligned fibre mats. It has been reported that the best mechanical properties for composites

364 are generally being obtained when the fibres are aligned parallel to the direction of the applied

365 load (Herrera-Franco and Valadez-Gonzalez 2005, Pickering, Efendy et al. 2015).

366 4. Conclusion
367 The high temperature treatment at 120 °C using 5wt% NaOH and 2wt% Na 2SO3, with a fibre to

368 solution ratio of 1:8, improved the tensile strength and Young’s modulus of hemp fibres by 51%

369 and 62% respectively compared to untreated fibre. In contrast, tensile strength and Young’s

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370 modulus of ambient temperature treated hemp fibre were lower than that of untreated fibres by

371 16% and 14% respectively. SEM, XRD, FTIR and TGA analyses support that the high

372 temperature treatment removes more non-strengthening components from the fibres compared to

373 ambient temperature treatment. Improvement of fibre strength with high temperature alkali

374 treatment compared with the reduction of fibre strength obtained with ambient temperature alkali

375 treatment suggests better packing of cellulose chains occur for high temperature treatment

376 providing better resistance to cellulose degradation. Therefore, high temperature treatment is

377 recommended for producing strong and stiff fibres for use in natural plant fibre composites.

378 Overall, significantly aligned short hemp fibre mats from high strength hemp fibres was produced

379 using DSF.

380 Acknowledgements
381 This research received no specific grant from any agency in the public, commercial, or not-for-

382 profit sectors. However, the authors would like to thank to the University of Waikato’s

383 Composites research group for their support.

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