Characterization of Mechanical Properties of

Jute/PLA Composites Containing Nano SiO2

Modi ed By Coupling Agents
Xueyang Song
Soochow University
Cuicui Fang
Soochow University
Yuanyuan Li
Soochow University
Ping Wang (  pingwang@[Link] )
Soochow University [Link]
Yan Zhang
Soochow University

Research Article

Keywords: laminating composite materials, Jute non-woven, PLA, biodegradable, nano-SiO2

Posted Date: September 20th, 2021

DOI: [Link]

License:   This work is licensed under a Creative Commons Attribution 4.0 International License.
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Version of Record: A version of this preprint was published at Cellulose on November 23rd, 2021. See the
published version at [Link]
 1 Characterization of mechanical properties of
2 jute/PLA composites containing nano SiO2
3 modified by coupling agents
4 Xueyang Song, Cuicui Fang, Yuanyuan Li, Ping Wang, Yan Zhang*
5 National Engineering Laboratory for Modern Silk, College of Textile and Clothing
6 Engineering, Soochow University, Suzhou, China
7 * Corresponding author: Yan Zhang (yanzhng86@[Link])
8

9 Abstract: Although jute fibers-reinforced PLA composites shows strong application

10 prospects, their low mechanical properties limit their applications to some extent. In
11 this paper, nano-SiO2 particles as well as modified nano SiO2 by coupling agents
12 which can efficiently improve the strength and toughness of composite materials are
13 introduced into the PLA matrix. The bending, stretching and thermal properties of
14 designed jute/PLA nonwoven composites were studied. The study shows that the
15 nano-SiO2 particles are beneficial to the interface performance between the PLA
16 matrix and jute leading to improvement in the mechanical property and thermal
17 stability. Moreover, thermomechanical properties indicate that the addition of SiO2
18 can improve the jute/PLA interfacial adhesion and increase the glass transition
19 temperature of the material. Finally, toughening mechanism of nano-SiO2 particles in
20 the jute/PLA composite was analyzed.
21 Keywords: laminating composite materials; Jute non-woven; PLA; biodegradable;
22 nano-SiO2
23
24 Introduction
25 In recent years, thermoplastic composites are increasingly applied in the
26 high-performance engineering field due to their low density, good recyclability, and
27 high production efficiency (Faruk et al. 2012). However, environmental compatibility
28 of these materials is still a huge challenge. In this case, fully biodegradable green
29 composite materials provide a feasible solution. To prepare a completely
30 biodegradable composite material, natural fiber is a desirable reinforcing material and
31 natural polymer can be selected as matrix material, such as jute/polylactic acid (PLA)
32 composite materials. PLA, a polymer material, is produced from renewable
33 agricultural raw materials. It has tremendous advantages such as high strength, high
34 hardness, transparency and industrial production, and is one of the most promising
35 biodegradable polymers (Qu et al. 2015). Among all biodegradable reinforced fibers,
36 jute fiber has low cost, biodegradability and excellent mechanical property, which has
37 made it as one of the most widely used natural plant fibers in the research of green
38 bio-based composites (Dong et al. 2014). There are wide possible applications for
39 jute/PLA composite, and a lot of research have been proposed to investigate its
40 mechanical properties (Bax and Mussig 2008; Mohammed et al. 2019; Nishino et al.
41 2003; Pan et al. 2007). However, PLA resin matrix lacks chemical bonds and
42 functional groups that react with jute. Therefore, the interface compatibility between
43 jute fiber and PLA is poor, leading to a poor mechanical property of final composite.
44 (Balla et al. 2019; Costa et al. 2012; He et al. 2019; Hossen et al. 2020; Pereira et al.
45 2019). At present, some physical and chemical methods have been proposed,
46 including fiber treatment technologies such as acylation, alkali treatment,
47 etherification and isocyanate treatment, as well as the use of coupling agents to
48 improve the interfacial bonding properties of jute/PLA composites (Dong et al. 2020;
49 Fang et al. 2020; Huda et al. 2007; Kumar et al. 2010; Kakroodi et al. 2012). Nano
50 particle is also a feasible option to toughen the polymer matrix and improve the
51 mechanical properties of fiber-reinforced composites.
52 In recent years, nano particles have been extensively applied to prepared
53 composites, which has significantly improved the mechanical properties of
54 composites materials (Gauvin et al. 2015; Jumahat et al. 2012; Jumahat et al. 2010).
55 Among the nanoparticles used as reinforcing materials, many researchers chose
56 doping nano-silica (nano-SiO2) to improve the mechanical properties of
57 fiber-reinforced composite materials (Jumahat et al. 2015; Jumahat et al. 2012;
58 Jumahat et al. 2010). Luo et al. (2018) used technology-resin film infusion (RFI)
59 technology to prepare nano-SiO2 modified carbon fiber reinforced composite
60 materials. When the content of nano-SiO2 is 4 wt%, the toughening and strengthening
61 effect is the best. The tensile strength and flexural strength increased to 595.69 and
62 703.76 MPa, respectively, which were 86.30% and 126.98% higher than the tensile
63 strength and flexural strength of intact sample without SiO2. Hashim et al. (2019)
64 studied the effect of SiO2 nanoparticles as a reinforcing filler on the tensile response
65 of basalt fiber reinforced polymer (BFRP) composites. It was found that the addition
66 of SiO2 nanoparticles showed significant improvement in tensile modulus with 6%,
67 14% and 19% for 5 wt%, 15 wt% and 25 wt% nano-SiO2 content, respectively. Reddy
68 et al. (2010) used traditional melt blending technology to prepare low nanoparticle
69 loaded polymer composites with improved mechanical properties. The results of
70 tensile tests indicate that the addition of SiO2-g-DGEBA particles to the polymer
71 matrix led to an increase of both elastic modulus and toughness (from 0.36 to 0.54
72 GPa, and 19.06 to 21.05 MJ/m3, respectively). Filling nano-SiO2 into thermoplastic
73 matrix can combine the rigidity of nano-SiO2 with the toughness of thermoplastic
74 matrix, which makes ultimate composite have comprehensive mechanical
75 performance (Hashim et al. 2019; Luo et al. 2018; Park et al. 2020).
76 In this study, nano-SiO2 particles were adopted and dispersed into the PLA
77 matrix aiming to improve the mechanical property of jute/PLA composite. Moreover,
78 considering the dispersibility, the nano-SiO2 was first modified with different silane
79 coupling agents, then combined into PLA-based composite films and finally
80 incorporated in final laminated composites. This use of sandwich-like lamination
81 structure layer can mix PLA and jute as evenly as possible. Therefore, the effect of
82 silane coupling agents on the mechanical property of as-prepared composites via
83 hot-pressing technology was comprehensively analyzed.
 84

85 Materials and methods

86 Materials
87 PLA (4032D; 1.24 g/cm3) was supplied by Nature Works, USA; Jute fibers (1.45
88 g/cm3) was purchased from Shandong Jiangke Linyi Co., Ltd; Nano silica (SiO2,
89 99.5%, 50±5 nm) was provided by Suzhou Great Medical Technology Co., Ltd;
90 Silane coupling agent (KH550, KH560, KH570) chemicals were provided by Jiangsu
91 Argon Krypton Xenon Material Technology Co., Ltd. KH550
92 (NH2CH2CH2CH2Si(OC2H5)3) belongs to aminosilane, KH560
93 (CH2OCHCH2O(CH2)3Si(OCH3)3) belongs to epoxy silane, KH570
94 (CH3CCH2COO(CH2)3Si(OCH3)3) belongs to formaldehyde acryloyloxy functional
95 group silane.
96

97 Preparation of modified SiO2

98 The absolute ethyl alcohol and deionized water were first mixed with a mass
99 ratio of 9:1, and 5 g of SiO2 was added into 100 mL of mixture. The SiO2 solution was
100 then sonicated in an ultrasonic cleaner for 1 h. The coupling agent, e.g. KH550, with a
101 volume of 5% of the mixture was prepared and adjusted to the pH of 4 with oxalic
102 acid. The above mixed solutions were magnetically stirred for 3 h at 60 ℃ for
103 reaction. Finally, it was centrifuged (model: TG16G) and then washed with absolute
104 ethanol solution for 3 times. The obtained precipitate was dried in an oven at 60 ℃
105 for 4 h to obtain modified SiO2 powders, named as KH550-SiO2, KH560-SiO2 and
106 KH570-SiO2 respectively. The scheme of preparation process of modified SiO2 is
107 illustrated in Figure 1.
108
109 Fig. 1 The scheme of preparation process of modified SiO2
110

111 Preparation of composite SiO2-PLA films

112 3 g of PLA raw material was dissolved it in dichloromethane, stirred
113 magnetically (model: DF-101S) for 1.5 h at room temperature; different mass
114 fractions of modified SiO2 (0.5 wt%, 1 wt%, 2 wt%, 4 wt% and 8 wt%) were mixed
115 into dichloromethane and ultrasonicated (model: VGT-1730QT) for 40 min. These
116 two solutions were mixed and magnetically stirred for 2 h, followed by
117 ultrasonication for 1 h at 35 ℃. Then, the solution was poured into a glass plate and
118 placed in a fume hood at room temperature to make the methylene chloride solvent
119 completely volatilize. Finally, the composite SiO2-PLA film was peeled from the
120 mold and placed in a vacuum oven at a temperature of 45 ℃ for 3 h, as shown in
121 Figure 2.

122
123 Fig. 2 The scheme of preparation process of composite SiO2-PLA film
124

125 Preparation of jute non-woven

126 The preparation process of jute non-woven is shown in Figure 3. The aspect ratio
127 of jute fiber is about 314:1. First, the fluffy jute fibers was combed, opened and mixed
128 through a coarse-garge carding machine (model: SSL-II) to make the fibers looser and
129 more uniform. Then the loose jute fibers were sent to the blender for further fine
130 opening. The fine opening and carding process make the jute fibers finally become a
131 fluffy and uniform fiber web. The fiber web obtained by cross-netting has higher
132 quality. In order to obtain a certain strength of non-woven fabrics, the four-layer jute
133 net were finally reinforced with a needle punch (model: CSZC). The final thickness of
134 the jute nonwoven is 0.51±0.04 mm, and the surface density is 200±2 g/m2.

135
136 Fig. 3 The preparation process of jute non-woven fabric

137

138 Preparation of composite material

139 To remove all moisture, SiO2-PLA films and jute nonwoven were first dried in a
140 vacuum oven at 80 ℃ for 6 h before hot pressing. The laminated composite material
141 was processed through a compression mold using a film stacking method, in which
142 two jute pads were arranged between three PLA films in parallel, as demonstrated in
143 Figure 4. The entire assembly was then placed in a steel mold controlled under
144 different time and temperature. The laminated material is compacted for 0.5 h under
145 the conditions of a temperature of 180 ℃ and a pressure of 1 MPa, and then is
146 naturally cooled in the vulcanization machine(model: HG-3621) for 8 h. After 8 h, the
147 sample was taken out of the laminating mold, and the width and length were 150 mm
148 ×150 mm and the thickness was 2 mm, and the mass ratio of PLA to jute was 10:3.
149 The samples are numbered according to the type of coupling agent and concentration.
150 For example, 550-0.5, in which 550 represents the silane coupling agent of KH550,
151 the sample untreated with the coupling agent is directly represented by SiO2, and 0.5
152 represents 0.5 wt% of the modified SiO2 mass fraction in SiO2-PLA film.

153
154 Fig. 1 The preparation process of composite material

155

156 Characterization of jute / PLA composites

157 In order to study that effect of different silicon dioxide on the mechanical
158 properties of jute/PLA composite, the SiO2 modified by silane coupling agent was
159 characterized by infrared transmission spectroscopy (5700, Nicli Instruments, USA)
160 and particle size analyzer (LS-909). At the same time, the mechanics of composite
161 materials were characterized by scanning electron microscope (TM3030, Hitachi,
162 Japan), dynamic mechanical thermal analysis (SDTQ800, V21.3, Build 96, USA) and
163 related mechanical testing methods (Instron 336, USA).
164

165 Results and discussions

166 The composition and physical property of modified SiO2

(b)
(a) KH570-SiO2 2987
1100
KH550 2940 1460
1718
KH560-SiO2 2940
Transmission (%)

Transmission (%)
460

2987 KH550-SiO2
KH560 1460

SiO2 800
1718
KH570 1100

4000 3500 3000 2500 2000 1500 1000 500 4000 3000 2000 1000
Wavenumber (cm-1)
167 Wavenumber (cm-1)

168 Fig. 5 (a) FTIR spectra of KH550, KH560 and KH570; (b) FTIR spectra of SiO2,

169 KH550-SiO2, KH560-SiO2 and KH570-SiO2 nanoparticle

170

171 Fourier-transform infrared spectroscopy (FTIR) can be used to verify the graft
172 polymerization of silane coupling agents on SBR surface. Figure 5 shows the infrared
173 spectra of KH550, KH560 and KH570 as well as corresponding silane coupling agent
174 grafted SiO2. It can be seen from Figure 5 (b) that the infrared spectrum of the SiO2
175 before and after modification has a large absorption peak near 1100 cm-1, which is the
176 antisymmetric absorption peak of Si-O-Si bond, and near 800 cm-1 is the symmetrical
177 contraction vibration of the Si-O-Si bond. The infrared spectrum of KH550-SiO2 is
178 relatively flat compared to others in the range of 3500-3100 cm-1, indicating that -NH2
179 in KH550 has been successfully grafted and modified on the surface of nano-SiO2. In
180 Figure 5 (a), KH550 shows characteristic peaks of -CH2- at 2940 cm-1 and 1640 cm-1,
181 while KH550-SiO2 also has a shoulder peak at 2940 cm-1 and 1460 cm-1, which
182 further indicates that KH550 has successfully modified nano-SiO2. Compared with
183 FTIR spectrum of SiO2, in the spectrum modified by KH560-SiO2, the stretching
184 vibration absorption peak of methyl appears near 2987 cm-1 which is related to
185 characteristic methyl peak of KH560, indicating that KH560 silane coupling agent has
186 been successfully grafted to the second Si-O surface (He et al. 2019). In the infrared
187 spectrum of KH570 and KH570-SiO2, there is a C=O stretching vibration absorption
188 peak on the carbonyl group at 1718 cm-1, which indicates that KH570 has been
189 successfully grafted onto nano-SiO2.
190 The particle size of original and modified SiO2 is shown in Table 1. The surface
191 morphology of original and modified SiO2 is shown in Figure 6. Nano-SiO2 has a
192 small particle size, a large specific surface area. Due to the large specific surface area,
193 the powder is easy to agglomerate together, so that the total surface area is reduced,
194 and the total energy is reduced. It can be clearly seen that the unmodified particles are
195 larger than modified particles, and KH560 has the best modification effect on SiO2
196 particles. Unmodified nano-SiO2 has a relatively high polydispersity index (PDI) and
197 the particle size, particle size, and unevenness appeared and severe aggregation. The
198 particle size and PDI of the modified nano-SiO2 powder are reduced, indicating that
199 the nano-SiO2 modified by the silane coupling agent can effectively prevent its
200 agglomeration and achieve the modification purpose. On the one hand, the hydroxyl
201 groups on the particle surfaces are replaced by organic functional groups, reducing the
202 number of active silanol groups, thereby reducing the tendency of nanoparticles to
203 agglomerate. On the other hand, the grafted long carbon chain increases the distance
204 between particles and the steric hindrance of the hydroxysilyl polycondensation
205 reaction on the particle surface, which increases the difficulty of effective collisions
206 and more conducive to the dispersion of nanoparticles.
207

208 Table 1 The spectification of prepared nano SiO2

Z-Average Peak Size Peak Intensity

Sample PDI
(nm) (nm) (%)

SiO2 300 220.8 65.2 0.343

KH550-SiO2 107.7 143.3 69.3 0.287

KH560-SiO2 67.6 92.7 100 0.210

KH570-SiO2 91 136.6 100 0.229

209
210 Fig. 6 The surface morphology of SiO2. (a) SiO2; (b) SiO2-550; (c) SiO2-560; (d) SiO2-570

211

212 Bending property

(a) 50 (b)
SiO2 4.0 SiO2
45
SiO2-550 SiO2-550
40 3.5
Bending Modulus (GPa)

SiO2-560 SiO2-560
35 SiO2-570 3.0 SiO2-570
Stress (MPa)

30 2.5
25
2.0
20
1.5
15
1.0
10
5 0.5

0 0.0
0 0.5 1 2 4 8 0 0.5 1 2 4 8
Mass Fraction (%) Mass Fraction (%)

213

5.0 (d) 96
(c) SiO2 SiO2
4.5 SiO2-550 SiO2-550
93
Bending Break Work (J/cm3)

SiO2-560 SiO2-560
Bending Strain (%)

4.0
SiO2-570 90 SiO2-570
3.5
87
3.0
84
2.5
81
2.0
78
1.5
75
1.0
0 0.5 1 2 4 8 0 0.5 1 2 4 8
Mass Fraction (%) Mass Fraction (%)
214
215 Fig. 7 The effect of nano-SiO2 on tensile properties of jute/PLA composite bending

216 performance. (a) Bending strength; (b) Modulus; (c) Bending strain; (d) Bending break work

217
218 The experiment was repeated at least 5 times for each sample. Figure 7 (a) and (b)
219 shows the bending strength and modulus of pure jute/PLA fibers composites involving
220 SiO2 and modified SiO2 nanoparticles with different mass fractions. It can be seen that
221 the bending modulus of jute/PLA fibers composites is relatively low. With
222 incorporation of SiO2, the bending strength and modulus of the composites is more or
223 less improved. Compared with pure jute/PLA composite material, there is no
224 significant improvement in the bending performance of the sample SiO2-4. However,
225 after adding the nano-SiO2 particles modified by the coupling agents, the bending
226 strength and modulus of 550-4 increased to 29.95 MPa and 1.25 GPa respectively,
227 which were 149.5% and 76.8% higher than those of the jute/PLA composite, and
228 increased by 137.4% and 72.0% compared with the unmodified SiO2 jute/PLA
229 composite. The bending strength and modulus of 560-4 were increased to 36 MPa and
230 2.17 GPa respectively, and the bending strength and modulus of 570-4 were 34 MPa
231 and 2.01 GPa. Compared with the jute/PLA fibers composites, the bending strength of
232 560-0.5, 560-1, 560-2, 560-4 and 560-8 composites increased by 2.8%, 96.6%, 74.7%,
233 74.2% and 68.3% respectively. It is also found from Figure 7 (a) and (b) that as the
234 mass fraction of different types of added SiO2 increases, the change trend of material
235 bending strength and modulus is basically same.
236 The similar phenomena can be also observed in the bending strain and bending
237 break work of jute/PLA composites. The bending break work was calculated by
238 integrating the tensile stress–strain curves. As shown in Figure 7 (b), the increase of
239 SiO2 improves the bending strain and bending break work of jute/PLA composites.
240 In short, the bending performance of the sample increases with the increase of
241 the SiO2 mass fraction, peaks at about 1wt%, and then decreases. That is, under the
242 same mass fraction, SiO2 treated with different silane coupling agents has the same
243 effect on the jute/PLA composite. The SiO2 sample modified with KH560 has the best
244 bending strength and modulus. It is mainly due to the fact that realize the interface
245 combination through the coupling agent, forming a better entirety, and then
246 strengthening the effect of stress transmission(Yang et al. 2009; Sanivada et al. 2020;
247 Fang et al. 2020; Li et al. 2013). Sample 560-1 has best bending performance
248 resulting from the excellent dispersibility and uniform particle size as illustrated in
249 Table 1.
250

251 The fracture morphology

252 In order to illustrate the toughening mechanism, the fracture morphology of the
253 reinforced PLA-based composite after the tensile test is shown in Figure 8. The tensile
254 fracture surface of the jute/PLA composite, illustrated in Figure 8 (a), shows large
255 amounts of fiber extraction leading to a lower mechanical resistance to some extent.
256 This is consistent with comparatively large elongation ratio of the composite material
257 which also indicates a poor interfacial cohesiveness. Figure 8 (b) shows the SiO2
258 particles modified by KH560 are evenly distributed in PLA matrix. At this time,
259 delamination occurs in the tensile section, and the bending strength is reduced. With
260 the increase of SiO2, there are more holes appeared which are prone to cause fracture.
261 Nano-SiO2 particles induce local plastic deformation of the PLA matrix, showing a
262 rougher fracture surface. And as the stress concentration point, SiO2 particles produce
263 a large number of small cracks, and has a small amount of fibers extraction, as shown
264 in the Figure 8 (d). There are a large number of cracks and fiber extraction at the
265 break of sample 560-4. Therefore, sample 560-4 consumes a lot of energy when it
266 breaks. Due to the poor dispersibility of SiO2, the modified SiO2 re-aggregated at 8%
267 by mass fraction. As the mass fraction of SiO2 increases, there are more contact points
268 between SiO2 and jute, which reduces the adhesion between jute and PLA, and the
269 mechanical properties dropped rapidly, as shown in Figure 8 (f).
270
271 Fig. 8 The fracture surface morphologies of jute/PLA composite (×200). (a) jute/PLA

272 composite. (b) Sample 560-0.5. (c) Sample 560-1. (d) Sample 560-2. (e)Sample 560-4. (f)
273 Sample 560-8

274

275 Stretching property

(a) 14 SiO2
(b) 3.0
SiO2
12 SiO2-550 2.7 SiO2-550
SiO2-560
Tensile Strength (MPa)

2.4 SiO2-560
Tensile Modulus (GPa)

SiO2-570
10 SiO2-570
2.1
8 1.8
1.5
6
1.2
4 0.9
0.6
2
0.3
0 0.0
0 0.5 1 2 4 8 0 0.5 1 2 4 8
Mass Fraction (%) Mass Fraction (%)

276

(c) SiO2
1.2 (d) 7 SiO2
SiO2-550
SiO2-550
Elongation at Break (%)

1.0 SiO2-560 6
Tensile Break Work (J/cm3)

SiO2-560
SiO2-570
5 SiO2-570
0.8
4
0.6
3
0.4
2
0.2
1

0.0
--
0 0.5 1 2 4 8 0 0.5 1 2 4 8
Mass Fraction (%) Mass Fraction (%)

277
278 Fig. 9 The effect of nano-SiO2 on tensile properties of jute/PLA fibers composites. (a) Tensile

279 strength; (b)modulus; (c) Elongation at break; (d) Tensile break work

280

281 The tensile property of the jute/PLA composite and the nano-SiO2 jute/PLA
282 composites is shown in Figure 9. The tensile strength of 560-0.5 increased from 1.47
283 MPa in the jute/PLA composites to 11.03 MPa. The elastic modulus of 560-0.5 is as
284 high as 2.01 GPa, which is 614.2% higher than the 0.28 GPa of the jute/PLA
285 composites. The tensile strength of 560-1 is 8 MPa and the elastic modulus of 560-1 is
286 0.81 GPa. The tensile strength of 560-2 is 7.59 MPa and the elastic modulus is 2.32
287 GPa. The tensile strength of 560-4 is 11.92 MPa and the elastic modulus is 2.57 GPa.
288 The tensile strength of 560-8 is 5.02 MPa and the elastic modulus is 1.20 GPa. The
289 tensile break work of SiO2-4, 550-4, 560-4, and 570-4 is increased by 138.0%,
290 389.7%, 609.5%, 417.0% compared with the jute/PLA fibers composites.
291 It is concluded from Figure 9 that the cooperation of nano-SiO2 can effectively
292 improve the tensile tolerance of composite materials. With the increase of nano-SiO2
293 content, the change trend of the tensile properties of the composite material before
294 and after modification is basically the same. And when the SiO2 mass fraction is same,
295 the sample modified by KH560 has the best tensile strength. This can be attributed to
296 the small particle size and uniform shape of SiO2 modified by KH560, which is
297 consistent with the DLS data.
298 When preparing jute/PLA laminates, SiO2 can be more evenly dispersed in the
299 matrix, thereby enhancing the effective load transfer between jute and PLA,
300 improving the tensile properties of the composite material. The silane coupling agent
301 can serve as a bridge to improve the compatibility of the interface between SiO2 and
302 jute/PLA, forming a better whole, and then strengthening the stress transmission.
303 Figure 10 shows the interaction between the silica particles and the interface of the
304 jute/PLA composite before and after the modification. The silane coupling agent can
305 react with the silicon hydroxyl group on the surface of SiO2 after being hydrolyzed.
306 The degree of aggregation of modified-SiO2 is reduced, exposing more binding sites
307 that can interact with PLA. At the same time, the long-chain structure of the coupling
308 agent will generate entanglement on the interface between jute fiber and PLA, which
309 efficiently enhances the interface bonding performance, expedites interfacial stress
310 transfer, and ultimately improves the mechanical property of the composite material.

311

312 Fig. 10 The interaction between the silica particles and the interface of the jute/PLA

313 composite before and after the modification of the silane coupling agent.

314

315 Dynamic mechanical thermal analysis (DMTA)

316 Figure 11 respectively show the dynamic storage modulus (E'), loss modulus (E'')
317 and loss coefficient tanδ（E''/E'）of jute/PLA composites with different contents of
318 SiO2 modified from room temperature to 180 ℃. As shown in Figure 11 (a) and (b),
319 the stored modulus values and corresponding temperatures of different samples at the
320 beginning of chain segment movement. In the temperature range studied, the storage
321 modulus of the jute/PLA composite modified by SiO2 is higher than that of the
322 untreated jute/PLA composite. In addition, different variables showed the same
323 change pattern. With the increase of SiO2 content, the storage modulus of the
324 modified jute/PLA composite material increases first and then decreases. The increase
325 in storage modulus and corresponding temperature of chain segment starting to move
326 indicates that the interface adhesion between jute and PLA has been improved,
327 resulting in greater stress transfer between them(Porras and Maranon. 2012). That is,
328 the increase of the SiO2 content can improve the interfacial adhesion, but because of
329 the poor dispersibility of SiO2, when the content is greater than 4%, the effect of the
330 coupling agent on SiO2 modification is not obvious, and the jute/PLA interface
331 adhesion begins to decrease.

(a) (b) 69
SiO2
3.5
SiO2-550
Storage Modulus (MPa)

3.0 SiO2-560 66

Temperature (℃)
SiO2-570
2.5
63
2.0
60
1.5
SiO2
1.0 SiO2-550
57
SiO2-560
0.5 SiO2-570
54
0.0
0 0.5 1 2 4 8 0 0.5 1 2 4 8
Mass Fraction (%) Mass Fraction (%)

332

(c) 250 SiO2 (d) 75

225 SiO2
SiO2-550 SiO2-550
200 SiO2-560 72
Temperature (℃)

SiO2-560
Loss Modulus (MPa)

175 SiO2-570 SiO2-570

69
150
125 66

100 63
75
60
50
25 57
0
0 0.5 1 2 4 8 0 0.5 1 2 4 8
Mass Fraction (%) Mass Fraction (%)

333

(e) (f)
SiO2 80 SiO2
0.25
SiO2-550 SiO2-550
SiO2-560 78 SiO2-560
Temperature (℃)

0.2
SiO2-570 SiO2-570
76
0.15
Tanδ

74

72
0.1

70

0.07
68
0 0.5 1 2 4 8 0 0.5 1 2 4 8
Mass Fraction (%) Mass Fraction (%)

334
 (g) 4 74.2 80.1
560-4 250 0.08
68.4
200
3 0.07
Storage Modulus (GPa) 150
2
100 0.06

Loss Modulus (MPa)

1 50
0.05

Tanδ
0 0
57.3
0.8 69.2 80
control group 0.30
70
0.6 56.7 60
0.25
50 0.20
0.4 40 0.15
30
0.2 20
0.10
10 0.05
0.0
20 40 60 80 100 120 140 160 180
Temperature (℃)

335
336 Fig. 11 The DMTA of jute/PLA composite. (a) Storage modulus; (b) The temperature
337 corresponding to storage modulus; (c) The maximum loss modulus; (d) The
338 temperature corresponding to the maximum loss modulus; (e) The maximum tanδ; (f)
339 The temperature corresponding to the maximum tanδ; (g) The comparison of DMTA
340 between jute/PLA composite and sample 560-4
341

342 The next study parameter is the loss modulus, which represents the energy
343 dissipated by the jute/PLA composite under stress (Laly et al. 2003; Doan et al. 2007).
344 It is observed in Figure 11 (c) and (d) that the loss modulus value of the
345 SiO2-modified jute/PLA composite is much higher than that of the untreated jute/PLA
346 composite. It is known that the maximum value of loss modulus corresponds to the
347 glass transition temperature (Tg) of the composite material. The Tg of the untreated
348 jute/PLA composite is around 57.3 ℃. In contrast, the Tg of the SiO2-modified
349 jute/PLA composite material moved to the high temperature zone, reaching a
350 maximum of about 74.2 °C.
351 Finally, loss factor, tanδ, which refers to the ratio of the loss modulus of the
352 composite material to the storage modulus of the composite material, and represents
353 the damping energy of the material. The decrease of the tanδ value indicates SiO 2
354 improves the bonding strength between PLA and jute, and reduces the fluidity of PLA
355 macromolecules in the composite material. Due to the improvement of the
356 hydrophobicity of the SiO2-modified Jute/PLA, the interfacial adhesion is enhanced,
357 and the fluidity of the polymer chains at the jute/PLA composite interface is reduced.
358 Among the unmodified SiO2 and SiO2 jute/PLA composites modified by KH550,
359 KH560 and KH570, the unmodified jute/PLA composites have the highest tanδ value,
360 and the KH560 modified SiO2 jute/PLA composites has the highest tanδ value,
361 indicating the dispersibility of SiO2 modified by KH560 is best. Among all SiO2
362 composite material modified by KH560, jute/PLA with a SiO2 content of 4% has the
363 best interface bonding. As shown in Figure 11 (e) and (f).
364 Comprehensive analysis of sample 560-4 has the best thermomechanical
365 properties. Compared with the jute/PLA composite, the storage modulus, glass
366 transition temperature and loss modulus have increased; tanδ has decreased. As shown
367 in Figure 11 (g), the comparison of DMTA between jute/PLA composite and sample
368 560-4. The glass transition temperature of sample 560-4 is 29.5% higher than that of
369 the jute/PLA composite, indicating that the experimental optimization has improved
370 the bonding strength of the interface between PLA and jute. The storage modulus
371 values of different samples decrease with increasing temperature. The tanδ value of
372 the jute/PLA composite material increased with the increase of temperature when the
373 mass fraction of SiO2 treated by KH560 was 4%, until it reached the maximum at
374 69.2℃, and then the opposite trend was observed in the rubber area.
375

376 Conclusions
377 In order to enhance the mechanical properties of the jute/PLA composite,
378 nano-SiO2 particles modified by different coupling agents were introduced into the
379 PLA matrix. The effect of the type of coupling agent and the mass fraction of SiO2 on
380 the bending, stretching and thermomechanical properties of the composite was studied.
381 The study shows that the addition of SiO2 improves the interface performance
382 between PLA and jute and improves the mechanical properties of the composite
383 material. Meanwhile, the smaller the particle size of SiO2 and the more uniform the
384 particles, the better the mechanical properties of the composite material. The analysis
385 of thermomechanical properties shows that the addition of SiO2 can improve the
386 thermomechanical properties and glass transition temperature of composite materials.
387 In addition, as shown in the tensile and bending tests, the strength, stiffness and
388 toughness of SiO2 composite material with mass fraction of 4% modified by the
389 KH560 coupling agent are significantly improved, and its elongation at break is
390 slightly affected. Compared with intact jute/PLA composite, the flexural strength and
391 flexural modulus of sample 560-4 increase by 150.3% and 77.4%, respectively, while
392 the tensile strength and tensile modulus increase by 816.9% and 700.1%, respectively.
393 Its excellent mechanical properties are the result of the better interface compatibility
394 of jute/PLA caused by the SiO2-CN bond. In addition, the fracture morphology of the
395 composite material shows that the plastic deformation of the matrix caused by SiO2
396 are the main toughening mechanisms.
397 In summary, adding SiO2 modified by coupling agent to jute/PLA composites
398 can improve the mechanical properties of composites, which can be used in packaging,
399 automotive and other industries. Make products more green and environmentally
400 friendly.
401

402 Acknowledgements
403 The work is gratefully supported by National Natural Science Foundation of
404 China (Grant No.11602156), Science and Technology Guiding Project of China
405 National Textile and Apparel Council (Grant No. 2020064).
406

407 Declaration of competing interest

408 The authors declare that they have no known competing financial interests or personal
409 relationships that could have appeared to influence the work reported in this paper.
410

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Figures

Figure 1

The scheme of preparation process of modi ed SiO2

Figure 2

The scheme of preparation process of composite SiO2-PLA lm

Figure 3

The preparation process of jute non-woven fabric

Figure 4

The preparation process of composite material

Figure 5

(a) FTIR spectra of KH550, KH560 and KH570; (b) FTIR spectra of SiO2, KH550-SiO2, KH560-SiO2 and
KH570-SiO2 nanoparticle
Figure 6

The surface morphology of SiO2. (a) SiO2; (b) SiO2-550; (c) SiO2-560; (d) SiO2-570

Figure 7

The effect of nano-SiO2 on tensile properties of jute/PLA composite bending performance. (a) Bending
strength; (b) Modulus; (c) Bending strain; (d) Bending break work
Figure 8

The fracture surface morphologies of jute/PLA composite (×200). (a) jute/PLA composite. (b) Sample
560-0.5. (c) Sample 560-1. (d) Sample 560-2. (e)Sample 560-4. (f) Sample 560-8
Figure 9

The effect of nano-SiO2 on tensile properties of jute/PLA bers composites. (a) Tensile strength;
(b)modulus; (c) Elongation at break; (d) Tensile break work
Figure 10

The interaction between the silica particles and the interface of the jute/PLA composite before and after
the modi cation of the silane coupling agent.
Figure 11

The DMTA of jute/PLA composite. (a) Storage modulus; (b) The temperature corresponding to storage
modulus; (c) The maximum loss modulus; (d) The temperature corresponding to the maximum loss
modulus; (e) The maximum tanδ; (f) The temperature corresponding to the maximum tanδ; (g) The
comparison of DMTA between jute/PLA composite and sample 560-4
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