Composite Structures 267 (2021) 113865

Contents lists available at ScienceDirect

Composite Structures
journal homepage: [Link]/locate/compstruct

Multi-scale analysis of the interface structure and failure behaviors

for n-SiO2@jute fiber/PP composites
Xuan Liu, Yihua Cui ⇑
Institute of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210000, China

A R T I C L E I N F O A B S T R A C T

Keywords: To enhance the interface bonding performance between jute fibers (JFs) and polypropylene (PP), nano‐SiO2
Plant fiber reinforced composites (n‐SiO2) layers were coated on the carboxymethyl treated JFs (JFs‐COOH). Molecular dynamics (MD) simula-
Nano particles tion, microscopic modelling and macroscopic tensile test were used to study the interface structure and failure
Interface structure behaviors of n‐SiO2@JF/PP composites at multi‐scale level. The results of MD simulation indicated that n‐SiO2
Failure behaviors
layer including gel and array formed an interphase between JFs‐COOH and PP, which was acted as a bridge to
Multi‐scale analysis
bond JFs‐COOH and PP by the chemical bonding interaction and the mechanical interlocking of molecular
chains. With n‐SiO2 interphase, the interface binding energy of JF/PP composites was enhanced by 27.21%.
n‐SiO2 interphase served as a medium to transfer the tensile stress from PP to JFs‐COOH, eliminating the tensile
stress concentration at the interface defects. The tensile strength of n‐SiO2@JF/PP composites was increased by
32.82% than that of JF/PP composites. Owing to the multi‐layer and multi‐phase structure of n‐SiO2@JF/PP
composites, the interface failure behaviors included n‐SiO2@JFs breakage, n‐SiO2@JFs internal debonding,
n‐SiO2 interphase interlaminar debonding, n‐SiO2/PP interface debonding, PP cohesive failure. The strong
interface may lead to PP cohesive failure or the internal debonding of n‐SiO2@JFs.

s1. Introduction thermoplastic matrix [7–9]. Bayart et al. [10] coated n‐SiO2 particles
on the flax fibers to reinforce polylactic acid (PLA) composites. The
Plant fiber reinforced thermoplastic composites (plant fiber/ther- results indicated that the moisture resistant capability and the mechan-
moplastic composites), a key component of environmental boom, have ical properties of flax fiber/PLA composites were improved signifi-
received great interest in civil infrastructure and transportation indus- cantly by coating n‐SiO2 particles. Sun et al. [11] used sol–gel
try owing to their excellent mechanical properties, light weight, and method to coat n‐SiO2 particles on sisal fibers, demonstrating that n‐
low cost [1]. Despite the above mentioned advantages, some draw- SiO2 particles were effective to improve the mechanical properties of
backs limited the applications of plant fiber/thermoplastic composites, sisal fiber/polypropylene (PP) composites due to the strong interface
for example the weak interface bonding performance between hydro- bonding performance and sufficient load transfer.
philic plant fibers and hydrophobic thermoplastic matrix [2,3]. The However, few researches about the interface structure and failure
interface bonding performance was considered as the crucial factor behaviors of nano‐particles coated plant fiber/thermoplastic compos-
to affect the mechanical properties of plant fiber/thermoplastic ites were reported. Nano‐particles coated on plant fibers formed an
composites. interphase between the plant fibers and thermoplastic matrix. Owing
Various solutions were introduced by researchers to enhance the to the presence of nano‐particles interphase, the interface of plant
interface bonding performance of plant fiber/thermoplastic compos- fiber/thermoplastic composites was changed from the single
ites. Recently, coating nano‐particles on plant fibers has been proposed microstructure to a multi‐phase and multi‐scale one. Therefore, the
as a more effective method, driven by the excellent characteristics of interface structure and failure behaviors of nano‐particles coated plant
the surface and mechanical properties for nano‐particles [4–6]. fiber/thermoplastic composites were difficult to characterize by
Nano‐SiO2 (n‐SiO2) particles with unique three‐dimensional spherical single scale evaluation system.
structure and outstanding physicochemical features were used to Molecular dynamics (MD) simulation was the effective method
improve the interface bonding performance between plant fibers and to build the interface structure of fiber reinforced composites at

⇑ Corresponding author.
E-mail address: cuiyh@[Link] (Y. Cui).

[Link]
Received 3 March 2021; Accepted 13 March 2021
Available online 19 March 2021
0263-8223/© 2021 Elsevier Ltd. All rights reserved.
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

molecular level and thus achieve the visualization of the interface 2.4. Fabrication of n-SiO2@JF/PP composites
structure [12,13]. Moreover, MD simulation could calculate the
energy variation of interface interaction which would provide the The non‐woven webs with n‐SiO2@JFs and PP fibers were formed
quantitative analysis for studying the failure behaviors of fiber by a carding machine. Then the non‐woven webs were placed into a
reinforced composites. Tam et al. [14] simulated the interface needle machine (SCZ1150, Qingdao Jiaonan Machinery Factory,
debonding process of carbon fiber/epoxy composites in hygrother- China) to prepare the mats. After that, the mats were molded by a vul-
mal condition. The MD simulation results proved that the interface canizing machine at 180 °C. The molding pressures were controlled at
bonding performance was weak in high‐temperature saltwater due 1.5 MPa, 3.5 MPa, and 5.0 MPa for 3 min, respectively, and then
to the epoxy mechanical degradation. Zhang et al. [15] studied 15.0 MPa for 20 min. n‐SiO2@JF/PP composites with the thickness
the molecular structure of the interface for carbon nanotube‐sized of 2 mm contained 30 wt% of n‐SiO2@JFs.
carbon fiber/epoxy composites by MD simulation. The results indi-
cated that the interface performance between the CNT‐sized carbon 2.5. Characterization of n-SiO2@JFs
fibers and epoxy were determined by multiple factors, including
the CNT/epoxy interface binding energy, the packing density of
the molecular chains, and the steric hindrance of the functionalized 2.5.1. Morphology analysis
CNTs. The morphologies of n‐SiO2@JFs were examined by a scanning
Additionally, the interface failure behaviors of nano‐particles electron microscope (SEM, Hitachi SU‐4800, Hitachi Co., Ltd, China).
coated plant fiber/thermoplastic composites were lack of the micro- All the samples were gold coated prior to the examination.
scopic models, resulting in that the relationships between the interface n‐SiO2@JFs were embedded into epoxy resin for preparing the
bonding performance and the macroscopic mechanical properties of fiber slices. The fiber slices were imaged by a transmission electron
nano‐particles coated plant fiber/thermoplastic composites were not microscope (TEM, Fei Tecnai G2 T20, FEI Co., USA) to characterize
clearly illustrated. the cross‐sectional morphology of n‐SiO2@JFs.
In this research, MD simulation, microscopic modelling and macro-
scopic mechanical test were carried out to study the interface structure 2.5.2. Fourier transform infrared spectroscopy (FT-IR)
of n‐SiO2 layer coated jute fiber (n‐SiO2@JF)/PP composites at multi‐ A FT‐IR spectrometer (Nicolet Nexus 870, Nicolet Co., USA) was
scale level. Combined with micromorphology characterizations, the carried out to record the absorption spectra of n‐SiO2@JFs, from the
interface failure models of n‐SiO2@JF/PP composites were estab- wave numbers of 4000 to 400 cm−1.
lished, which illustrated the interface failure behaviors at microscopic
level. The results were expected to reveal the interface structure and 2.6. Tensile test of n-SiO2@JF/PP composites
failure behaviors of n‐SiO2@JF/PP composites
The tensile test of n‐SiO2@JF/PP composites
2. Experimental (150 mm × 20 mm × 2 mm) was proceeded on the electronic strength
tester (3369, Instron, USA) with a load cell of 5 kN. More than 5 samples
2.1. Materials and reagents of each group were tested with a cross head speed of 5 mm/min.
The fractured surfaces of n‐SiO2@JF/PP composites were ob-
JFs with the diameter of 15 ~ 55 μm were supplied by Hunan served by SEM. All the fractured surfaces were gold coated prior to
Shangke Co. Ltd., China. Tetraethoxysilane (TEOS), sodium hypochlo- the examination.
rite, ammonia hydroxide, sulfuric acid (98%), sodium hydroxide, 4‐
dimethylaminopyridine and ethanol were purchased from Shanghai 3. MD simulation
Macklin Biochemical Co. Ltd., China. PP fibers with the length of
50 mm were purchased from Shandong Hualong Co. Ltd., China. COMPASS force field was applied to build the molecular model of
the multi‐phase interfaces for n‐SiO2@JF/PP composites and conduct
2.2. Carboxymethyl treatment of JFs MD simulation. Atom‐based and Ewald summation methods were used
to calculate the van der Waals (vdW) interaction and electrostatic
1 g of JFs were soaked in the sodium hydroxide (10 wt%)/iso- interaction, respectively.
propanol (20 wt%) solution with the ultrasonic treatment at 40 °C
for 90 min. After that, 2.5 mol/L sodium hypochlorite, 8.0 wt% iso- 3.1 . Molecular models of JFs and JFs-COOH surfaces
propanol and 0.04 mol/L 4‐dimethylaminopyridine were added into
the above mixture. After a magnetic stirring at 60 °C for 4 h, the JFs The molecular model of JFs surface referred to the model used in
were washed by distilled water to remove the undesired byproducts. previous study, as Fig. 1 (a) illustrated [13]. The lattice parameters
Then, the JFs were immersed in 0.05 mol/L sulfuric acid solution at of JFs surface were set as 32.84 Å× 31.14 Å with three layers. The
25 °C for 2 h. Finally, the carboxymethyl treated JFs (JFs‐COOH) were FT‐IR spectra of n‐SiO2@JFs was shown in Fig. 2. The new peak
washed by distilled water, and dried at 70 °C for 2 h. (1600 cm−1) related to the carboxyl groups (–COOH) was appeared
after the carboxymethyl treatment [16], which demonstrated that
2.3. Preparation of n-SiO2@JFs the carboxyl groups were introduced on the JFs. There were three
kinds of hydroxyl groups presenting on the cellulose. According to
n‐SiO2@JFs were prepared by sol–gel technique. 0.1 g of JFs‐ the carboxymethylation of hydroxyl groups in the order of
COOH were immersed in a mixed solution of ethanol (30 ml) and C2 > C6 > C3, the hydroxyl groups (–OH) linked C2 were easily sub-
TEOS (0.8 ml). The ethanol (10 ml)/distilled water (1.6 ml) solution stituted by carboxyl groups [17], as Fig. 1 (b) showed.
and the ethanol (5 ml)/ammonia hydroxide (2 ml) solution were
slowly added into the mixture, respectively. Afterward, the solution 3.2 . Molecular model of n-SiO2 interphase
was kept for 1 h with the ultrasonic treatment at 25 °C and 5 h with
the mechanical stirring at 40 °C. Finally, n‐SiO2@JFs were rinsed by The molecular model of n‐SiO2 in an amorphous cell was applied to
distilled water, and dried at 70 °C for 2 h. build the surface [1 0 0] of n‐SiO2 interphase. The lattice parameters of

2
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

Fig. 1. Molecular models of (a) JFs surface and (b) JFs-COOH surface.

model of PP surface. The density of molecular model was

0.91 g/cm3. The lattice parameters of molecular model for PP surface
were the same as that of JFs surface and the thickness was set as 10 Å,
as shown in Fig. 4.
Each model (JFs and JFs‐COOH surfaces, n‐SiO2 interphase and PP
surface) was optimized using a smart method for 5000 iterations. The
Atom‐based summation method with a cut‐off distance of 9.5 Å was
applied for vdW interaction.

3.4. Molecular models of the multi-phase interfaces for n-SiO2@JF/PP

composites

n‐SiO2@JF/PP composites contained two interfaces, the one

between the JFs and n‐SiO2 interphase (JF/n‐SiO2 interface), another
between n‐SiO2 interphase and PP (n‐SiO2/PP interface).

3.4.1. Molecular model of JF/n-SiO2 interface

According to the FT‐IR spectra (Fig. 2), the new peak (470 cm−1) of
Si‐O‐Si bending vibration was obviously detected, which verified that
Fig. 2. FT-IR spectra of n-SiO2@JFs. n‐SiO2 interphase was successfully coated on the JFs [18]. The peak at
1055 cm−1 related to C‐OH of the JFs was hardly shifted, which
was attributed to the non‐bonding interaction between the JFs and
molecular model for n‐SiO2 interphase were the same as that of JFs n‐SiO2 interphase.
surface and the thickness was set as 0.5 Å, as Fig. 3 showed. In the case of carboxymethyl treatment, the new peak at
1080 cm−1 indicated that the hydroxyl groups of n‐SiO2 interphase
3.3. Molecular model of PP surface were formed C‐O‐Si chemical bonds with the introduced carboxyl
groups on JFs‐COOH [19]. Therefore, there were two kinds of interac-
Based on the amorphous cell module, 4 molecular chains of PP with tions between JFs‐COOH and n‐SiO2 interphase, namely, non‐bonding
polymerization degree of 20 were used to establish the molecular interaction and C‐O‐Si chemical bonding interaction.

Fig. 3. Molecular model of n-SiO2 interphase. Fig. 4. Molecular model of PP surface.

3
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

3.4.2. Molecular model of n-SiO2/PP interface interphase was tightly adsorbed on the JFs surface through non‐
To build the molecular model of n‐SiO2/PP interface, the model of bonding interaction which consisted of O–H‐O hydrogen bonds (the
PP surface was inserted into the cell of n‐SiO2@JFs surface. PP was blue dotted lines in Fig. 6), vdW interaction and electrostatic interac-
combined with n‐SiO2 interphase by non‐bonding interaction. tion [21].
With carboxymethyl treatment, C‐O‐Si chemical bond was formed
3.5 . Energy calculation of interface interaction between JFs‐COOH and n‐SiO2 interphase. C‐O‐Si chemical bond cre-
ated a strong connection at the interface, which resulted in the over-
MDsimulationwascarriedoutinNVTensemblefor1000pswiththether- lapping of molecule chains between JFs‐COOH and n‐SiO2
mostat of Andersen. For JF/n‐SiO2 interface and n‐SiO2/PP interface, the interphase, as shown in Fig. 6 (b). Notably, O–H‐O hydrogen bonds
simulation temperatures were set at 313 K and 453 K, respectively. The at the interface between JFs‐COOH and n‐SiO2 interphase seemed to
cut‐off distance of Atom‐based method was 12.5 Å for vdW interaction. be stronger than that between the control ones. This may be because
The interface binding energy (E BE ) and the interface interaction energy the strong intermolecular hydrogen bonds between the cellulose
(E IE ) included the valence energy (diag. terms, E VE ), valence energy (cross chains of JFs were broken by the introduced carboxyl groups that
terms, E CE ) and non‐bonding energy (E NE ); the non‐bonding energy con- made JFs‐COOH relatively free to interact with n‐SiO2 interphase. This
sisted of the potential energies for vdW force (E V ), electrostatic force (E E ) observation could be explained by the range of contact layer which
andlongrange correction(E L ), asgiveninEqs. (1)–(4)[20]. was considered as the area that included the atoms of the JFs and n‐
SiO2 interphase. The range of contact layer between JFs‐COOH and
E BE ¼ E IE ð1Þ
n‐SiO2 interphase (1.91 Å) was increased 59.17% than that of the con-
E IE ¼ E TE  ðE JFs þ E PP Þ ð2Þ trol ones (1.20 Å), as Fig. 7 showed. This result was attributed to the
introduced carboxyl groups which improved the physical and chemical
E TE ¼ E VE þ E CE þ E NE ð3Þ interactions between JFs‐COOH and n‐SiO2 interphase.
(2) Interaction energies
E NE ¼ E V þE E þE L ð4Þ The interaction of JF/n‐SiO2 interface and JF‐COOH/n‐SiO2 inter-
face could be quantitatively evaluated by the interaction energies, as
listed in Table 1. The positive interface binding energy indicated that
4. Results and discussion the interaction between the JFs and n‐SiO2 interphase was sponta-
neous and exothermic (123.22 kcal/mol), reflecting the strong attrac-
4.1. Macroscopic tensile test of n-SiO2@JF/PP composites tion at the interface [20].
Owing to the introduced carboxyl groups, the interface binding
Fig. 5 showed the tensile strengths of PP, JF/PP composites and n‐ energy between JFs‐COOH and n‐SiO2 interphase was increased
SiO2@JF/PP composites. The tensile strength of JF/PP composites was remarkably (271.27 kcal/mol) than that between the control ones
increasedby22.09%thanthatofPP,whichindicatedthattheJFspossessed (123.22 kcal/mol). However, the non‐bonding energy between JFs‐
good reinforcing [Link]‐SiO2@JF/PPcom- COOH and n‐SiO2 interphase (−11450.77 kcal/mol) was lower than
positeswasenhancedby32.82%thanthatofJF/[Link] that between the control ones (−12232.66 kcal/mol). This was attrib-
reflected that n‐SiO2 coating treatment was an effective modification uted to that non‐bonding energy was mainly determined by the ener-
methodtoimprovethetensilestrengthof JF/PPcomposites. gies from vdW force and electrostatic force. The more negative
electrostatic energy (−13103.72 kcal/mol) indicated that the intro-
4.2. MD simulation analysis of the interface structure and interaction for n- duced carboxyl groups with the electron‐rich effect promoted the elec-
SiO2@JF/PP composites trostatic interaction between JFs‐COOH and n‐SiO2 interphase.
Nevertheless, the positive vdW energy (1677.03 kcal/mol) suggested
that the introduced carboxyl groups had the negative effect on the
4.2.1. JF/n-SiO2 interface vdW interaction at the interface. This was because the molecule chains
(1) Interface structure between JFs‐COOH and n‐SiO2 interphase tended to be close to each
The molecular models of JF/n‐SiO2 interface and JF‐COOH/n‐SiO2 other and even overlapped, as shown in Fig. 6 (b), resulting in that
interface were illustrated in Fig. 6. In Fig. 6 (a), the surface of n‐SiO2 the attraction of vdW force transformed to more powerful repulsion.
The attractive energy from the electrostatic force was outweighed by
the repulsive energy from vdW force, resulting in that the non‐
bonding energy between JFs‐COOH and n‐SiO2 interphase was lower
than that between the control ones.
This result highlighted the important role of C‐O‐Si chemical bond
at the interface between JFs‐COOH and n‐SiO2 interphase. The inter-
face binding energy of JF‐COOH/n‐SiO2 interface was increased by
the combination results of C‐O‐Si chemical bonding interaction and
electrostatic interaction.

4.2.2. n-SiO2/PP interface

(1) Interface structure
The molecular models of JF/PP interface and n‐SiO2@JF/PP inter-
face were illustrated in Fig. 8. As Fig. 8 (a) showed, owing to the dif-
ference of polarity (JFs: polarity; PP: non‐polarity) and the steric
hindrance effect of hydroxyl groups in the crystalline region of cellu-
lose, the molecular chains of JFs and PP were hardly interacted with
each other. The range of contact layer at JF/PP interface was just
about 0.41 Å, as Fig. 9 (a) illustrated.
Fig. 5. Tensile strengths of PP, JF/PP composites and n-SiO2@JF/PP In Fig. 8 (b), the molecular chains of PP distributed evenly on n‐
composites. SiO2@JFs. Moreover, the molecular chains of PP and n‐SiO2 interphase

4
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

Fig. 6. Molecular models of (a) JF/n-SiO2 interface and (b) JF-COOH/n-SiO2 interface.

Fig. 7. Relative concentrations of (a) JF/n-SiO2 interface and (b) JF-COOH/n-SiO2 interface.

Table 1
Interaction energies of JF/n-SiO2 interface and JF-COOH/n-SiO2 interface.

Interface Energy (kcal/mol)

EBE EIE ENE EV EE

JF/n-SiO2 123.22 −123.22 −12232.66 −173.76 −12041.16

JF-COOH/n-SiO2 271.27 −271.27 −11450.77 1677.03 −13103.72

Fig. 8. Molecular models of (a) JF/PP interface and (b) n-SiO2@JF/PP interface.

5
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

Fig. 9. Relative concentrations of (a) JF/PP interface and (b) n-SiO2@JF/PP interface.

were adsorbed and interlocked at the interface. This was because n‐ parallel distributing along the longitudinal direction of JFs‐COOH,
SiO2 interphase with amorphous structure was relatively free to inter- which increased the surface roughness of JFs‐COOH at nano‐scale. In
act with PP chains, increasing the contact area and the mechanical Fig. 10 (b), n‐SiO2 layer which included n‐SiO2 gel and array was
interlocking between n‐SiO2 interphase and PP at molecular level. coated on JFs‐COOH. At initial stage of n‐SiO2 coating, a thin layer
The range of contact layer at n‐SiO2@JF/PP interface was about of n‐SiO2 gel was covered on JFs‐COOH. With the increase of coating
4.07 Å, as Fig. 9 (b) showed. time, n‐SiO2 arrays composed of uniform particles (60–70 nm) were
(2) Interaction energies aligned orderly in the surface flaws of JFs‐COOH, which made the sur-
The interaction energies of JF/PP interface and n‐SiO2@JF/PP face of JFs‐COOH smooth at nano‐scale.
interface were shown in Table. 2. The positive interface binding
energy proved the attractive interaction at JF/PP interface and n‐ 4.3.2. Cross-sectional morphologies of JFs-COOH and n-SiO2@JFs
SiO2@JF/PP interface. For JF/PP interface, the energy from vdW force The cross‐sectional morphologies of JFs‐COOH and n‐SiO2@JFs
(−286.34 kcal/mol) was negative while the electrostatic energy were shown in Fig. 11. A compact and thin n‐SiO2 layer with the
(3034.20 kcal/mol) was positive. This was because that the strongly thickness ranging from 70 nm to 100 nm formed an interphase
linked hydroxyl groups in the crystalline region of cellulose were inac- between JFs‐COOH and polymer, which endowed n‐SiO2@JF/PP com-
cessible, which were responsible for the repulsive interaction of elec- posites with the multi‐phase and multi‐scale structure, as shown in
trostatic force [22]. Fig. 11 (b). n‐SiO2 interphase created a distinct transition region
On the contrary, n‐SiO2 interphase was more active to interact with between JFs‐COOH and PP, which served as a medium to transfer
PP, eliminating the steric hindrance effect at the interface and thus the stress from PP to JFs‐COOH and thus contributed to the
showing the strong electrostatic energy (−13580.14 kcal/mol) strengthening effect of interface on the mechanical properties of
between n‐SiO2@JFs and PP. However, the energy from the vdW force n‐SiO2@JF/PP composites.
(1642.27 kcal/mol) presented the positive value. This was because the
overlapped molecular chains between n‐SiO2 interphase and PP 4.3.3. Microscopic modelling of the failure behaviors for n-SiO2@JF/PP
resulted in the repulsive interaction of vdW force. The attractive elec- composites
trostatic energy was stronger than the repulsive energy from vdW According to the interface transfer theory, when the plant fiber/
force, which provided the primary driving force for the interaction thermoplastic composites underwent the load parallel to the direction
between n‐SiO2 interphase and PP. Thus, the interface binding energy of reinforcing fibers, the interface bonding performance was one of
of n‐SiO2/PP interface was enhanced by 27.21% than that of the con- important factors to affect the failure behaviors of the composites
trol ones. [23,24].
In Fig. 12 (a), the JFs were pulled out from PP during the tensile
4.3. Microscopic analysis of the failure behaviors for n-SiO2@JF/PP process. The SEM micrograph obviously showed the interface defects
composites between the JFs and PP. This was because the hydrophobic PP with
a high viscosity was difficult to fill up the surface flaws of JFs, resulting
in the formation of defects at the interface, as Fig. 15 (a) illustrated.
4.3.1. Surface morphologies of JFs-COOH and n-SiO2@JFs The cracks were easy to propagate at the interface defects, which
The surface morphologies of JFs‐COOH and n‐SiO2@JFs were caused the interface sliding and the JFs pull‐out. Therefore, the rein-
shown in Fig. 10. As Fig. 10 (a) showed, a few surface flaws oriented forcing effect of JFs was limited.

Table 2
Interaction energies of JF/PP interface and n-SiO2@JF/PP interface.

Interface Energy (kcal/mol)

EBE EIE ENE EV EE

JF/PP 150.41 −150.41 2724.05 −286.34 3034.20

n-SiO2@JF/PP 191.35 −191.35 −11976.00 1642.27 −13580.14

6
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

Fig. 10. Surface morphologies of (a) JFs-COOH and (b) n-SiO2@JFs.

Fig. 11. Cross-sectional morphologies of (a) JFs-COOH and (b) n-SiO2@JFs.

Fig. 12. Tensile fracture morphologies of (a) JF/PP composites and (b) n-SiO2@JF/PP composites.

In Fig. 12 (b), n‐SiO2@JFs were closely bonded with PP, and the the interface debonding and sliding; (2) As Fig. 15 (b) showed, n‐SiO2
part of PP was fractured almost simultaneously with n‐SiO2@JFs interphase served as a medium to transfer the tensile stress effectively
instead of the interface sliding. This result could be attributed to two from PP to JFs‐COOH, eliminating the tensile stress concentration at
aspects: (1) according to the results of MD simulations, n‐SiO2 layer the interface defects and thus causing the fiber fracture directly
including gel and array formed a stable interphase between JFs‐ [25–27].
COOH and PP by the chemical bonding interaction and the mechanical As Fig. 13 showed, the interface debonding of n‐SiO2@JF/PP com-
interlocking of molecular chains, which was strong enough to restrain posites was also occurred, which made n‐SiO2@JFs pulled out from

7
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

Fig 13. Surface morphologies of pull-out n-SiO2@JFs: (a) n-SiO2 interphase interlaminar debonding, (b) n-SiO2/PP interface debonding, (c) PP cohesive failure.

PP. There were three kinds of interface debonding models for

n‐SiO2@JF/PP composites: (1) n‐SiO2 interphase interlaminar debond-
ing. Under tensile stress, JFs‐COOH with n‐SiO2 gel were pulled out
from PP, while n‐SiO2 arrays were left in PP, as Fig. 15 (c) showed.
n‐SiO2 gel could be a shielding layer to prevent JFs‐COOH from dam-
age directly, which was proved by some cracks on n‐SiO2 gel in Fig. 13
(a). (2) n‐SiO2/PP interface debonding. The interface failure was taken
place between n‐SiO2 interphase and PP, which made n‐SiO2
interphase pulled out with JFs‐COOH, as Fig. 15 (d) showed. In
Fig. 13 (b), n‐SiO2 arrays were mainly remained in the surface flaws
of JFs‐COOH. It suggested that the surface flaws of JFs‐COOH may
protect n‐SiO2 arrays from falling off. (3) PP cohesive failure. As
Fig. 13 (c) showed, PP was covered on the pull‐out n‐SiO2@JFs. This
was because n‐SiO2 interphase acted as a medium during stretching,
which transferred the tensile stress effectively from PP to JFs‐COOH
and thus the interface failure changed to the cohesive failure of PP,
as Fig. 15 (e) illustrated.
It was worth mentioning that a fibril was pulled out from the bun-
dle of n‐SiO2@JFs obviously, whereas n‐SiO2@JFs were still bonded Fig. 14. Morphology of the internal debonding for n-SiO2@JFs.
with PP, as Fig. 14 showed. This was ascribed to the multi‐layer
microstructure of JFs‐COOH. Li et al [28] proposed a multi‐layer inter-
face failure model with the interface debonding between the plant mary cell wall of plant fibers and PP was stronger than the shear
fibers and polymer in the initial stage owing to the weak interface strength of secondary cell wall in the plant fibers, the interface
strength, then the interface debonding between the fibrils in plant debonding was occurred between the fibrils. Thus, the internal
fibers and finally the interface between the cell walls of plant fibers. debonding of n‐SiO2@JFs was taken as evidence for the strong inter-
Bos et al [29] proved that when the interface strength between the pri- face between n‐SiO2@JFs and PP, as Fig. 15 (f) illustrated.

8
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

Fig. 15. Tensile failure models of n-SiO2@JF/PP composites: (a) JF/PP interface debonding, (b) n-SiO2@JFs breakage, (c) n-SiO2 interphase interlaminar
debonding, (d) n-SiO2/PP interface debonding, (e) PP cohesive failure, (f) n-SiO2@JFs internal debonding.

5. Conclusion mechanical interlocking of molecular chains, which enhanced

the interface binding energy effectively. With n‐SiO2 interphase,
In this research, the interface structure and failure behaviors of n‐ the interface binding energy of JF/PP composites was enhanced
SiO2@JF/PP composites were analyzed at multi‐scale level by MD sim- by 27.21%.
ulation, microscopic modelling and macroscopic mechanical test. The (2) n‐SiO2 interphase served as a medium to transfer the tensile
following conclusions were obtained: stress from PP to JFs‐COOH effectively, which eliminated the
tensile stress concentration at the interface defects and thus
(1) From the viewpoint of the interface molecular structures and improved the tensile strength of n‐SiO2@JF/PP composites.
interaction energies, n‐SiO2 interphase acted as a bridge to bond The tensile strength of n‐SiO2@JF/PP composites was increased
JFs‐COOH and PP by the chemical bonding interaction and the by 32.82% than that of JF/PP composites.

9
X. Liu, Y. Cui Composite Structures 267 (2021) 113865

(3) Owing to JFs‐COOH with multi‐layer microstructure and the [12] Jiao W, Zheng T, Liu W, Jiao W, Wang R. Molecular dynamics simulations of the
effect of sizing agent on the interface property in carbon fiber reinforced vinyl
presence of n‐SiO2 interphase, the structure of n‐SiO2@JF/PP
ester resin composite. Appl Surf Sci 2019;479:1192–9.
composites was multi‐layer and multi‐phase. The interface fail- [13] Liu X, Cui Y, Lee KL, Zhang M, Nie W. Multiscale modelling of nano-SiO2 deposited
ure behaviors of n‐SiO2@JF/PP composites included n‐ on jute fibers via macroscopic evaluations and the interface interaction by
SiO2@JFs breakage, n‐SiO2@JFs internal debonding, n‐SiO2 molecular dynamics simulation. Compos Sci Technol 2020;118:107987.
[14] Tam L-h, Zhou Ao, Wu C. Nanomechanical behavior of carbon fiber/epoxy
interphase interlaminar debonding, n‐SiO2/PP interface interface in hygrothermal conditioning: A molecular dynamics study. Mater Today
debonding, PP cohesive failure. The strong interface may lead Commun 2019;19:495–505.
to PP cohesive failure or the internal debonding of n‐SiO2@JFs. [15] Zhang W, Deng Xi, Sui G, Yang X. Improving interfacial and mechanical properties
of carbon nanotube-sized carbon fiber/epoxy composites. Carbon
2019;145:629–39.
[16] Salama HE, Abdel Aziz MS, Alsehli M. Carboxymethyl cellulose/sodium
Declaration of Competing Interest alginate/chitosan biguanidine hydrochloride ternary system for edible coatings.
Int J Biol Macromol 2019;139:614–20.
The authors declare that they have no known competing financial [17] Adinugraha MP, Marseno DW, Haryadi. Synthesis and characterization of sodium
carboxymethylcellulose from cavendish banana pseudo stem (Musa cavendishii
interests or personal relationships that could have appeared to influ- LAMBERT). Carbohyd Polym 2005;62:164-169.
ence the work reported in this paper. [18] Liu X, Cui X, Zhang C, Zhang X, Wu G. Effects of different silanization followed via
the sol-gel growing of silica nanoparticles on carbon fiber on interface strength of
silicone resin composites. Chem Phys Lett 2018;707:1–7.
References [19] Wang H, Xian G, Li H. Grafting of nano-TiO2 on flax fibers and the enhancement of
themechanical properties of the flax fiber and flax fiber/epoxy composite. Compos
[1] Militello C, Bongiorno F, Epasto G, Zuccarello B. Low-velocity impact behaviour of Part A: Appl Sci Manuf 2015;76:172–80.
green epoxy biocomposite laminates reinforced by sisal fibers. Compos Struct [20] He L, Li W, Chen D, Zhou D, Lu G, Yuan J. Effects of amino silicone oil
2020;253:112744. [Link] modification on properties of ramie fiber and ramie fiber/polypropylene
[2] Woigk W, Fuentes CA, Rion J, Hegemann D, van Vuure AW, Dransfeld C, et al. composites. Mater Design 2015;77:142–8.
Interface properties and their effect on the mechanical performance of flax fibre [21] Sanchez F, Zhang L. Interaction energies, structure, and dynamics at functionalized
thermoplastic composites. Compos Part A: Appl Sci Manuf 2019;122:8–17. graphitic structure-liquid phase interfaces in an aqueous calcium sulfate solution
[3] Muneer Ahmed M, Dhakal HN, Zhang ZY, Barouni A, Zahari R. Enhancement of by molecular dynamics simulation. Carbon 2010;48(4):1210–23.
impact toughness and damage behaviour of natural fibre reinforced composites [22] Kabir MM, Wang H, Lau KT, Cardona F. Effects of chemical treatments on hemp
and their hybrids through novel improvement techniques: A critical review. fibre structure. Appl Surf Sci 2013;276:13–23.
Compos Struct 2021;259:113496. [Link] [23] Prasad V, Sekar K, Varghese S, Joseph MA. Evaluation of interlaminar fracture
[Link].2020.113496. toughness and dynamic mechanical properties of nano TiO2 coated flax fibre epoxy
[4] Li Y, Sun H, Zhang Y, Xu M, Shi SQ. The three-dimensional heterostructure composites. Polym Test 2020;91:106784. [Link]
synthesis of ZnO/cellulosic fibers and its application for rubber composites. polymertesting.2020.106784.
Compos Sci Technol 2019;177:10–7. [24] Sun J, Zhao F, Yao Y, Jin Z, Liu X, Huang Y. High efficient and continuous surface
[5] Sarker F, Karim N, Afroj S, Koncherry V, Novoselov KS, Potluri P. High- modification of carbon fibers with improved tensile strength and interface
performance graphene-based natural fiber composites. Acs Appl Mater Inter adhesion. Appl Surf Sci 2017;412:424–35.
2018;10(40):34502–12. [25] Foruzanmehr M, Vuillaume PY, Elkoun S, Robert M. Physical and mechanical
[6] Li Y, Chen C, Xu J, Zhang Z, Yuan B, Huang X. Improved mechanical properties of properties of PLA composites reinforced by TiO2 grafted flax fibers. Mater Design
carbon nanotubes-coated flax fiber reinforced composites. J Mater Sci 2015;50 2016;106:295–304.
(3):1117–28. [26] Landowski M, Strugała G, Budzik M, Imielińska K. Impact damage in SiO2
[7] Zhang T, Song Y, Zhao Y, Zhang B. Effect of hybrid sizing with nano-SiO2 on the nanoparticle enhanced epoxy-Carbon fibre composites. Compos Part B-Eng
interface adhesion of carbon fibers/nylon 6 composites. Colloid Surface A 2017;113:91–9. [Link]
2018;553:125–33. [27] Wu G, Ma L, Jiang H, Liu L, Huang Y. Improving the interface strength of silicone
[8] Liu X, Cui Y, Hao S, Chen H. Influence of depositing nano-SiO2 particles on the resin composites by chemically grafting silica nanoparticles on carbon fiber.
surface microstructure and properties of jute fibers via in situ synthesis. Compos Compos Sci Technol 2017;153:160–7.
Part A: Appl Sci Manuf 2018;109:368–75. [28] Li Q, Li Y, Zhang Z, Zhou L. Multi-layer interfacial fatigue and interlaminar
[9] Zhang T, Xu Y, Li H, Zhang B. Interface adhesion between carbon fibers and nylon fracture behaviors for sisal fiber reinforced composites with nano- and macro-scale
6: Effect of fiber surface chemistry and grafting of nano-SiO2. Compos Part A: Appl analysis. Compos Part A: Appl Sci Manuf 2020;135:105911. [Link]
Sci Manuf 2019;121:157–68. 10.1016/[Link].105911.
[10] Bayart M, Gauvin F, Foruzanmehr MR, Elkoun S, Robert M. Mechanical and [29] Bos HarriëtteL, Müssig Jörg, van den Oever MJA. Mechanical properties of short-
moisture absorption characterization of PLA composites reinforced with nano- flax-fibre reinforced compounds. Compos Part A: Appl Sci Manuf 2006;37
coated flax fibers. Fiber Polym 2017;18(7):1288–95. (10):1591–604.
[11] Sun Z, Wu M. Effects of sol-gel modification on the interface and mechanical
properties of sisal fiber reinforced polypropylene composites. Ind Crop Prod
2019;137:89–97.

10