Accepted Manuscript

Grafting of silane and graphene oxide onto PBO fibers: Multifunctional interphase for fiber/polymer matrix composites with simultaneously improved interfacial and atomic oxygen resistant properties
Lei Chen, Feng Wei, Li Liu, Weilu Cheng, Zhen Hu, Guangshun Wu, Yunzhe
Du, Chunhua Zhang, Yudong Huang
PII:
DOI:
Reference:

S0266-3538(14)00383-2
http://dx.doi.org/10.1016/j.compscitech.2014.10.021
CSTE 5970

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Composites Science and Technology

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Revised Date:
Accepted Date:

1 July 2014
6 October 2014
24 October 2014

Please cite this article as: Chen, L., Wei, F., Liu, L., Cheng, W., Hu, Z., Wu, G., Du, Y., Zhang, C., Huang, Y.,
Grafting of silane and graphene oxide onto PBO fibers: Multifunctional interphase for fiber/polymer matrix
composites with simultaneously improved interfacial and atomic oxygen resistant properties, Composites Science
and Technology (2014), doi: http://dx.doi.org/10.1016/j.compscitech.2014.10.021

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Grafting of silane and graphene oxide onto PBO fibers: multifunctional interphase for
fiber/polymer matrix composites with simultaneously improved interfacial and atomic
oxygen resistant properties
Lei Chen,a Feng Wei,a Li Liu,a Weilu Cheng,a Zhen Hu,a Guangshun Wu,a Yunzhe
Du,a Chunhua Zhang,a Yudong Huang ,a ,b
a School of Chemical Engineering and Technology, Harbin Institute of Technology,
Harbin 150001, PR China
b State Key Laboratory of Urban Water Resource and Environment, Harbin Institute
of Technology, Harbin 150001, PR China
Abstract
Atomic oxygen (AO) is a dominant component of the low earth orbit and can
erode most spacecraft materials. In this work, both silane and graphene oxide (GO)
were introduced onto poly(p-phenylene benzobisoxazole) (PBO) fibers to prevent AO
from penetrating into the interface of PBO fiber/epoxy composites. The
microstructure, mechanical properties and AO erosion resistance of PBO fibers before
and after modification were investigated. Experimental results revealed that the GO
was successfully grafted onto PBO fibers using 3-aminopropyltrimethoxysilane
(APTMS) as the bridging agent. The surface roughness (Ra) and wettability of the
obtained hybrid fibers (PBO-APTMS-GO) were obviously increased in comparison
with those of an untreated one. In addition, PBO-APTMS-GO showed simultaneously
remarkable enhancement in interfacial shear strength (IFSS) and AO erosion
Corresponding author. Tel/Fax: +86 451 86414806.
E-mail addresses: ydhuang.hit1@aliyun.com (Y.D. Huang).
1

resistance. Meanwhile, single filament tensile strength (TS) had no obvious decrease
after the grafting processes. We believe the facile and effective method may provide a
novel interface design strategy for developing multifunctional fibers.
1. Introduction
The low Earth orbit (LEO) space environment presents many obstacles to a
successful spacecraft mission. The degrading environment for polymers includes
atomic oxygen (AO), high-energy ultraviolet (UV), ultrahigh vacuum (UHV), thermal
cycles,

micrometeoroids and orbital debris [1-3]. It is well-known that

poly(p-phenylene benzobisoxazole) (PBO) fiber reinforced resin composites exhibit

excellent performance combined with high strength, high modulus and light weight,
and have great potential in space applications [4-6]. When the spacecraft flights
during thermal cycles in LEO, many micro cracks will occur in the interface of
composites due to a great difference of coefficient of thermal expansion (CTE)
between PBO fibers and resin matrix. Once damage occurs to the AO-resistant
coating of the composites, AO would penetrate into these micro cracks and further
corrode the interface and even the fiber reinforcements [7]. As a result, the in-plane
properties of the composites would degrade significantly after AO erosion. Given the
harsh environment, steps must be taken to protect the interface of PBO fiber
composites used on spacecraft. Unfortunately, there are few articles have reported the
protection of composites interface.
As is well known, a strong fiber and strong matrix may not necessarily result in a
strong composite because the interface is equally important in determining the overall
2

strength of the resulting material [8, 9]. An optimum interface can significantly
improve the mechanical properties and environmental stability of the composites and
transfer the stress efficiently from matrix to PBO fibers. With this in mind, the first
priority of preparing the AO-resistant interface is to maintain and even improve the
interfacial bonding between PBO fibers and resin matrix.
The good wettability, large specific surface area and excellent mechanical
properties of graphene oxide (GO) make it an ideal hierarchical reinforcement in
composite fields [10]. Very recently, several researchers have made effort to graft GO
onto different kinds of fibers for enhancing the interfacial properties. Our group
grafted GO onto PBO fibers by using solvothermal method, and found that the
interfacial shear strength (IFSS) of GO-grafted PBO fibers was remarkably improved
[11]. However, the high temperature required for solvothermal method would degrade
the mechanical properties of PBO fibers. Li et al. introduced GO onto carbon fibers
using poly(amido amine) (PAMAM) as the bridging agent to prepare a new
hierarchical reinforcement [12]. Altough the reaction condition is milder compared to
the solvothermal method, PAMAM used as the bridging agent is very expensive.
Furthermore, both of the methods mentioned above are not suitable for preparing the
AO-resistant interface between fibers and resin matrix.
Previous studies have indicated that silicone coating possesses both low crack
tendency and low erosion rate in AO exposure experiments [13, 14]. Silane coupling
agents with the Si-O bond have led AO-irradiated samples to form a SiO2 passivation
layer, which protects the underlying polymer from further AO attack. The
3

bifunctional structures of silane coupling agents have also been of interest in applying
them to create chemical bridges between the fiber and resin matrix [15, 16]. Therefore,
3-aminopropyltrimethoxysilane (APTMS) with both amine and methoxyl groups
instead of PAMAM is selected as the bridging agent in this study.
In the present work, we proposed a multifunctional interphase consisting of
APTMS and GO in PBO fiber/epoxy composites via chemical grafting. The
microstructure, interfacial properties and AO erosion resistance of PBO fibers before
and after modification were systematically characterized and investigated. The results
suggested that the modified PBO fibers with simultaneously improved interfacial
properties and AO erosion resistance could be prepared using the facile method
proposed herein.
2. Experimental
2.1 Materials
The PBO fibers (HM) having a single filament diameter of 12 m were supplied
by Toyobo Ltd., Japan. Prior to use, sizing agent of PBO fibers were removed by
Soxhlet extraction with acetone at 70 for 48 h. 3-aminopropyltrimethoxysilane
(APTMS) was received from TCI Ltd., Japan. Graphite, thionyl chloride (SOCl2),
dimethylformamide (DMF) and tetrahydrofuran (THF) were purchased from
Sinopharm Chemical Reagent Co., Ltd., China, and the three solvents were distilled
prior to use.
2.2 Preparation of graphene oxide (GO) and acylated graphene oxide (GO-Cl)
GO was prepared by using the modified Hummers method [17]. The obtained
4

GO (0.1 g) was mixed with SOCl2 (40 mL) containning a catalytic amount of DMF (2
mL). The mixture was subject to intense ultrasonic treatment for 30 min and then
moved into a three-necked flask (100 mL). The homogeneous suspension was under
reflux for 48 h with magnetic stirring. After removal of the excess of SOCl2 by
filtration, being washed with THF and dried at 50 in vacuum, a dark powder
(GO-Cl) was obtained.
2.3 Preparation of PBO-APTMS-GO
The PBO-APTMS-GO hybrid reinforcement was prepared through several steps
of chemical reactions. First, the PBO fibers were oxidized in 60 wt% H2SO4 for 3 h to
generate some polar groups. After being washed with deionized water for several
times and dried in vacuum, the fibers were submersed in LiAlH4-THF saturated
solution, and then refluxed for 1 h to reduce carboxyl groups to hydroxyl groups
following Zhangs report [18]. The resulting fibers (PBO-OH) with homogeneously
hydroxyl groups were available for the subsequent interaction with APTMS. After
being washed with ethanol for several times, the PBO-OH was mixed with APTMS
(0.5 mL) in ethanol (50 mL) reacting at 40 for 24 h to obtain APTMS
functionalized PBO fibers, denoted as PBO-APTMS. Finally, PBO-APTMS was
mixed with GO-Cl (0.1 g) in DMF (50 mL) at 80 for 48 h under nitrogen
atmosphere. The obtained PBO-APTMS-GO was repeatedly rinsed in excess DMF to
remove unreacted GO. The whole grafting processes are schemed in Fig. 1.
2.4 Characterization of GO and PBO fibers
The morphology and structure of GO and PBO-APTMS-GO were elucidated by
5

TEM (Hitachi H-7650, Japan) measurements. The thickness of GO and the surface
roughness (Ra) of PBO fibers were determined using an AFM (Bruker Dimension
Icon-PT). The crystal structures of graphite and GO were examined by XRD
(RIGAKU D/MAX-r, Japan) with Cu K radiation (=1.5406 nm) generated at 40
kV and 100 mA. The surface morphology of PBO fibers was observed by a SEM
(Hitachi S-4700, Japan).
The chemical composition of the fiber surface was conducted on a XPS (Thermo
Scientific, USA). XPS analysis was performed on a mono-chromated Al K
radioactive source (1486.6 eV) at a base pressure of 210-9 mbar.
The wettability was tested by measuring the increasing weight of PBO fibers
when they were dipped into the epoxy resin (E-51). At first the value was recorded
with intervals of 1 s, then 3 s, at last 30 s.
2.5 Mechanical property tests of PBO fibers
Single filament pull-out tests were performed to determine the IFSS of PBO
fibers using an interfacial strength testing machine (Tohei Sanyon Co Ltd, Japan). The
values of IFSS were calculated according to equation (1), which was averaged from
the 50 valid data for each sample.

(1)
where Fmax is the peak pullout force, N; d is the average diameter of PBO fiber, m;
and l is the embedded length of single filament in epoxy resin.
Single filament tensile tests were performed on a universal testing machine
(Instron 5500R, USA) according to the ASTM D3379-75. A gauge length of 100 mm
6

and cross-head speed of 10 mm/min were used for all samples. At least 60 specimens
of each type of fiber were tested, and the results were analyzed by Weibull statistical
method.
2.6 AO exposure tests of PBO fibers
AO exposure tests were conducted in a ground-based AO effect simulation
facility designed by Beijing University of Aeronautics and Astronautics [19]. In the
experiment, all samples were placed on a circular holder in the vacuum chamber of
the facility, in which the vacuum pressure was 1.510-1 Pa. The flux of AO was
determined to be 2.11015 atoms/cm2s, and the test periods were within 8 h.
3. Results and discussion
The TEM image of the obtained GO is shown in Fig. 2a. The transparent sheets
are observed to be several micrometers in size. Note the wrinkled surface texture of
the GO, which can play an important role in enhancing mechanical interlocking and
load transfer between the PBO fibers and resin matrix [20]. AFM image (Fig. 2b)
reveals that the thickness of wrinkled graphene oxide used for grafting was around
0.987 nm. The XRD patterns of graphite and GO are presented in Fig. 2c. Graphite
shows a diffraction peak at 26.6, which disappears after strong oxidation. The
diffraction peak (002) of GO at 11.1 is ascribed to the formation of active functional
groups on both basal planes and edges of carbon sheets [21].
Fig. 3 shows the FTIR spectra of untreated-PBO, PBO-oxidation, PBO-OH,
PBO-APTMS and PBO-APTMS-GO. All the samples present the characteristic peaks
of PBO, a C=N stretch at 1636 cm-1, a C-O-C stretch at 1054 cm-1 and an aromatic
7

C-H stretch at 3000 cm-1 [11].

For the PBO-oxidation, new characteristic peaks

appear at 1726 and 3450 cm-1 which are assigned to the stretching vibration of
carboxyl and hydroxyl groups, respectively, indicating that the PBO fiber has been
etched and oxidized by the acid treatment. After the reduction treatment, the
stretching vibration of carboxyl group at 1726 cm-1 disappears, and the peak intensity
of the stretching vibration of hydroxyl group at 3450 cm-1 significantly increases,
suggesting that the carboxyl groups on the fiber surface have been reduced to
hydroxyl groups [18]. After further interaction with APTMSthe hydroxyl peak is
broadened and shifted to 3320 cm-1, originating from the stretching vibration of the
N-H [22]. For the PBO-APTMS-GO, the peaks in the range of 1690-1630 cm-1 are
assigned to the C=O stretching of amide (amide I band), and the peak at 1550 cm-1
corresponds to the scissoring vibration of the N-H of the amide functionality (amide II
band), indicating that GO is grafted onto the PBO fibers through covalent bonds [23].
Such binding properties could be further assessed by XPS, as shown in Fig. 4.
From the wide-scan survey XPS spectra (Fig. 4a), we can find that both the surface of
untreated-PBO and PBO-oxidation is composed of carbon, oxygen and nitrogen
elements. After funcitionalized with APTMS and further with GO, a new peak appears
at 102 eV corresponding to the Si2p [22], suggesting the bridging agent is
successfully introduced onto the PBO fiber surface. The N1s peak positions are
derived from peak deconvolution results. For the untreated-PBO (Fig. 4b), there is
only one C=N-C peak at 398.6 eV can be observed. After GO grafting (Fig. 4c), a new
binding energy peak at 400.4 eV ascribed to N-C=O appears at the sample of
8

PBO-APTMS-GO, indicating amine groups on the PBO fiber surface are reacted with
acyl chloride groups on GO functionalized by SOCl2.
The surface morphologies of PBO fibers before and after GO-grafting are
observed by SEM, as shown in Fig. 5. Its evident from the figure that the surface of
untreated-PBO is neat and smooth (Fig. 5a). Fig. 5b and c show the surface
morphologies of PBO-oxidation and PBO-OH where some narrow grooves are visible
along the axial direction of PBO fibers. It seems that the reduction treatment does not
give rise to any obvious change on the surface of PBO-OH in comparison with
PBO-oxidation. However, after interaction with APTMS, the surface morphology of
PBO fiber changes a lot, as shown in Fig. 5d. We can see that the grooves are covered
by a compact silane layer, which can not only provide many amine groups as reactive
sites for the next step, but also impede the corrosion of AO. After further GO-grafting
(Fig. 5e), quite a number of different sized GO sheets are attached to the PBO fiber
surface, forming a new hierarchical structure. Interestingly, some of GO sheets stand
stably on the PBO fiber, while some of them coat tightly on the fiber surface. This
phenomenon is analogous to the grafting of GO sheets onto carbon fibers observed by
Li et al [12].
To explore the interface of the GO sheets on the PBO fiber, TEM image of the
new hierarchical structure is shown in Fig. 6. Clearly, the GO sheets stably stand on
the PBO fiber surface, which makes the modified PBO fiber look like a branched fiber,
supplying the opportunity that GO can stick into the resin matrix and locally stiffen
the interface of the resulting composites [11].
9

The mechanical properties of PBO fibers and their composites are evaluated by
TS and IFSS. As is well known, TS is very important when PBO fibers are used as
reinforcing material. Therefore, TS of PBO fibers before and after modification is
inspected, as shown in Fig. 7a. The TS results of untreated-PBO, PBO-oxidation,
PBO-OH, PBO-APTMS and PBO-APTMS-GO are 5.8, 5.51, 4.96, 5.37 and 5.23 GPa,
respectively. It is found that the multi-step processes do not cause serious degradation
in the TS of PBO fibers. The mild treatment condition of oxidation and chemical
grafting procedures is the main contributor to the satisfactory TS. Fig. 7b shows the
interfacial property testing results of PBO fibers. After acid-treatment, the IFSS
increases from 40.4 MPa for untreated-PBO to 48 MPa by 18.8%. Compared to
PBO-oxidation, the IFSS of PBO-OH has a slight decrease to 45.8 MPa. After
functionalization with APTMS, the IFSS increases to 54.9 MPa, which is mainly
attributed to the high activity and wettability of amine groups with epoxy matrix [24].
When GO is further grafted onto the fiber surface, the IFSS has a remarkable increase
to 65.3 MPa, which gives rise to a 18.9% improvement compared to PBO-APTMS,
and a 61.6% improvement compared to untreated-PBO. This might be related to the
increase of active functional groups and Ra caused by the introduction of GO into the
interfacial region. Moreover, based on its large specific surface area and excellent
mechanical properties, it would consume more energy to pull PBO-APTMS-GO from
the resin matrix. The above results suggest that the method is potential and
competitive to improve the interfacial properties of PBO fiber composites.
In order to further identify the reason for the improvement of interfacial
10

properties of PBO-APTMS-GO/epoxy composites, the surface roughness and

wettability of PBO fibers are examined by AFM and dynamic wetting tests,
respectively. AFM results of untreated-PBO and PBO-APTMS-GO with Ra are
presented in Figure 8a and b, respectively. Compared to untreated-PBO, Ra of
PBO-APTMS-GO increases from 26.6 nm to 45.1 nm. The wrinkles and defects of
GO sheets lead to a rough surface of PBO-APTMS-GO. Dynamic wetting curves of
the two samples in epoxy resin are presented in Figure 8c. It is found that the
adsorption weight and wetting velocity for PBO-APTMS-GO increase remarkably,
which is mainly attributed to the increased quantity of active functional groups.
Figure 8d and e depict the surface morphology of PBO fibers de-bonding from
the resin matrix. For untreated-PBO (Fig. 8d), there are few epoxy fragments remain
on the de-bonded fiber surface. This means that the interface is easily de-bonded
because of the weak van der Waals force between fiber and resin matrix. In the case of
PBO-APTMS-GO (Fig. 8e), numerous epoxy fragments and micro-cracks are traced,
which means the mechanical interlocking between fiber and matrix becomes stronger.
Additionally, we can observe that some GO sheets (marked by frame) are still visible
on the de-bonded fiber surface, suggesting a strong bonding between GO and PBO
fiber due to the chemical grafting.
GO reinforced hierarchical composites with superior interfacial properties have
been fabricated by many researchers, but the AO erosion resistance has rarely been
studied. In this section, the effects of AO attack on the mechanical properties of PBO
fibers and their composites are evaluated. Fig 9a and b show a striking difference
11

between the untreated-PBO and PBO-APTMS-GO after AO exposure. The untreated

PBO fiber is severely eroded and roughened, giving a corduroy-like appearance
(Fig. 9a). In contrast, the surface of PBO-APTMS-GO shows less roughness (Fig. 9b).
We can observe from Fig. 9c that the TS retention ratio of untreated-PBO and
PBO-APTMS-GO after 8 h AO accelerated aging is 68.4% and 85.7%, respectively.
Obviously, the TS of PBO-APTMS-GO decreases slower than that of untreated one.
Fig. 9d and e demonstrate the images of a micro-droplet before and after AO
exposure. The surface of the pure epoxy resin sample is smooth and intact before AO
exposure. After the AO exposure experiment, the surface of droplet exhibits a rough
texture with numerous ravines and crack paths, through which AO can further
penetrate into the interfacial region of the composites. The IFSS retention of PBO
fiber composites versus AO exposure time are shown in Fig. 9f. After 8 h AO
accelerated aging, the IFSS retention ratio of untreated-PBO and PBO-APTMS-GO is
61.3% and 93.1%, respectively. This implies that the interface of composites is
effectively protected by APTMS and GO.
Two factors may contribute to such an improvement in AO erosion resistance.
Firstly, a recent experimental study has shown that GO sheets can serve as barriers to
protect the material underneath from AO attack [19]. Also, when PBO fibers are
treated with APTMS, the fiber surface is covered by uniform siloxane oligomer,
which can form a SiO2 layer upon exposure to AO. SiO2 possesses a high energy
barrier for AO penetration. High-resolution XPS spectra of Si2p peak of
PBO-APTMS-GO before and after AO exposure are given in Fig. 10. Before AO
12

exposure, most of the silicon atoms are present at low binding energy (102 eV). After
8 h AO exposure, the Si2p peak shifts to the high binding energy direction, and it
contains a shoulder at 103.6 eV. This indicates that the silane has reacted with AO,
thus the binding energy of inner electrons has increased, and the oxidation state of the
silicon essentially converts into a passivation layer in the form of SiO2 [25].
4. Conclusions
In summary, a new hierarchical reinforcement was realized by grafting GO
sheets onto PBO fibers using APTMS as the coupling agent. Experimental results
suggested that the surface roughness and wettability of PBO fiber increased obviously
after GO grafting. The IFSS was greatly improved with increasing amplitude of
61.6%. Meanwhile, the grafting processes did not lead to any discernable decrease in
TS. Furthermore, the AO erosion resistance of PBO-APTMS-GO and its composites
was superior to those of untreated one. We anticipate that this study will pave a novel
way for preparing multifunctional PBO fibers with simultaneously improved
interfacial properties and AO erosion resistance.
Acknowledgement
We gratefully acknowledge financial support from the National High
Technology

Research

and

Development

Program

of

China

(863 Program, No. 2012AA03A212), the Chang Jiang Scholars Program and the
National Science Foundation of China (No. 51073047, No. 91016015, No. 51103031,
No. 51173032, NO. 51273050).
References
13

[1] Everett ML, Hoflund GB. Erosion study of poly(ethylene tetrafluoroethylene)

(Tefzel) by hyperthermal atomic oxygen. Macromolecules 2004;37:6013-8.
[2] Tagawa M, Yokota K, Kishida K, Okamoto A, Minton TK. Energy dependence of
hyperthermal oxygen atom erosion of a fluorocarbon polymer: relevance to space
environmental effects. ACS Appl Mater Interfaces 2010;2:1866-71.
[3] Misak HE, Sabelkin V, Mall S, Kladitis PE. Thermal fatigue and hypothermal
atomic oxygen exposure behavior of carbon nanotube wire. Carbon 2013;57:42-9.
[4] Choe EW, Kim SN. Synthesis, spinning, and fiber mechanical properties of
poly(p-phenylenebenzobisoxazole). Macromolecules 1981;14:920-4.
[5] Leal AA, Deitzel JM, Gillespie Jr JW. Assessment of compressive properties of
high performance organic fibers. Compos Sci Technol 2007;67:2786-94.
[6] Hu Z, Li J, Tang PY, Li DL, Song YJ, Li YW, et al. One-pot preparation and
continuous

spinning

of

carbon

nanotube/poly(p-phenylene

benzobisoxazole)

copolymer fibers. J Mater Chem 2012;22:19863-71.

[7] He JM, Zheng N, Ye ZM, Huang YD. Investigation on atomic oxygen erosion
resistance of self-assembly film at the interphase of carbon fiber composites. J Reinf
Plast Compos 2012;31:1291-9.
[8] Zhao F, Huang YD. Grafting of polyhedral oligomeric silsesquioxanes on a carbon
fiber surface: novel coupling agents for fiber/polymer matrix composites. J Mater
Chem 2011;21:3695-703.
[9] An Q, Rider AN, Thostenson ET. Hierarchical composite structures prepared by
electrophoretic deposition of carbon nanotubes onto glass fibers. ACS Appl Mater
14

Interfaces 2013;5:2022-32.
[10] Sun XM, Sun H, Li HP, Peng HS. Developing polymer composite materials:
carbon nanotubes or graphene? Adv Mater 2013;25:5153-76.
[11] Li YW, Zhao F, Song YJ, Li J, Hu Z, Huang YD. Interfacial microstructure and
properties of poly (phenylene benzobisoxazole) fiber grafted with graphene oxide via
solvothermal method. Appl Surf Sci 2013;266:306-12.
[12] Li YB, Peng QY, He XD, Hu PA, Wang C, Shang YY, et al. Synthesis and
characterization of a new hierarchical reinforcement by chemically grafting graphene
oxide onto carbon fibers. J Mater Chem 2012;22:18748-52.
[13] Duo SW, Li MS, Zhu M, Zhou YC. Polydimethylsiloxane/silica hybrid coatings
protecting Kapton from atomic oxygen attack. Mater Chem Phys 2008;112:1093-8.
[14] Fischer HR, Tempelaars K, Kerpershoek A, Dingemans T, Iqbal M, Lonkhuyzen
HV, et al. Development of flexible LEO-resistant PI films for space applications using
a self-healing mechanism by surface-directed phase separation of block copolymers.
ACS Appl Mater Interfaces 2010;2:2218-25.
[15] Park SJ, Jin JS. Effect of silane coupling agent on interphase and performance of
glass fibers/unsaturated polyester composites. J Colloid interface Sci 2001;242:174-9.
[16] Xie YJ, Hill CAS, Xiao ZF, Militz H, Mai C. Silane coupling agents used for
natural fiber/polymer composites: a review. Compos A 2010;41:806-19.
[17] Becerril HA, Mao J, Liu Z, Stoltenberg RM, Bao ZN, Chen YS. Evaluation of
solution-processed reduced graphene oxide films as transparent conductors. ACS
Nano 2008;2:463-70.
15

[18] Zhang XZ, Huang YD, Wang TY, Liu L. Influence of fibre surface
oxidationreduction followed by silsesquioxane coating treatment on interfacial
mechanical properties of carbon fibre/polyarylacetylene composites. Compos A
2007;38:936-44.
[19] Zhang M, Yi M, Shen ZG, Zhao XH, Zhang XJ, Ma SL. Graphene-reinforced
epoxy resin with enhanced atomic oxygen erosion resistance. J Mater Sci 2013;
48:2416-23.
[20] Zhang XQ, Fan XY, Yan C, Li HZ, Zhu YD, Li XT, et al. Interfacial
microstructure and properties of carbon fiber composites modified with graphene
oxide. ACS Appl Mater Interfaces 2012;4:1543-52.
[21] Stankovich S, Dikin DA, Piner RD, Kohlhaas KA, Kleinhammes A, Jia YY, et al.
Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite
oxide. Carbon 2007;45:1558-65.
[22] Lee JR, Choi SY, Bae SJ, Yoon SM, Choi JS, Yoon MJ. Visible light-sensitive
APTES-bound ZnO nanowire toward a potent nanoinjector sensing biomolecules in a
living cell. Nanoscale 2013;5:10275-82.
[23] Li YX, Li YB, Ding YJ, Peng QY, Wang C, Wang RG, et al. Tuning the
interfacial property of hierarchical composites by changing the grafting density of
carbon nanotube using 1,3-propodiamine. Compos Sci Technol 2013;85:36-42.
[24] Peng QY, Li YB, He XD, Lv HZ, Hu PG, Shang YY, et al. Interfacial
enhancement of carbon fiber composites by poly(amido amine) functionalization.
Compos Sci Technol 2013;74:37-42.
16

[25] Lei XF, Chen Y, Zhang HP, Li XJ, Yao P, Zhang QY. Space survivable
polyimides with excellent optical transparency and self-healing properties derived
from hyperbranched polysiloxane. ACS Appl Mater Interfaces 2013;5:10207-20.

17

Figure captions
Fig. 1. Schematic of grafting processes.
Fig. 2. Characterization of GO: (a) TEM image of GO; (b) AFM image of GO; (c)
XRD patterns of graphite and GO.
Fig. 3. FTIR spectra of PBO fibers.
Fig. 4. (a) Wide-scan survey XPS spectra of PBO fibers; XPS spectra of N1s peaks:
(b) untreated-PBO and (c) PBO-APTMS-GO.
Fig. 5. SEM images of (a) untreated-PBO; (b) PBO-oxidation; (c) PBO-OH; (d)
PBO-APTMS and (e)-(g) PBO-APTMS-GO.
Fig. 6. Cross-sectional TEM image of PBO-APTMS-GO.
Fig. 7. (a) TS of PBO fibers and (b) IFSS of PBO fiber composites.
Fig. 8. AFM images of (a) untreated-PBO and (b) PBO-APTMS-GO; (c) Dynamic
wetting curves of PBO fibers; SEM images of (d) untreated-PBO and (e)
PBO-APTMS-GO after de-bonding.
Fig. 9. SEM images of (a) untreated-PBO and (b) PBO-APTMS-GO exposed to AO
for 8 h; (c) TS retention of PBO fibers after AO exposure; SEM images of a
micro-droplet (d) before and (e) after AO exposure; (f) IFSS retention of PBO fiber
composites after AO exposure.
Fig. 10. XPS spectra of Si2p peak of PBO-APTMS-GO (a) before and (b) after AO
exposure.

18

Fig. 1.

Fig. 2.

19

Fig. 3.

Fig. 4.

20

Fig. 5.

Fig. 6.
21

Fig. 7.

Fig. 8.

22

Fig. 9.

Fig. 10.

23