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Co-depositing mussel-inspired nanohybrids onto 1D fibers under “green” conditions for significantly enhanced surfacial/interfacial properties Xiaobin Yang, Hongpeng Du, Songwei Li, Zhen Xing Wang, and Lu Shao ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b00290 • Publication Date (Web): 12 Feb 2018 Downloaded from http://pubs.acs.org on February 13, 2018

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ACS Sustainable Chemistry & Engineering

Co-depositing mussel-inspired nanohybrids onto 1D fibers under “green” conditions for significantly enhanced surfacial/interfacial properties

Xiaobin Yang,† Hongpeng Du,‡ Songwei Li,† Zhenxing Wang,† and Lu Shao*†



MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion

and Storage, State Key Laboratory of Urban Water Resource and Environment, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China. ‡

Hangzhou Fortune Gas Cryogenic Group CO., LTD, Hangzhou 310000, China.

Mailing address: No 92, West Dazhi Street, Harbin 150001, China. *Corresponding author: L. Shao. Tel: +86-451-86413711. Fax: +86-451-86418270. Email: [email protected]

KEYWORDS:

Surface

modification,

mussel-inspired,

interfacial combination, tensile strength

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composite

materials,

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ABSTRACT: Co-deposition of mussel-inspired nanohybrid coating was realized onto carbon fiber (CF) surface via co-incubation in the dopamine (DA) and octaammonium polyhedral oligomeric silsesquioxane (POSS-NH2) mixed aqueous solution. The deposition procedure was conducted under ambient conditions, and no harsh conditions and toxic solvents were needed. The surface morphology, compositions, and energies of CFs were investigated. The interfacial shear strength (IFSS) were measured to demonstrate the interfacial combination and compatibility of fiber and epoxy resin, and the single-filament tensile strength (TS) was also determined to evaluate the damage degree brought by the modification procedure to the fiber intrinsic strength. As a result, the nanohybrid coating could greatly enhance surface wettability, interfacial compatibility, and interfacial mechanical strength, and bring no deterioration to fiber intrinsic strength. Our facile strategy presents a promising platform to modify various 1D fiber surface for advanced composite materials towards broadly mechanical-demanding and energy-saving usages.

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INTRODUCTION

The increasing social demands and appeals on energy conservation and emission reduction has accelerated the development of advanced composite materials with high strength and light weight for applications in automobile lightening, wind turbine blades, and airbus. Therein, one dimensional (1D) carbon fiber (CF) as a representative reinforcement not only possesses high strength and low density, but also combine high flexible knittability, which enables the composite materials to produce enormous value annually.1-6 Generally, the surface/interfacial structure and chemistry are critical factors for the overall performance of composite materials,7-17 in particular the surface inertia of CFs leads to non-ideal interfacial combination effect with matrix.18 Given this point, continuous endeavor on surface modification of CFs, such as chemical oxidation, radical irradiation, and chemical coating, has been devoted to breaking through that limit.19-26 Noticeably, the majority of surface modification procedure involves the incorporation of strong acids, toxic polar organic reagents, the high energy consumption (high incubation temperature, ray irradiation), and catalyst processing, etc.18,23-30 It aggravates environmental pollution and energy consumption to some extent, which impedes its environmental and sustainable development. Moreover, most of those approaches easily bring defects and weak spots to fiber surface and result in deterioration of intrinsic tensile strength of CFs owing to the harsh modifying conditions. Thus, our initiative is to realize the similar CF surface activation and interfacial strengthening effect and avoid damage to intrinsic tensile strength of fibers via a relatively “green” and high-efficient strategy.

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On the other hand, bio-inspired by the strong adhesive marine mussel byssus from nature, dopamine (DA) with similar functional moieties has been developed to simulate superior bioadhesion. It results in substrate-independent surfacial coating via self-polymerizing into polydopamine (PDA) in a typical alkalescent aqueous solution (Tris-HCl, pH 8.5).31-34 Given the secondary reactivity of PDA, Michael addition and Schiff base reactions could occur between PDA and the amino-containing species via the two-step or one-step methods.31,35-38 In addition, octaammonium polyhedral oligomeric silsesquioxane (POSS-NH2) with amino moieties hanging outside typically possesses a cage-like siloxane framework with a pore aperture and cavity diameter of 0.53 nm and 1-3 nm, respectively.39 Thus, nanoporous POSS-NH2 could participate in DA self-polymerization, based on which POSS-NH2 could be immobilized on the fiber surfaces. Even though several works were reported by incorporating POSS to fiber surface modification.2,19,24,39-48 Those procedures were either involved with strong acids, organic reagents, the high energy consumption, or the multi-step manipulation. However, our initiative is to exploit the equally effective and powerful strategy via eco-friendly and resource-saving technology and engineering. To clarify the differences among the strategies, the modification details are summed up in Table S1. Therefore, considering inherent high strength and modulus, excellent thermal and chemical resistance of POSS,49-51 it is fascinating to explore the concept availability of such environmentally friendly PDA/POSS hybrid coating on CFs for advanced composites.

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Herein, we designed to construct nanoporous PDA/POSS hybrid scaffolds on CFs via one-step co-incubation in the DA and POSS-NH2 mixed aqueous solution (Figure 1). The whole co-deposition procedure was conducted under ambient conditions, and no harsh conditions and toxic solvents were needed. The surface morphology, compositions, and energies of CFs were investigated to evaluate the surfacial wettability. To demonstrate interfacial compatibility of fiber and resin (epoxy resin as matrix), the interfacial shear strength (IFSS) and damage morphology were measured through pulling off the cured resin beads from the single filaments. Moreover, the single-filament tensile strength (TS) was also determined as the parameter to evaluate the damage degree to the fiber intrinsic strength brought by the modification procedure. The results indicated that the PDA/POSS co-deposition on fiber surface could greatly enhance surface wettability, interfacial compatibility, and interfacial mechanical strength, and bring no deterioration to fiber intrinsic strength. And this strategy applicable on diverse 1D fiber surface due to the unique adhesion ability of PDA will promisingly accelerate advanced composite materials towards broadly mechanical-demanding and energy-saving usages.

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Figure 1. Schematic of possible mechanism of PDA/POSS hybrid coating co-deposited on surfaces of CFs through incubation CFs in the DA and octaammonium polyhedral oligomeric silsesquioxane (POSS-NH2) mixed aqueous buffer solution at room temperature.

EXPERIMENTAL SECTION Materials. Carbon fibers T700-12K-50C with the diameter 7 µm were supplied by Toray Industries Inc., and followed by Soxhlet extraction according to our former work before using. Dopamine hydrochloride was obtained from Sigma-Aldrich. Tris(hydroxymethyl)aminomethane (Tris) were supplied by Aladdin (China). Acetone, hydrochloric acid (HCl), and ethylene glycol were purchased from Tianjin Kermel Chemical Reagent Co., Ltd (China). Epoxy resin matrix (E-51, epoxide value 0.51± 0.3 eq/100 g) was supplied by Bluestar Wuxi Petrochemical Co., Ltd (China). The curing agent (H-256) was received from Jiangyin Wayfar Synthetic Material Co., Ltd (China). Ultrapure water was homemade by a Sartorius AG arium system. All

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chemical reagents were used as received.

Preparation of PDA/POSS coated CFs. PDA/POSS co-deposited CFs (denoted as CF-PDA/POSS) was prepared through incubating the pristine CFs in the DA and POSS-NH2 mixed aqueous solution with respective concentration of 2 g L-1 (Tris-HCl, pH 8.5) at room temperature for 6 h. After incubation, resultant CFs were vigorously rinsed with water several times and dried at 70 °C overnight. In contrast, pure PDA functionalized CFs (denoted as CF-PDA) was also prepared by immersing pristine CFs in only DA aqueous solution (2 g L-1, Tris-HCl, pH 8.5), maintaining other conditions unchanged.

Characterizations of CFs. Fourier transform infrared spectroscopy (FTIR) spectra were recorded by a Spectrum One instrument (Perkin Elmer, USA). X-ray photoelectron spectroscopy (XPS) spectra were performed using an AXIS ULTRA DLD spectrometer (SHIMADZU, Japan). Scanning electron microscopy (SEM, Hitachi S-4500, Japan) was utilized to observe the morphologies of CFs and also conducted elemental composition analysis using appendant energy-dispersive X-ray spectroscopy (EDX). Atomic force microscopy (AFM) (Solver P47 AFM, Russia) was used to collect the stereo topographies and measure the roughness of CFs in the tapping mode. The weight loss of CFs with or without PDA-based modification were measured from room temperature to 1000 °C by a thermal gravimetric analyzer (Q500, TA Instruments, USA) with a 10 °C min−1 heating rate under nitrogen. Dynamic

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contact angle tests were recorded through immersing CFs into two testing solutions by a dynamic contact angle meter and tensiometer (DCAT21, Data Physics Instruments, Germany) and followed by the calculation of surface energies of CFs using the d collected contact angles. Two test liquids were used, ethylene glycol ( γ l = 29.0 mN p d p m-1, γ l = 19.0 mN m-1) and water ( γ l = 21.8 mN m-1, γ l = 51 mN m-1). Eight valid

values were recorded per sample and averaged to calculate its surface energies.

Mechanical Performance Tests of CFs and Composites. The single-filament TS of CFs was evaluated on a universal testing machine (Instron 5500R, USA) as per ASTM D3379-75. Every 80 specimens were conducted and analyzed by Weibull statistical method per sample with the gauge length and loading speed of 20 mm and 10 mm min−1. The IFSS was conducted on an interfacial evaluation equipment (FA620, Japan) through pulling off the cured resin beads from the single fibers. The beads were prepared by dropping small resin droplets (E-51/H-256, w/w, 100/32) with a pin and followed by curing procedure at 90, 120, 150 °C for 2, 2, 3 h, respectively. The filament was fixed at two ends of the metal holder, then the blade was tuned to block a resin marble on the fibers and pulled out it when the metal holder was advancing at the slow mode and the blade was fixed. Every 50 specimens were tested per sample.

RESULTS AND DISCUSSION Possible Mechanism underlying the PDA/POSS co-deposition. The typical

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polymerization mechanism of PDA was presented in Figure S1 (Supporting information). In a typical alkalescent aqueous solution, DA first undergoes the interval

oxidation,

intramolecular

cyclization,

and

rearrangement

into

5,6-dihydroxyindole (DHI) and its quinone type. Afterwards, it lead to the mutual branching reactions and covalent binding among aryl rings. The synergetic effects between the covalent bindings and noncovalent bindings (π−π stacking, hydrogen bonding, and charge transfer interactions) could result in adhesive deposition of PDA onto substrates. Meanwhile, the quinone type oxidized from the catechol moieties in PDA could in situ or followingly react with amino-containing species via Michael addition or Schiff base reactions and formed the covalent −C−NH or −CN bond under the alkaline solution.35-38 Therein, the PDA network and POSS-NH2 framework could be crosslinked together during the co-deposition (The mechanism was shown in Figure 2).

Figure 2. The possible mehcanism ocurred in the co-incubation of DA and octaammonium polyhedral oligomeric silsesquioxane (POSS-NH2) in Tris-HCl buffer solution (pH=8.5).

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Physicochemical Characterization of CFs. FTIR spectra were used to clarify the surface functional moieties of pristine CF, CF-PDA, and CF-PDA/POSS. As shown in Figure 3, pristine CF presents C-H stretching vibrations at 2920-2854 cm-1 and that of -OH at 3400 cm-1 centred location. After pure PDA modification, as for CF-PDA, the component located at 1710 cm-1 is ascribed to C=O stretching vibration owing to the quinone structure oxidized from the catechol group from PDA. The peaks at 1615 and 1513 cm-1 are attributed to aromatic C=C stretching vibration and N–H shearing vibration, respectively. The broad peak ranged from 3600 to 3100 cm-1 is attributed to the synergistic traits of stretching vibrations of –OH/–NH2 groups. As for CF-PDA/POSS, its characteristic curve not only embodies the features of CF-PDA but also arises some new peaks. The component at 2920-2854 cm-1 is assigned to the stretching vibrations of -CH2- moieties. The spectrum located at 1382 cm-1 corresponds to C=N stretching vibration owing to the in situ Schiff base reaction occurred between the catechol groups of PDA and amino groups from POSS-NH2.34,36 The peak at 1120-1110 cm-1 refers to the trait of Si-O-Si groups derived from the typical POSS framework. The results indicated that pristine 1D CF surfaces were successfully coated by PDA and PDA/POSS owing to PDA-based strong and substrate-independent adhesion. Given previous studies about interactions between mussel foot proteins (origin of DA) and substrates,52,53 the anchoring effects derived from catechol moieties and additional benzene π−π stacking interactions all contributes to the adhesion between PDA/POSS coating and CF surface.31,35,54,55 The as-fabricated nanohybrid coating could withstand harsh rinsing and display good

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stability (Supporting Information, Figure S2). The appending functional moieties of the resultant hierarchical microstructure endow inert CFs with excellent reactive potential and serve as a bridge to joint CFs and matrix.

Figure 3. FTIR spectra of POSS-NH2, pristine CFs, CFs after PDA treatment (CF-PDA), and CFs after co-deposition of DA and POSS-NH2 (CF-PDA/POSS).

Additionally, the surfacial chemistry of CFs was analysed by XPS (Table 1, Figure 4). According to the wide spectra results, the intensity of N element presented a gradually increasing trend for spectra of CFs after PDA coating and PDA/POSS coating as compared to that of pristine CF. Meanwhile, a new Si peak attributed to POSS arises for spectrum of CF-PDA/POSS coating, confirming successful coatings on CFs. The emerging chemical bonds could also detected from FTIR spectra (Figure 3); the C-O and C-N peaks appeared in PDA coating and a new C=N peak appeared in PDA/POSS coating. As for C 1s analysis of CFs, pristine CF presented C-C bond (284.6 eV) and C-O bond (286.0 eV). As for CF-PDA, the peak location of the C-O 11

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bond exhibited a red shift to 286.2 eV because of the adjacent aromatic ring strcture. In addition, it emerged nitrous carbons (C-N, 285.7 eV), carbonyl carbons (C=O, 288.2 eV) as compared to the characteristics of pristine CFs. CF-PDA/POSS presented a new C-Si peak (284.0 eV) attributed to the incorporated POSS framework and C=N peak (287 eV) ascribed to the reaction product of PDA and amino amino-containing species via Schiff base reactions under the alkaline solution. The O/C and N/C ratios of CF-PDA and CF-PDA/POSS increased obviously as compared to that of pristine CF (Table 1), which could enhance surface activity of CFs.

Table 1. Surface element characterization of CFs Composition (At. %)

Atom ratio

Samples C

O

N

Si

O/C

N/C

pristine CF

89.98 9.67

0.35 -

0.107 0.004

CF-PDA

84.59 12.6

2.81 -

0.149 0.033

CF-PDA/POSS 77.72 14.55 3.13 4.60 0.187 0.040

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Figure 4. (a) Wide XPS spectra, and respective C 1s fitting analysis of (b) pristine CFs, (c) CF-PDA, and (d) CF-PDA/POSS.

In addition, SEM was utilized to monitor the surfacial morphology evolution of CFs during modification (Figure 5a-c, the larger version see Figure S3, Supporting Information). As shown in Figure 5a, the surfaces of pristine CFs are typically smooth. After incubation in fresh DA precursor solution, the surfaces of resultant CF-PDA emerge some scattered nanoparticles owing to the self-polymerized PDA. As for CF-PDA/POSS, much more surface-bound nanoparticles are visible and exhibit a ridge-and-valley morphology because the nanoscale POSS could immobilize into the PDA-based nanohybrid coating with the aid of the favourable adhesion. The increasing surface-bound nanoparticles could augment the surface roughness, in turn 13

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enhancing the potential curing reactive area and the capacity of mechanical interlocking. EDX mappings indicated the uniformity of the surfacial nanohybrid coating (Figure 5d-f); N was derived from typical PDA and POSS-NH2, Si from POSS-NH2. Moreover, similar results on CF surfacial morphology evolution during modification could also be deduced from AFM images (Figure 5g-i). The stereo topographies of CFs well confirmed the excellent physicochemical manipulation on CF surface via PDA-based strategy. Also, the average arithmetic roughness, Ra, calculated from AFM results was utilized to evaluate surface roughness. After de-sizing through Soxhelet extraction, the surfaces of pristine CFs are typically smooth (Ra=6.3 nm). After PDA-based surface modification of pristine CFs, CF-PDA (Ra=11.3 nm) and CF-PDA/POSS (Ra=23.7 nm) demonstrate the great increment in Ra by 77% and 270%, respectively, when compared to that of pristine CFs. As for CF-PDA/POSS, the PDA/POSS nanohybrid coating largely augmented the surface roughness in contrast with CF-PDA owing to the nanoscale POSS particles incorporation. The elevated surface roughness could supply more reactive sites in following curing reaction and boost the interfacial mechanical interlocking between fibers and epoxy resin matrix. In addition, thermogravimetric analysis (TGA) test was conducted on CFs under the same calcination conditions (Supporting information, Figure S4). CF-PDA and CF-PDA/POSS exhibited weight loss difference of ca. 2.2 wt. % and ca. 1.2 wt. %, respectively, as compared to that of pristine CFs up to 950 °C. Meanwhile, the similar curve tendency displayed benign thermal stability of the as-deposited PDA-based coating layer on the fiber surface.

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Figure 5. (a-c) SEM images on the surfaces of CFs, (d-f) EDX mapping images on the surface of CF-PDA/POSS (the green rectangle circled the detected region, (e,f) images displayed the element distribution of N and Si, respectively, (g-i) AFM images on the surface of CFs labelled with the Ra values.

The surface energy is critical to evaluate the specific activity of CFs and determines surfacial resin impregnation effect.40,56 The optical image of DCAT21 machine and relevant measuring schematic were shown as Figure 6a.The values of surface energy were obtained by the statistic calculation of the recorded contact angles of water and ethylene glycol according to Equations 1 and 2: 1/2

1/2

γ l (1 + cosθ ) = 2 (γ lpγ fp ) + 2 ( γ ld γ df )

(1)

γ f = γ df + γ fp

(2)

where γ and θ correspond to the surface energy and recorded contact angles, respectively. The superscripts d and p refer to its dispersive and polar components, l and f to the testing liquid and fiber, respectively. As shown in Figure 6b, c, and Table

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S2 (Supporting information), the surface energies of PDA and PDA/POSS coatings exhibited an increment to various extent, which is attributed to plenty of functional moieties of resultant PDA-based coatings and nanoporous POSS frameworks. The external hybrid coating commendably covered the non-ideal graphitic basal planes on the surfaces of pristine CFs. Compared to that of pristine CFs (40.0 mN m-1), the surface energies of CF-PDA and CF-PDA/POSS increased by 33.5% and 65.3%, respectively. The polar functional moieties hanging outside and surfacial micro-structures jointly enhanced the polar compositions. As a result, the elevated surface energy could facilitate resin impregnation and following curing reactivity.2, 18

Figure 6. (a) The optical image of the dynamic angle test machine (DCAT21) and the schematic illustration of the contact angle measurement as for fiber specimen. (b) Contact angles of water and ethylene glycol on CFs, and (c) the calculated surface energies of CFs.

Mechanical Performance Tests of CFs and Composites. Two critical parameters are used to comprehensively evaluate the mechanical properties of CFs (tensile strength, TS) and corresponding composites (interfacial shear strength, IFSS). IFSS is generally used to predict the real mechanical properties of resultant composites. The

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schematic of IFSS measurement of the single filament was displayed in Figure 7a. The filament was fixed at two ends, the blade was fixed and pulled out the resin marble when the metal holder was advancing. The values of IFSS were recorded through pulling out the cured resin marbles from single filament and calculated by Equation 3: IFSS =

Fmax

π dl

(3)

where Fmax corresponds to the maximum recorded load, d is the diameter of single filament, and l is the gauge length embedded under a resin marble. As shown in Figure 7b, the IFSS value of pristine CF is 71.5 MPa. As for CF-PDA, it reaches 91.9 MPa with a 28.5% amplification as compared to that of pristine CF because the PDA coating effectively activated the inert surfaces of CFs and enhanced resin infiltration for better interfacial interaction. As for CF-PDA/POSS, the recorded IFSS is 117.1 MPa (63.8% amplification to that of pristine CF). The amino moieties hanging outside PDA-based coating could participate in the curing reaction with epoxy resin, which greatly strengthened the adhesion between the resin system and the fiber surfaces. Compared to pure PDA coating, PDA/POSS nanohybrid modification combined binary merits and exhibited a synergistic effect, resulting a higher amplification in IFSS evaluation of CFs. The densely-distributed nanoparticles on CF-PDA/POSS surfaces and the derived enhanced surface roughness effectively avoided the “lubricant” effect brought by the typical smooth surfaces of CFs and augmented the “fortified” effect. The above analysis was also verified by SEM images of filaments after IFSS test (Figure 7c-e, the magnified figures see Figure S5, Supporting

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information). The exposed fiber surface of pristine CF was almost neat and there appeared gap between fiber and resin. It emerged few remain epoxy fragments on CF-PDA, more fragments on CF-PDA/POSS, simultaneously showed benign bonding between fiber and resin. Combining the contrast of IFSS of CF/epoxy resin composites (Supporting information, Table S3), the PDA/POSS co-deposition strategy could be considered as a commendable alternative to improve fiber/resin interface combination and effectively realize the applied stress transfer and high-efficient load implementation.

Figure 7. (a) The schematic of interfacial shear strength (IFSS) measurement of the single filament. (b)IFSS evaluation of CFs through pulling out the cured resin marbles from the single filament, and SEM images of the samples of (c) the pristine CF, (d) CF-PDA, and (e) CF-PDA/POSS after IFSS measurement. The arrows points to the remained resin.

Single filament tensile test is used to determine TS of CF, which is the intrinsic

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property of 1D fibers (Figure 8a). The recorded TS represents its inherent mechanical property and further affects the in-plane properties of resultant composites. Compared with the negative influence on inherent mechanical properties of CFs by conventional surface modification approaches, we surprisingly found that the mussel-inspired hybrid coating bring no deterioration to TS of CFs. As shown in Figure 8b, the TS values of CFs with and without PDA-based coating were determined. All recorded data were further statistically analysed by the Weibull distribution function to obtain reliable results. Most interestingly, the PDA-based coatings did not bring any deterioration on CFs and even endowed the resultant CFs with a little higher inherent mechanical properties in contrast to the pristine CFs; the TS values of CF-PDA and CF-PDA/POSS were 4.59 and 4.69 GPa, respectively, as compared to that of pristine CFs (4.56 GPa). It may be owing to the mild incubation conditions during PDA-based coating and it could effectively prevent from bringing surfacial defects to fiber surface. In addition, to some extent, the PDA/POSS hybrid coating might present the possible repair effect toward the flaws on fiber surface benefited by the PDA-based boost adhesion. Some of external forces could be consumed and dissipated within the PDA/POSS hybrid networks. Meanwhile, the Weibull shape parameters (the inset table in Figure 8b) were critical to quantitatively evaluate the scatter traits of CFs.57 Theoretically, the larger the shape parameter is, the less defects CFs have. CF-PDA exhibited an obvious enhancement in Weibull shape parameter owing to the aforementioned repair mechanism of the mussel-inspired PDA coating. As for CF-PDA/POSS, the binary nanohybrid co-deposition leads to the decrease of the

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Weibull shape parameter to the similar level of pristine CFs due to the incorporated nanoscale porous POSS frameworks. Furthermore, as compensation, the rigid nanoporous structures of incorporated POSS frameworks could also absorb the interior and exterior load well. All in all, the scaffolded PDA/POSS coating constructed on the surfaces of CFs could avoid the deterioration of in-plane properties of resultant composites. This simple surface modification strategy could be considered as a powerful alternative method to carry forward the advanced fiber-reinforced composite materials.

Figure 8. (a) The schematic of tensile strength (TS) measurement of single filament. The filament was fixed at a coordinate paper with removal of the central test zone, then we fixed two ends of the coordinate paper with the clamps of universal testing machine. We cut open a cut with scissors on both sides prior testing. (b) TS evaluation of CFs, including pristine CF, CF-PDA, and CF-PDA/POSS (The inset table listed the Weibull shape parameters).

CONCLUSIONS

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In summary, a mussel-inspired strategy to construct PDA/POSS nanohybrid architecture onto the surfaces of 1D CFs was realized by one-step co-incubating in DA and POSS-NH2 aqueous solution at ambient conditions. As a result, this strategy locked the POSS-NH2 frameworks appending with abundant amino moieties and the robust adhesive PDA networks together with the aid of the occurred Michael addition and Schiff base reactions, and in situ anchoring the entire hierarchical nanohybrid frameworks onto the fiber surfaces. The PDA/POSS nanohybrid coating resulted in the enhanced surface roughness for interfacial interlocking and surfacial wettability for interfacial compatibility with a greater degree to that of CF-PDA as compared to pristine CF. The nanohybrid coating also led to enhancement in interfacial shear strength and served as a benign interface to effectively realize the applied stress transfer and load implementation. In addition, the modification procedure did not bring deterioration to fiber intrinsic strength. Based on the aforementioned investigation, the analogous PDA-based functionalization is a promising strategy to modify

1D

fiber

surface

for

advanced

composite

materials

towards

mechanical-demanding and energy-saving applications.

ASSOCIATED CONTENT Supporting Information. Polymerization mechanism of PDA, SEM images of CFs before and after rinsing, the larger version of the morphology evolution of fiber surfaces, SEM images of the fiber samples after IFSS measurement, contrast details about incubation conditions and maximum IFSS values about POSS-grafted CFs,

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surface chemical compositions and surface energy evaluation, contrast of IFSS of CF/epoxy resin composites.

AUTHOR INFORMATION Corresponding Author *L.

Shao.

Tel:

+86-451-86413711.

Fax:

+86-451-86418270.

Email:

[email protected] Notes The authors declare no competing financial interest.

ACKONWLEDGEMENTS This work was financially supported by National Natural Science Foundation of China (21676063), State Key Laboratory of Urban Water Resource and Environment (Harbin Institute Technology) (No. 2017DX07), and HIT Environment and Ecology Innovation Special Funds (HSCJ201619).

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Graphical abstract

(7.5 cm × 4.76 cm)

An eco-friendly PDA/POSS co-deposition strategy for fiber surface modification was advanced for enhancing fiber/resin combination without deteriorating fiber intrinsic strength.

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