Polyacrylonitrile

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General Research

Constructing Flexible and CuS-coated Meta#aramid/ Polyacrylonitrile Composite Films with Excellent Coating Adhesion Zengxiao Wang, Ting Li, Junrong Yu, Zuming Hu, Jing Zhu, and Yan Wang Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.9b03221 • Publication Date (Web): 02 Sep 2019 Downloaded from pubs.acs.org on September 3, 2019

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Industrial & Engineering Chemistry Research

Constructing Flexible and CuS-coated Meta-aramid /Polyacrylonitrile Composite Films with Excellent Coating Adhesion Zengxiao Wang, Ting Li, Junrong Yu*, Zuming Hu, Jing Zhu, Yan Wang State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, P. R. China *Corresponding author: [email protected]

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Abstract To achieve electrically conductivity comparable to metallic materials, electroless deposition has attracted much interest for low-cost fabrication of conductive organic materials in recent years. However, the metallized coatings constructed by such kind of method usually have to utilize expensive sensitizer and activator, hindered its use in practical applications. Here, a novel method, no need of sensitizer and activator, was developed for fabricating flexible and conductive meta‐Aramid/Polyacrylonitrile (PMIA/PAN) composite film with excellent coating adhesion. We used the PMIA as the matrix and introduced PAN components to prepare a series of PMIA/PAN composite films. A strongly bonded conductive CuS coating is obtained by a redox chemical reaction. It was found that PMIA/PAN=10/1 is the best blending ratio for preparing PMIA/PAN-CuS composite film. And excellent adhesion is exhibited between CuS coating and pure PMIA/PAN organic substrate even after more than 15 times of tape stripping treatment or 170 min ultrasonic treatment. Keywords: poly (m-etaphenylene isophthamide), polyacrylonitrile, composite film, CuS, electrically conductivity

1. Introduction PMIA fiber, with excellent performances, has been accepted as a superiorperformance polymeric-fiber, such as good flame retardancy, superior thermal stability, strong mechanical properties, excellent chemical resistance and so on.1-5 Till date, the modification of PMIA materials mainly involves the introduction of characteristic structural units on the PMIA molecular backbone by copolymerization modification,6 the introduction of functional side groups for structural and functional modification,7 blending with other high polymers or filling fiber,8-12 and mineral powder or other inorganic filler for composite modification.13-15 It is easy to see that blending and composite modification of PMIA is an economical and effective method relative to copolymerization and structural modification. Remarkably, the preparation of electrical conductive materials has attracted widespread attention among researchers, due to its potential applications of electromagnetic shielding, stretchable electronics, eliminating static electricity and so on.16-20 Meanwhile, the electroless deposition is widely used for surface metallization of non-metallic materials because it has no need of special equipment and no special requirement on the shape of the materials.21-25 In our previous work, we exploit a


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method of simply dipping the PMIA fibers into a mixed aqueous suspension of dimethylsulfoxide (DMSO) and prefabricated nano-silver sol to deposit the metal silver nanoparticles on the surface of PMIA fibers, the silver nanoparticles functioned as the catalyst as well as the anchor for the subsequent nickel coating layer, and the nickel-coated PMIA composite fibers exhibit low electrical resistance and homogeneous surface topography, which were prepared by the electroless nickel plating.18 However, it is worth noting there are many factors that impair the wider application of electroless plating, such as, the electroless plating baths have stringent PH requirements and require a variety of chemical reagents for formulation; the matrix material always needs to undergo tedious sensitization and activation treatment, however, the sensitizers and activators used are often expensive.22, 26-29 In addition, for the conductivity research of meta-aramid-based materials, the main focus of the past is on the research of fiber materials and composite resin materials, and rarely on the thin film. Hence, it is urgent to develop a new method for surface metallization for aramid film materials with superior coating adhesion and no need of any cumbersome sensitization or activation treatment. The nitrile group (-CN) in the polyacrylonitrile has a strong adsorption effect on the metal copper ions in the copper sulfate (CuSO4).30 This provides a theoretical basis for the feasibility of forming a conductive coating on the surface of the PMIA/PAN composite film, where a chemical reaction method can be utilized to form a strong metal copper sulfide conductive coating on the surface of the PMIA/PAN composite film by adsorption and reducing agent reduction. Herein, we report a facile two-step method to constructing flexible and electrically conductive PMIA/PAN-CuS composite film with excellent coating adhesion. Specifically, no sensitizers or activators are needed, and only two kinds of inexpensive chemical reagents are required during the entire conductive coating generation process.

2. Experimental Section 2.1 Materials



Polyacrylonitrile (PAN) was provided by Shanghai Petrochemical Shanghai Petrochemical Co., Ltd. (Shanghai, China) and the weight-average molecular weight of the PAN was 78000. m-Aramid was provided by X-FIPER New Material Co., Ltd (Jiangsu, China). Copper sulfate (CuSO4), sodium thiosulfate (Na2S2O3) and N, Ndimethylacetamide (DMAc) were purchased from Ling Feng Chemical Reagent Co. Ltd (Shanghai). lithium chloride anhydrous (LiCl) was purchased from J&K Chemical Technology. And all of them used without further purification. 2.2 Preparation of The PMIA/PAN Composite Film Firstly, the 18.5 wt % PMIA solution was diluted to 15 wt % using DMAc. Preparing a 15 wt % PAN solution using DMAc as solvent. Subsequently, the PMIA solution (15%) and the PAN solution (15%) were blended in a mass ratio of PMIA/PAN=7:1, adding lithium chloride LiCl as compatibilizer and mechanically stirred at 65 °C for 5 h until the blend solution was stirred evenly. The 10:1, 13:1 and 16:1 blending solutions were prepared according to the same experimental procedure. Secondly, the PMIA/PAN blend solution (PMIA/PAN=7:1) was poured onto a clean and dry glass plate, using a wiper to evenly spread the blending solution in one direction, and then the glass plates were immersed in coagulation bath (70 wt % aqueous solution), solidification for 5min at room temperature. The films were dried under vacuum at 45 °C for 12 h, after being desalting with distilled water at 60 °C for 36 hours. Subsequently, the 10:1, 13:1 and 16:1 composite films were prepared according to the same experimental procedure. 2.3 Preparation of Electrically Conductive PMIA/PAN-CuS Composite Film Preparing 2 wt % aqueous copper sulfate solution (160 g) and 2 wt % aqueous sodium thiosulfate solution (20 g), respectively. The formulated copper sulfate aqueous solution was poured into a three-necked flask, followed by a series of labeled PMIA/PAN composite films with different blend ratios. Heating to 65 °C under nitrogen atmosphere, 10 g of sodium thiosulfate solution was added to the system, and reacting at constant temperature for 0.5 h, then heating to 85 °C, another 10 g of sodium thiosulfate solution was added to the system, and reacting at constant temperature for 0.5 h, finally heating to 105 °C, and reacting at constant temperature for 1.5h, mechanical stirring throughout the process. Finally, the blend films were taken out and washed three times with deionized water, followed by vacuum


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drying at 45 °C for 12 h. 2.4 Characterization. The surface morphologies of the PMIA/PAN composite films were evaluated by field emission scanning electron microscopy at an accelerating voltage of 5 kV (FESEM, Hitachi SU8010, Japan). The crystalline structure of the all film samples were evaluated by the powder XRD tests, XRD patterns were obtained over the 2θ range of 10−75° (D/Max2500VB2+/PC, Rigaku, Japan). And chemical composition of the PMIA/PAN-CuS composite films were evaluated by the X-ray photoelectron spectroscopy (Thermo Scientific Escalab 250Xi, USA). Thermal stabilities of the PMIA/PAN composite films were analyzed by means of TA Instruments, the PMIA/PAN composite films were heated at 20 °C min-1 within a range of 50-800 °C under nitrogen atmosphere (TG 209 F1 Iris, Germany Chi Instrument Manufacturing Co., Ltd.). All film samples were subjected to tensile test using C44.104 model microcomputercontrolled electronic universal testing machine (Meters Industrial Systems (China) Co., Ltd.). The sample width was 10 mm. The thickness was measured by a thickness gauge. The tensile rate was 5 mm/min. The sample gauge length was 20 mm. Each sample was measured five times and averaged. The sheet resistivity measurements of PMIA/PAN-CuS composite films were measured by a four-probe method.



Scheme 1. Schematic illustration for fabrication of PMIA/PAN-CuS composite films and proposed mechanism for formation of CuS coating.

Results and Discussion 2.1.

Preparation and Characterization of PMIA/PAN Composite Films

The cross sections of PMIA/PAN Composite Films at varied blending ratios were observed by SEM. As shown in Figure1(a1-d1), due to the rapid solidification of the blend films during double diffusion, the dactylopore structures exist in all PMIA/PAN composite films, which is the main reason for the poor mechanical properties of the blend films. Specially, typical two-phase separation structure is shown in the enlarged cross-sectional images (Figure1 a2-d2), the PMIA with a large content in the blend system forms a continuous phase, and the PAN with a small content forms a spherical dispersed phase, respectively. The XRD measurements were utilized to further investigate the effect of blend ratio on PMIA/PAN film structure (Figure 2a), It can be seen from the figure that the PAN curve has a sharp diffraction peak at 2θ=17°, while the strongest diffraction peak of the PMIA film appears at 2θ=25°. The diffraction peak shapes of the PMIA/PAN composite films are basically consistent with the pure PMIA film, and all of the PMIA/PAN composite films have strong diffraction peaks at 2θ=17° respectively. In addition, there is no obvious new diffraction peak in the diffraction peak of the blend films, which indicates that there is no chemical reaction during the blending of PMIA and PAN solution.


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Figure 1. Cross-sectional images of PMIA/PAN composite films at a series of blending ratios of (a1 and a2) 7/1, (b1 and b2) 10/1, (c1 and c2) 13/1, (d1 and d2) 16/1.

The superior thermal stability of PMIA/PAN composite films is essential for potential practical applications. Typical TGA curves for pure PMIA film, pure PAN film and PMIA/PAN composite films are shown in Figure 2b, PMIA has no obvious thermal decomposition below 400 °C, which indicates its good thermal stability. The thermogravimetric curve of the PAN film rapidly decreases at around 320 °C. Nevertheless, the PMIA/PAN composite films substantially retains the good thermal stability compared to the pure PMIA film, and meets the application of special fields with higher temperature requirements. The typical mechanical properties of the PMIA/PAN composite films are shown in Figure 2c. It is a pity that the pure PAN film is so brittle that it cannot be tested for mechanical properties. And the tensile strength and young’s modulus of the PMIA/PAN composite films increased with increasing the blending ratio of PMIA



component, which indicated the continuous PMIA phase contributed primarily to the mechanical properties of the composite films.

Figure 2. (a)WARD patterns and (b) TG curves of pure PMIA film, pure PAN film and PMIA/PAN composite films; (c) the mechanical properties of pure PMIA film and PMIA/PAN composite films

2.2.

Preparation and Characterization of PMIA/PAN-CuS Composite Films

The blending ratio changes for constructing PMIA/PAN Composite Films not only cause the changes of the mechanical properties but also inevitably affect the appearance and performance of the subsequent CuS-coating. Figure 3 shows SEM images of PMIA/PAN-CuS composite films at a series of blending ratios, it can be seen in Figure 3a and b that the CuS coatings are compact and dense, and there is almost no crack or hole defect on the surface of the CuS-coated layer. However, the surface roughness of PMIA/PAN-CuS composite films increases with the further decrease of the PAN solution concentration (Figure 3c-d). Specially, as shown in Figure 3d1-d2, the CuS-coating shows serious defects on both overall appearance and partial enlargement morphology. One proposed mechanism for formation of CuS Coating on the surface of the PMIA/PAN composite films is briefly depicted in the scheme 1. Since the -CN group in the polyacrylonitrile component has a strong adsorption effect on the metal copper ions in the copper sulfate (CuSO4), a conductive CuS coating can be formed on the surface of the PMIA/PAN blend film by adsorption and reducing agent reduction. The first stage: Cu2+ in the reaction solution is reduced to Cu+, then Cu+ in the reaction solution is complexed with -CN group in the PAN component; the second stage: Cu+,


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complexed with the -CN group, reacts with S2O32- and forms a strong CuS conductive coating on the surface of the PMIA/PAN-CuS composite films.

Figure 3. SEM images of PMIA/PAN-CuS composite films at a series of blending ratios of (a1 and a2) 7/1, (b1 and b2) 10/1, (c1 and c2) 13/1, (d1 and d2) 16/1.

X-ray photoelectron spectroscopy (XPS) was used for analyzing the surface chemical composition of the PMIA/PAN-CuS composite films. Figure 4 shows the wide XPS spectra of the PMIA/PAN-CuS composite films, containing Cu 2s, Cu 2p1, Cu 2p3, Cu 3p, S 2p and S 2s perks. However, there are many kinds of copper-sulfur compounds (CuxSy) in which S is combined with Cu. Hence, only the XPS characterization does not determine whether a CuS conductive coating has been introduced, further analysis of the conductive coating is still required. In order to further study whether the conductive coating on the conductive PMIA/PAN blend film surface is CuS coating, we performed X-ray diffraction test on



the sample to obtain more accurate phase analysis results. Figure 4b is XRD spectrum of the PMIA/PAN-CuS composite films, the PAN-CuS composite film and CuS black precipitate. The yellow curve in the figure is the curve of the black precipitate formed in the reaction system, which is roughly consistent with the position of the diffraction peak in the standard PDF card of CuS, indicating that the black precipitate formed in the experiment is mainly CuS. The conductive PMIA/PAN-CuS composite films and PAN-CuS film showed sharp diffraction peaks at 2θ=28°, 32° and 48°, which is consistent with the diffraction peak position in the standard PDF card of CuS, indicating that the strong conductive coating formed on the surface of the PMIA/PAN composite film is indeed the CuS coating. Considering that when the blending ratio of PMIA/PAN is greater than 10/1, the morphology of the CuS-coated PMIA/PAN composite films begin to deteriorate, and at the same time, when the blending ratio of PMIA/PAN is 7/1, the mechanical properties are relatively poor. Hence, we chose PMIA/PAN = 10/1 as the best blending ratio. Subsequent experiments were carried out using the PMIA/PAN composite film with a blend ratio of 10/1.

Figure 4. (a) Wide XPS spectra of PMIA/PAN-CuS composite film (PMIA/PAN=10/1); (b) XRD spectrum of the PMIA/PAN-CuS composite films, the PAN-CuS composite film and CuS black precipitate.


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Figure 5. SEM images of (a1 and b1) PMIA/PAN-CuS composite film, (a2 and b2) PMIA/PANCuS composite film after 15 times of tape stripping treatment, (c) Effect of tape stripping treatment on electrical resistivity of PMIA/PAN-CuS composite film (PMIA/PAN=10/1), (d) Schematic illustration of tape stripping treatment, (e) digital pictures of stick tape after tape stripping treatment.

The superior electrically conductive stability of the CuS-coated PMIA/PAN composite films is essential for a variety potential practical applications. Figure 5c shows the resistivity changes of the PMIA/PAN-CuS composite film during 15 times of tape stripping treatment, after first 11 stripping cycles, the resistivity of PMIA/PAN-CuS composite film tends to be stable. The top-view images of PMIA/PAN-CuS composite film before and after 15 stripping cycles are presented in Figure 5a-b, there was only few microcracks scattered on the surface of the treated composite film, and no obvious plating peelings were found in the image (Figure 5b2). In addition, the tape was very clean and almost no impurities were visible (Figure 5e). Hence, the conductivity of the PMIA/PAN-CuS composite film is still within an acceptable range during the overall tape stripping treatment, although its resistivity increases by approximately 7 times after 15 times of tape stripping treatment.



Figure 6. The SEM images of PMIA/PAN-CuS composite films (PMIA/PAN=10/1) after being ultrasonic treated for different time (a:20 min, b:40 min, c:80 min, d: 110 min, e: 140 min, f: 170 min); (g) PMIA/PAN composite film (PMIA/PAN=10/1) after CuS-coating; (h) The resistivity changes of PMIA/PAN-CuS composite films after being ultrasonic treated for different time.

Compact, smooth and dense CuS coating on the surface of PMIA/PAN composite film, with almost no apparent defects, were presented in Figure 6g. Figure 6a-f depicts the SEM images of PMIA/PAN-CuS composite films after being ultrasonic treated for different time. When the sonication time was less than 110 minutes, only a few cracking tendencies appeared on the surface of the coating. When the sonication time exceeded 140 minutes, a large number of microcracks appeared on the surface of the coating. Until the sonication time was 170 minutes, the number of microcracks on the surface of the coating increased relatively, but the overall shape of the coating was still very complete. Moreover, the resistivity changes of PMIA/PAN-CuS composite film during ultrasonic treatment were evaluated and recorded in Figure 6h, because of the superior adhesion stability of the CuS coating, the PMIA/PAN-CuS composite film can preserve its electrical property even in an ultrasonic treatment test for 140 min. In addition, the PMIA/PAN-CuS composite films was successfully utilized to illumine light-


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emitting diode (LED) under being flattened (Fig. 7a), bended (Fig. 7b) and folded (Fig. 7c), respectively. The phenomenon clearly confirms that the conductive composite film has excellent flexibility and mechanical robustness. 31

Figure 7. digital pictures of red light-emitting diodes (LEDs) placed between the PMIA/PAN-CuS composite film under the conditions of (a) flattening, (b) bending and (c) folding.

Conclusions Electrical conductive CuS coating, with superior adhesion stability, has been successfully deposited on the surface of the PMIA/PAN films. The prepared PMIA/PAN-CuS composite films not only exhibit satisfying flexibility, but also simultaneously show improved superior adhesion stability of the CuS coating. The PMIA/PAN-CuS composite films shows a low resistivity of 2.97 Ω·cm (PMIA/PAN=10/1). In particular, there is no need of colloidal noble metal seed particles as catalyst, and no need of a large number of chemical reagents, meeting the demand of green chemistry. And the integrated performances of the pure PMIA material are maintained.

Notes The authors declare no competing financial interest.

Acknowledgments This work was supported by the Natural Science Foundation of China (No. 51473031) and Shanghai International S&T Cooperation Fund (No. 16160731302).



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Using Hybrid Structures of Continuous Metal Nanofiber Networks for Flexible Optoelectronics, ACS Appl. Mater. Interfaces, 2017, 9, 0299.



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Polyacrylonitrile

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