Journal of Applied Polymer Science

Fabrication of microcapsules with graphene/organic hybrid shell based on

Pickering emulsions for self-healing anti-corrosive coatings

--Manuscript Draft--

Full Title: Fabrication of microcapsules with graphene/organic hybrid shell based on

Pickering emulsions for self-healing anti-corrosive coatings

Manuscript Number: app.20233208

Article Type: Research Article

Order of Authors: Zhen Yan

Yujie Liu

Yizhao Cao

Guipeng Quan

Weiwen Li

Daimei Li

Yunhuan Wu

Linghan Xiao

Fei Yu

Manuscript Classifications: Coatings; Conducting Polymers; Electrochemistry; Mechanical Properties; Membranes

Author Comments:

Powered by Editorial Manager® and ProduXion Manager® from Aries Systems Corporation
Complete Manuscript

Fabrication of microcapsules with graphene/organic hybrid shell based on

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2 Pickering emulsions for self-healing anti-corrosive coatings
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4 Zhen Yana, Yujie Liua, Yizhao Caob, Guipeng Quana, Weiwen Lia, DaiMei Lia,
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Yunhuan Wua, Linghan Xiaoa, *, Fei Yuc,*
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7 a Jilin Province Key Laboratory of Carbon Fiber Development and Application,
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9 College of Chemistry and Life Science, Changchun University of Technology,
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11 Changchun130012, People’s Republic of China
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13 b College of Polymer Material and Engineering, Qingdao University of Science and
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15 Technology, Qingdao 266000, People’s Republic of China
16 c Jilin Joinature Polymer Co., Ltd. No.1177, Zhongyan Road, Luyuan Economic
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18 Development Zone, Changchun, Jilin, Province, China
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20 * Corresponding authors: Linghan Xiao, Fei Yu
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22 E-mail: xiaolinghan1981@163.com, flyfly19940424@163.com
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24 Keywords: GO; Pickering emulsion; Microcapsules; Synergistic effect; Self-healing
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26 coatings
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29 Abstract ： During the use of organic coatings, microcracks could appear due to
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31 external environmental influences and inherent aging, which would notably reduce the
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34 lifespan of the coating. This study combined the Pickering emulsion template method
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36 with interfacial polymerization to prepare graphene oxide/polyurethane/polyaniline
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39 (GO/PU/PANI) organic-inorganic hybrid shell microcapsules with isophorone
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41 diisocyanate (IPDI) as the core material. The prepared capsules were added to
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photocurable resin to obtain a corrosion-resistant coating with self-healing properties.
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46 These capsules are characterized by their small size, high encapsulation rate, excellent
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48 dispersion, and robust hybrid shell. The average particle diameter of the capsules is
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51 3.11μm, with an encapsulation rate of 78.19%. Scanning electron microscopy results
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53 show that the addition of only 5% microcapsules can achieve almost complete repair.
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56 After soaking the repaired coating in a 5 wt% NaCl solution for 250 hours, the
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58 alternating current impedance value still remains at 6.9×105 Ω·cm2. The excellent
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 corrosion resistance of this coating is due to the synergistic effect of the anti-corrosion
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2 properties of polyaniline and the self-healing properties of IPDI. The addition of
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5 microcapsules endows the coating with self-healing and outstanding corrosion
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7 resistance, which can potentially broaden the application range of the coating under
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10 harsh conditions in the future.
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12 1. Introduction
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14 Organic coatings are widely applied to metallic surfaces due to their convenience
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16 and cost-effectiveness, effectively reducing the occurrence of corrosion[1-5]. However,
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19 during usage, organic coatings may develop microscopic cracks due to aging and
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21 external impact. The presence of these cracks accelerates the detachment of the coating,
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24 leading to severe corrosion of the underlying metal[6-8]. Designing a self-healing coating
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26 capable of autonomously repairing these microscopic cracks holds paramount
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29 significance[9,10].
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31 Inspired by biomimicry from nature, researchers have developed a range of self-
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repairing materials categorized as intrinsic self-repairing materials[11-13] and extrinsic
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36 self-repairing materials[14-18] based on the presence of healing agents. In 2001, White et
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38 al[19]. reported a microcapsule-based self-healing material using urea-formaldehyde
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41 coated dicyclopentadiene (DCPD) microcapsules and a Grubbs catalyst embedded in
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43 the substrate. Upon material damage, the dicyclopentadiene inside the microcapsules
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46 flows out, reacts with the catalyst in the substrate, and repairs the damaged area. Yin et
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48 al[20].explored a dual-component self-healing system using polyurea-formaldehyde
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microcapsules enclosing epoxy resin and a CuBr2(2-MeIm)4 latent catalyst. The
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53 substrate material, when heated for 60 minutes at 130 °C, could complete self-repair,
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55 with an efficiency reaching as high as 111%. Li et al[21].prepared a two-component
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58 microencapsulated self-healing material by encapsulating the restorative agent,
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60 bisphenol A epoxy diglycidyl ester, and the catalyst, polyether amine, respectively, with
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 poly(methyl methacrylate) (PMMA). When the microcapsule content is 15 wt%, the
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2 repair efficiency of the damaged area of the self-healing coating reaches 84.5% after
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5 being left at room temperature for 24 hours. However, during the preparation of self-
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7 healing materials, the dual-component repair system still faces issues with the catalyst
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10 deactivation and uneven distribution of curing agent microcapsules and catalyst, which
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12 can affect the stability of the material's self-healing properties[16,18,21-23].
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15 IPDI serves as a catalyst-free restorative agent for moist environments, reacting
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17 with water to extend chains and create polymers of enhanced strength.
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Microencapsulation of it can prepare single-component self-healing materials with
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22 good repair effects, effectively avoiding the problem of insufficient mixing between the
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24 repairing agent and catalyst[24-27]. Li et al[28]. created a single-component PU
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27 microcapsule loaded with CPU-IPDI using interfacial polymerization. The capsule has
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29 a particle size of 26.3 μm and an encapsulation efficiency of 51.3%. At a microcapsule
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32 content of 10 wt%, repair of the damaged area is achievable. Credico et al[29].
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34 manufactured a PU/PUF microcapsule encapsulating IPDI. The particle size is 99.8 μm,
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with an encapsulation efficiency of 50-70%. At a microcapsule concentration of 15 wt%,
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39 the damaged area can achieve full repair under humid conditions within 48 hours.
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41 Additionally, polymer-based capsules have shortcomings such as large particle size,
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44 low effective core material content, and a complex and tedious preparation process that
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46 uses a large amount of organic solvents. To achieve effective repair, a large number of
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49 microcapsules need to be added, which can reduce the mechanical properties of the base
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51 material and easily cause new cracks[30].
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54 Graphene oxide (GO) is a unique two-dimensional material produced by oxidizing
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56 graphene[31-33]. The amphiphilicity and large specific surface area of GO allow it to
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effectively serve as an emulsifier for Pickering emulsions[34,35]. Moreover, the
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 preparation process has minimal environmental pollution, is easier to separate, and is
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2 convenient for subsequent processing[36-38]. Wang et al[39].prepared a two-component
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5 microcapsule self-healing system with epoxy resin-amine catalyst using GO and boron
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7 nitride as emulsifiers for epoxy resin microcapsules and amine microcapsules Pickering
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10 emulsion, respectively. The average particle size of the GO microcapsules was 3.62 μm,
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12 and they achieved an encapsulation efficiency of 86% Fabricating GO as a
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15 microcapsule shell can effectively enhance the stability of the capsules, reduce the size
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17 of the microcapsules, increase the encapsulation rate of the core material, and mitigate
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the problem of significant reduction in the mechanical strength of the base material
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22 after the addition of microcapsules.
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24 In this research, we prepared sturdy hybrid shell microcapsules loaded with IPDI,
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27 using GO as the emulsifying agent for Pickering emulsion. Because PANI contacts the
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29 metal base, it passivates the metal, forming a protective layer[40-42]. It is commonly
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32 employed as a nanomaterial additive in coatings to enhance their corrosion
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34 resistance[43,44]. In this experiment, PANI was deposited on the surface of the capsules
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via interfacial polymerization, enhancing the corrosion resistance of the self-healing
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39 coating. The self-healing ability of IPDI and the synergistic effect of PANI improved
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41 the anti-corrosion performance of the coating on metal. The prepared microcapsules
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44 have good dispersion, small size, and a sturdy hybrid shell, which can effectively
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46 mitigate the harmful impact of a significant decrease in the mechanical properties of
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49 the base material after microcapsule addition. Considering its outstanding self-healing
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51 and anti-corrosion performance, this coating holds immense potential for broad
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54 application.
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22 Fig. 1 Synthesis process of hybridized shell microcapsules and preparation process
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24 and repair principle of self-repairing anticorrosive composite coating
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27 2. Experimental
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29 2.1. Materials
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32 Isophorone diisocyanate (IPDI), polyvinyl alcohol (PVA), and ethylenediamine
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34 (EDA) were purchased from Aladdin Reagent Co. Graphene oxide (GO) was prepared
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37 from graphite (XFNANO, China) using the modified Hummers method. 1,4-butanediol,
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39 aniline (AN), 4,4′-methylene bis(phenyl isocyanate) (4,4-MDI) and ammonium
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43 persulfate (APS) were purchased from McLean Reagent Co. Hydrochloric acid (HCI)
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45 and acetone (AC) were purchased from Beijing Chemical Reagent Factory. Bisphenol
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48 A epoxy acrylate (YC3380), tripropylene glycol and acrylate (YPGDA), photoinitiator
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50 (1173) were purchased from Shanghai Yinchang New Materials Co. 2-Hydroxyethyl
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Methacrylate Phosphate (KM2110) was purchased from Guangzhou Honour Chemical
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55 Technology Co. Deionised water was provided by Changchun University of
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57 Technology. All the chemical reagents used in the experiments were used as is without
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60 further purification.
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 2.2. Preparation of IPDI@GO/PU hybrid shell microcapsules
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2 Initially, 8 mg of GO was dispersed in 4 ml of deionized water by ultrasonication
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5 for 3 hours, resulting in a GO water dispersion with a concentration of 2 mg/ml. The
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7 pH of the dispersion was adjusted to 7 by gradually adding a diluted EDA aqueous
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10 solution, and the pH value was measured with a PHS-25 pH meter. Subsequently, 1 ml
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12 of a 1 mg/ml polyvinyl alcohol PVA solution was added to the system, followed by an
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15 additional hour of sonication. To prepare the isocyanate mixture, 0.1 g of 4,4-MDI was
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17 combined with 0.4 g of IPDI, and the mixture was heated and thoroughly stirred until
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it became clear. The isocyanate mixture (0.2 g) was then gradually added to the GO
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22 water dispersion, followed by intense shearing for 5 minutes to achieve complete
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24 emulsification and obtain a stable (W/O) Pickering emulsion. The Pickering emulsion
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27 was transferred to a three-neck flask and mechanically stirred at 40 °C. During stirring,
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29 0.04 g of 1,4-butanediol was gradually added to the flask. The reaction was allowed to
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32 proceed for 3 hours to yield IPDI@GO/PU hybrid shell microcapsules. Finally, the
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34 resulting IPDI@GO/PU microcapsules were washed multiple times with acetone and
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thoroughly dried in a 40 °C environment. The screening of preparation conditions for
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39 IPDI@GO/PU hybrid shell microcapsules is detailed in the Supporting Materials.
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41 2.3 Preparation of IPDI@GO/PU/PANI hybrid shell microcapsules
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44 Begin by combining 20 ml of a 1mol hydrochloric acid solution with 0.093 g of
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46 AN in a three-neck flask, and stir mechanically for a period of 12 hours to create a
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49 homogeneous aniline acid solution. Subsequently, add 0.2 g of dried IPDI@GO/PU
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51 hybrid shell microcapsules to this acidic solution, ensuring thorough mixing via
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54 mechanical stirring. Following this, transfer the three-neck flask to an ice-water bath
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56 and incrementally introduce 0.046 g of APS into the system. Proceed to conduct
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interfacial polymerization, employing a mechanical stirring speed of approximately 400
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 rpm for duration of 12 hours. This procedure facilitates the deposition of PANI onto the
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2 surface of the IPDI@GO/PU hybrid shell microcapsules. Upon concluding the 12-hour
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5 period, purify the product through a series of washes with distilled water and acetone.
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7 The washing process is considered complete once the washing solution becomes
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10 colorless. Finally, thoroughly dry the product in an environment maintained at 40 ℃.
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13 This results in the yield of IPDI@GO/PU/PANI hybrid shell microcapsules.
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16 2.4 Preparation of self-healing light-curing coatings
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18 Initially, diluent YPGDA was added to epoxy acrylate YC3380. Subsequently,
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21 appropriate amounts of photoinitiator 1173 and adhesion promoter KM2110 were
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23 incorporated to form a light-curing resin matrix. The hybrid shell microcapsules were
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26 then mixed with the flow matrix using ultrasonication and mechanical mixing,
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28 maintaining the solid content of the coating at 1%, 3%, 5%, and 10%. The Q215 mild
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steel plate was thoroughly cleaned with acetone to remove the protective layer of grease
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33 and particulate impurities, then dried and prepared for further use. The flow matrix was
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35 degassed in a vacuum to remove any air bubbles, and then applied to the surface of the
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38 steel plate. The coating was allowed to level off before being exposed to a light-curing
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40 machine multiple times to complete the light-curing process, resulting in the formation
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43 of self-repairing light-curing coatings. The thickness of all the inspected coatings was
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45 measured to be approximately 150±10 μm.
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Prepared microcapsules are added to commercial photocurable resin, with the
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50 solid content maintained at 1%, 3%, 5%, and 10%. The defoamed resin was poured into
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52 a mold and subjected to multiple exposures in a light-curing machine to achieve light
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55 curing of the material. After the resin was fully cured, the sample strips were removed
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57 from the mold and prepared for three-point bending and tensile testing.
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60 2.5 Characterizations
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 The morphology of the microcapsules, both in aqueous solution and in the
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2 Pickering emulsion state, was investigated using a metallographic microscope (Model:
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5 YYJ-400E, Origin: China). The average diameter and diameter distribution of the
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7 microcapsules were evaluated by measuring the diameters of 100 random
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10 microcapsules using Image J software. Further investigation of the surface morphology
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12 of the microcapsules was conducted using a Scanning Electron Microscope (SEM,
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15 Model: ZEISS Sigma500, Origin: German). This allowed for a detailed observation of
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17 the microcapsule surface. For the analysis of the chemical structure of the
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microcapsules, Infrared Spectroscopy was utilized (Model: Nicolet iS50, Origin: USA).
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22 The samples were pulverized and compacted with potassium bromide, followed by
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24 analysis within the wave number range of 400-4000 cm-1. The thermal stability of the
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27 microcapsules was evaluated using a Thermogravimetric Analyzer (TGA, Model:
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29 Mettler-Toledo TGA 2, Origin: Switzerland). The samples underwent heating in a
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32 nitrogen environment from 30 to 800°C, with a temperature escalation rate of 5 °C/min.
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34 To characterise the self-repairing coating's restorative effect, we conducted salt
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solution impregnation experiments. We created artificial scratches, each 2 cm long and
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39 3 μm wide, on the coating's surface using a razor blade, ensuring each scratch reached
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41 the steel substrate. The damaged coating was then immersed in a 5 wt% NaCl salt
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44 solution, and we documented the alterations in the scratch locations using a digital
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46 video camera. We utilised Scanning Electron Microscopy (SEM) to monitor the scratch
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49 locations before and after the repair process. We assessed the material's corrosion
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51 resistance by monitoring the coating's AC impedance changes through electrochemistry.
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54 For the electrochemical tests, we employed a standard three-electrode system, with the
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56 working electrode being a self-repairing coating applied on a 1 cm2 piece of mild steel
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(glass-carbon electrode), a platinum electrode as the counter electrode, and Ag/AgCl
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 (0.205 V/SHE) as the reference electrode. The electrolyte was a 5 wt% NaCl solution.
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2 The test frequency range was from 10-1 to 104 Hz with a sinusoidal voltage signal
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5 vibration of 5 mV. All experiments were performed under standard ambient conditions
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7 at a room temperature of 25 °C.
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10 We evaluated the mechanical properties of the self-healing materials using a
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12 universal mechanical testing machine ((Model: Zwick Roell Z100, Origin: German).
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15 The tensile strength of the self-healing materials was evaluated in compliance with the
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17 tensile test standard ASTMD638. In a similar fashion, their flexural strength was
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assessed following the three-point bending test standard ASTMD790.To assess the self-
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22 repairing capabilities of the material, we stretched the strips to a 5% deformation at a
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24 rate of 1 mm/min using the testing machine. After allowing the strips to self-repair at
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27 room temperature for 72 hours, we tested the tensile properties of the repaired strips
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29 using the same method. Each experiment was conducted five times, and the mean value
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32 was calculated to ensure the precision of the experimental data.
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35 3. Results and discussion
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38 3.1 Chemical structure of microcapsules
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Fig. 2a presents the FTIR absorption spectra of GO, IPDI, IPDI@GO/PU
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43 microcapsules, and IPDI@GO/PU/PANI microcapsules. The C=O stretching vibration
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45 characteristic peak of the carboxyl and carbonyl groups in graphene oxide is observed
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48 at 1730 cm-1. The -OH stretching vibration is represented by the characteristic peak at
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50 3423 cm-1. The C-O-C and C=C stretching vibrations in the aromatic ring are denoted
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53 by the characteristic peaks at 1060 cm-1 and 1620 cm-1, respectively. The -NCO
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55 stretching vibration absorption peak is found at 2250 cm-1. In the FT-IR spectra of IPDI
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58 and microcapsules, the -NCO absorption peak also appears at 2250 cm-1, suggesting
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60 successful encapsulation of IPDI to form microcapsules. The IPDI@GO/PU and
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 IPDI@GO/PU/PANI microcapsules exhibit the main characteristic peaks of PU at 1620
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2 cm-1 for C=O stretching vibration and 1520 cm-1 for N-H bending vibration, indicating
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5 the formation of the PU wall. The peak at 1109 cm-1 is attributed to the vibration
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7 associated with the C-H and C-N+ stretching vibration in the N=Q=N (Q represents
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10 quinone) conductive polarons structure of PANI. However, in this scenario, the
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12 vibrational peaks of PANI overlapped with those of PU, rendering it challenging to
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15 distinguish between PU shells and PU/PANI shells solely through FTIR spectroscopy.
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17 XPS wide scans were used to characterize the chemical composition of different
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microcapsules. As shown in Fig. 2b, the IPDI@GO/PU microcapsules are mainly
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22 composed of carbon, nitrogen, and oxygen. A new Cl2p peak emerged in the
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24 IPDI@GO/PU/PANI microcapsules due to the deposition of hydrochloric acid-doped
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27 polyaniline. As shown in Fig. 2c-d, high-resolution C1s and N1s spectra obtained more
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29 chemical information about different microcapsules. The C1s spectrum of
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32 IPDI@GO/PU microcapsules has six distinct peaks at 284.8 eV for C-C, 285.5 eV for
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34 C-N, 286.1 eV for C-N+, 286.4 eV for C-O, 287.3 eV for C=O, and 288.9 eV for O-
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C=O. Compared with the C1s spectrum of IPDI@GO/PU microcapsules, the C1s
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39 spectrum of IPDI@GO/PU/PANI microcapsules did not show new peaks, but the
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41 proportions of each peak changed. This is due to the formation of new C=N and C=N+
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44 peaks from the generation of polyaniline, which overlapped with the initial peaks[45-47].
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46 The comparison of the N1s spectra of IPDI@GO/PU/PANI microcapsules and
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49 IPDI@GO/PU microcapsules clearly shows a new peak at 401.1 eV（Fig. 2e-f）[46].
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52 This peak corresponds to -N+= after the successful deposition of polyaniline, thereby
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55 demonstrating the successful deposition of polyaniline on the capsule surface.
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43 Fig. 2 (a)FTIR spectra of IPDI, GO, IPDI@GO/PU microcapsules and
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IPDI@GO/PU/PANI microcapsules; XPS survey spectra (b) of IPDI@GO/PU/PANI,
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48 and IPDI@GO/PU; High-resolution C1s and N1s spectra of (c-f) IPDI@GO/PU and
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50 IPDI@GO/PU/PANI.
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53 3.2 Morphology of microcapsules
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56 Fig. 3a-b display the macroscopic morphology of the dried IPDI@GO/PU and
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59 IPDI@GO/PU/PANI hybrid shell microcapsules, as observed through a digital camera
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 and a metallographic microscope. The IPDI@GO/PU microcapsules are spherical with
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2 a yellow-brown color. When PANI is deposited on the capsule surface, the
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5 IPDI@GO/PU/PANI microcapsules turn into dark green spheres, a transformation
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7 attributed to the presence of PANI. A comparative analysis using a metallographic
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10 microscope reveals a significant deepening in shell color after the PANI deposition, as
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12 shown in Fig. 3c and 3d. The average diameter of the microcapsules is determined by
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15 measuring 100 of them using Image J. The average particle sizes for the
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17 IPDI@GO/PU/PANI and IPDI@GO/PU microcapsules are 2.98 μm and 3.11 μm,
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respectively. The core material content of the IPDI@GO/PU/PANI microcapsules,
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22 calculated by extracting the core material with acetone, is found to be 78.19%. Scanning
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24 electron microscope observations further reveal that both the single IPDI@GO/PU and
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27 IPDI@GO/PU/PANI microcapsules possess a spherical structure and a relatively rough
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29 surface. This roughness enhances the bonding between the microcapsules and the
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32 coating substrate, thereby strengthening the bond. By comparing SEM images before
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34 and after the deposition of polyaniline, it is clear that polyaniline is deposited on the
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37 surface of the microcapsules（Fig. 3e-f）.
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 Fig. 3 Morphology of microcapsules：(a)Digital camera photo of dry IPDI@GO/PU
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4 (b) Digital camera photo of dry IPDI@GO/PU/PANI (c) OM images of IPDI@GO/PU
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6 (d) OM images of IPDI@GO/PU/PANI (e) SEM morphology of IPDI@GO/PU (f)
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SEM morphology of IPDI@GO/PU/PANI.
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3.3 Thermal stability of microcapsules
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We evaluated the thermal properties of the microcapsules using the heat loss
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17 method. The mass loss versus temperature curves for all materials are depicted in Fig.
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19 4. Pure IPDI began to evaporate at 112 °C, while the decomposition temperatures of
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22 IPDI@GO/PU/PANI and IPDI@GO/PU microcapsules were 156 °C and 172 °C,
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24 respectively. This suggests that the shell layer effectively protects the core material, and
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27 the hybrid shell layer continues to encapsulate the IPDI vapour even when the pure
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29 IPDI reaches its evaporation temperature. The residual mass at 800 °C for
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IPDI@GO/PU and IPDI@GO/PU/PANI microcapsules was 11.56 wt% and 13.84 wt%,
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34 respectively. For the IPDI@GO/PU microcapsules, 11.56% of the residue corresponds
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36 to GO and partially undecomposed PU. For the IPDI@GO/PU/PANI microcapsules,
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39 13.84% of the residue corresponds to GO and partially undecomposed PU, PANI.
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 Fig. 4 TGA curves of pure IPDI, IPDI@GO/PU microcapsules and
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2 IPDI@GO/PU/PANI microcapsules.
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5 3.4 Mechanical properties of self-healing materials
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8 In typical scenarios, the integration of microcapsules can significantly affect the
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11 mechanical performance of a coating, thereby limiting the application range of
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13 composite coatings. The inclusion of large microcapsules notably influences the
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16 material's mechanical properties, whereas the addition of smaller microcapsules has a
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18 less pronounced effect on the bending and tensile stress of self-healing materials. In this
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study, three-point bending and tensile experiments were conducted on self-healing
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23 materials with varying microcapsule contents (0, 1, 3, 5, 10 wt%). As shown in Fig. 5a-
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25 5b, the tensile and bending performance of the self-healing material significantly
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28 improves with the addition of a minimal amount of microcapsules. Specifically, when
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30 the microcapsule content is 1wt%, the tensile strength of the self-healing material
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33 reaches 99.3MPa (113.88%), and the bending strength is 226 MPa (110.78%). This
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35 enhancement can be attributed to the better dispersion of microcapsules in the self-
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38 healing material when their content is low. The microcapsules, with a particle size of
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40 about 3.11μm, can effectively increase the material's toughness due to their smaller size.
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The resulting increase in material toughness allows for some deformation during the
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45 stretching process, which absorbs energy and reduces stress concentration. However,
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47 as the microcapsule content increases, the tensile strength of the self-healing material
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50 gradually decreases. This decline is due to the uneven dispersion of an excessive
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52 number of microcapsules in the matrix, which may even lead to microcapsule
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55 aggregation. Furthermore, the presence of numerous microcapsules can create
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57 microscopic voids in the material, increasing its brittleness and making it more
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susceptible to fracture. This, in turn, leads to a decrease in the material's mechanical
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 properties. Nevertheless, even when the microcapsule content is 10 wt%, the tensile
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2 strength and bending strength of the self-healing material can still maintain 80.73% and
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5 76.41% of the original matrix material performance, respectively.
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7 Fig. 5c presents the results of a secondary tensile strength test conducted after the
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10 self-healing material has undergone repair. The data indicates that when the
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12 microcapsule content is low, the material's mechanical properties experience a more
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15 significant decrease post-repair. This outcome can be attributed to an insufficient
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17 number of microcapsules in the system to effectively mend the cracks. As the
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microcapsule content within the system increases, so does the volume of the effective
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22 healing agent contained within the microcapsules. This increase allows for the full
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24 filling of the damaged area, thereby enhancing the repair efficiency of the self-healing
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27 material and leading to an increase in secondary tensile strength. In summary, when the
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29 microcapsule addition is at 5wt%, the tensile strength is 84.8 MPa (97.25%), and the
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32 bending strength is 193 MPa (94.61%). At this level, the self-healing material
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34 demonstrates a relatively good repair effect, and the material's overall performance is
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also relatively good. Indeed, the experimental results validate the benefits of this study.
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39 The microcapsules prepared in this experiment have a minimal impact on the
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41 mechanical properties of the self-healing materials. This means the materials retain
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44 their original strength while gaining the ability to self-heal.
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41 Fig. 5 (a) the variation in tensile stress of resin specimens with different proportions of
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43 microcapsules (b) the change in bending strength of resin specimens with differing
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amounts of microcapsules (c) the tensile stress of resin specimen with different addition
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48 of microcapsules during two stretch.
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51 3.5 Properties of Composite Coatings
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54 The uniform dispersion of microcapsules is indeed a crucial factor in the
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56 preparation of coatings. As observed from the microscopic photos of the coating (Fig.
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59 6a), the composite coating that contains 5% IPDI@GO/PU/PANI microcapsules
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 appears green, indicating the capsules are well dispersed with no noticeable
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2 agglomeration. Therefore, all subsequent tests are conducted at this concentration to
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5 ensure the consistency and reliability of the results.
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7 To assess the self-healing and anti-corrosion performance of the composite coating,
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10 various coatings were prepared: one without microcapsules, one containing 5 wt%
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12 IPDI@GO/PU microcapsules, and one containing 5 wt% IPDI@GO/PU/PANI
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15 microcapsules. These coatings were applied to the surface of a steel plate. Scratches
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17 were then made on the surface with a blade, and the samples were soaked in a 5 wt%
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NaCl aqueous solution at room temperature for 18 days to study the performance of the
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22 composite coating. From Figure 6b, it is evident that the pure epoxy coating rusted after
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24 just one day of soaking in the solution. In contrast, the composite coating with 5 wt%
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27 IPDI@GO/PU microcapsules began to show visible rusting on the tenth day, while the
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29 composite coating with 5 wt% IPDI@GO/PU/PANI microcapsules did not show
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32 surface rusting until the fifteenth day. The corrosion spread of the composite coating
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34 containing IPDI@GO/PU/PANI microcapsules was slower compared to the composite
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coating containing IPDI@GO/PU microcapsules, with noticeable spread of corrosion
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39 not appearing until the eighteenth day of soaking. These results indicate that the
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41 composite coating containing 5 wt% IPDI@GO/PU/PANI microcapsules provides the
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44 best anti-corrosion effect on the surface of low carbon steel.
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32 Fig. 6 (a) OM images of Composite coating (a1) contains 5% IPDI@GO/PU (a2)
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34 contains 5% IPDI@GO/PU/PANI (b) pure coatings damaged by immersion in salt
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37 solution(b1)0 day (b2) 1 day (b3) 3 day (b4) 5 day (b5) 10 day (b6) 15 day (b7) 18 day
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39 (c) contains 5% IPDI@GO/PU coatings damaged by immersion in salt solution(c1)0
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42 day (c2) 1 day (c3) 3 day (c4) 5 day (c5) 10 day (c6) 15 day (c7) 18 day (d) contains
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44 5% IPDI@GO/PU/PANI coatings damaged by immersion in salt solution(d1)0 day (d2)
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1 day (d3) 3 day (d4) 5 day (d5) 10 day (d6) 15 day (d7) 18 day.
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49 In our quest to comprehend the repair capabilities of self-healing materials, we
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51 employed a scanning electron microscope to examine the surface morphology of the
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54 coating after repair. A comparative analysis showed that the scratches on the pure
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56 coating remained largely unaltered (Fig. 7a). However, the scratches on the composite
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59 coating, which incorporates IPDI@GO/PU/PANI and IPDI@GO/PU microcapsules,
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 were completely filled after a three-day healing period (Fig.7b-c). The irregular edges
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2 shown in Fig. 7b serve as clear evidence of the repair filling elements within the
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5 scratched area. The repair process is facilitated by the IPDI repair agent, released from
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7 the ruptured microcapsules at the crack site. This repair agent, driven by capillary action,
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10 infiltrates the crack and reacts with the ambient water vapor, resulting in a polymer that
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12 effectively repairs the crack. This polymer film acts as a barrier, preventing the
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15 electrolyte solution from directly contacting the metal substrate. Essentially, it
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17 reinstates a protective layer at the crack site, thereby inhibiting further corrosion of the
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metal substrate by the electrolyte.
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Fig. 7 SEM morphology of the scratched area on the epoxy resin coatings after repair
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45 (a) pure coatings (b) contains 5% IPDI@GO/PU (c) contains 5% IPDI@GO/PU/PANI
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47 To further assess the anti-corrosion capabilities of the composite coating, we
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50 conducted electrochemical impedance tests on various coatings. The scratched coating
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52 was immersed in a 5 wt% NaCl aqueous solution, with the impedance test diagram
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55 presented in Fig. 8. For the pure epoxy coating devoid of capsules, the impedance
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57 modulus of the damaged coating approximates the properties of the metal. This occurs
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60 when a substantial amount of electrolyte solution infiltrates the interface between the
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 coating and the metal substrate, causing the coating to lose its protective effect on the
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2 metal substrate. However, the addition of 5 wt% microcapsules enhances the coating's
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5 corrosion resistance. The repaired impedance modulus of the two composite coatings
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7 is of the same order of magnitude as that of the undamaged pure coatings. This suggests
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10 that no corrosion reaction occurred at the interface between the metal and the coating
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12 during the test, indirectly indicating the composite coating's robust self-healing ability.
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15 Moreover, after the same duration of immersion in the NaCl solution, the impedance
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17 semicircle of the composite coating containing 5 wt% IPDI@GO/PU/PANI
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microcapsules decreases slower than that of the coating containing 5 wt%
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22 IPDI@GO/PU microcapsules. This implies that the incorporation of polyaniline in the
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24 system further bolsters the coating's anti-corrosion ability. Polyaniline can form a
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27 passivation layer on the metal surface, thereby delaying metal corrosion. Furthermore,
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29 the central atom N in aniline compounds possesses unshared electron pairs. When
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32 empty d orbitals are present on the metal surface, the electron pairs of the central atom
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34 in the polar group form a coordination bond with the empty d orbitals. This results in
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the adsorption of aniline molecules on the metal surface, forming a hydrophobic
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39 adsorption layer. The presence of this adsorption layer significantly reduces the
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41 corrosion rate of the metal surface and delays metal corrosion. After soaking the
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44 repaired coating in a 5 wt% NaCl solution for 250 hours, the alternating current
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46 impedance value still remains at 6.9×105Ω·cm2. The combined action of IPDI and PANI
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49 effectively shields the metal substrate from corrosion, with the synergistic mechanism
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51 illustrated in Fig. 8d. In conclusion, the coating containing IPDI@GO/PU/PANI
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54 microcapsules exhibits superior anti-corrosion effects.
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29 Fig. 8 (a) the Nyquist plots of the pure coating (b) the Nyquist plots of the contains 5%
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32 IPDI@GO/PU coating (c) the Nyquist plots of the contains 5% IPDI@GO/PU/PANI
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34 coating (d) the mechanism of synergistic self-healing and corrosion protection
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37 4. Conclusions
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40 This study employs graphene oxide as a Pickering emulsifier to create a type of
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IPDI@GO/PU hybrid shell microcapsule using the Pickering emulsion template
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45 method. Through interfacial polymerization, conductive polyaniline was successfully
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47 deposited on the capsule surface, resulting in the successful preparation of
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50 IPDI@GO/PU/PANI hybrid shell microcapsules. The construction of the GO/polymer
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52 capsule wall enhances the barrier and mechanical properties of the capsule wall. The
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55 prepared microcapsules were then added to a photocurable resin to produce a self-
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57 healing coating. Thanks to the good dispersion, small size, and robust core-shell
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60 structure of the capsules, the addition of microcapsules has a minimal impact on the
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 mechanical properties of the substrate. With the addition of 5% microcapsules the
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2 tensile strength of the self-healing material is 84.8 MPa (97.25%), and the bending
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5 strength is 193 MPa (94.61%). The synergy of IPDI self-healing and the excellent anti-
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7 corrosion performance of conductive polyaniline resulted in a self-healing coating with
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10 superior anti-corrosion performance. The synergistic anti-corrosion effect was
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12 confirmed by alternating current impedance and salt solution immersion experiments.
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15 The IPDI@GO/PU/PANI hybrid shell microcapsules prepared in this study exhibit
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17 characteristics of simple preparation, high load, small size, robust core-shell structure,
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and a clever synergistic anti-corrosion effect. They can meet the requirements of high-
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22 performance anti-corrosion composite coatings, and we anticipate these capsules to be
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24 widely used.
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27 Declaration of Competing Interest
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30 The authors declare that they have no known competing financial interests or
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33 personal relationships that could have appeared to influence the work reported in this
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35 paper.
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38 Acknowledgements
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41 This work was supported by the National Foreign Expert Foundation of China
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(Grant No. DL2023009001L) and the Jilin Province Science and Technology Platform
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46 Foundation Project of China (Grant No.YDZJ202301ZYTS479).
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Table Click here to access/download;Table;Table of Contents.docx

The present work establishes an efficient, simple and environmentally friendly

method for the preparation of hybrid shell microcapsules. The prepared microcapsules

are well dispersed, small in size, and have a strong hybrid shell. Adding the

microcapsules to the coating has little effect on the mechanical properties of the

substrate. A one-component self-healing light-curing coating with excellent

anticorrosion properties was prepared.

Graphical Abstract Image
Supporting Information

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Supporting Information
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