Progress latest antifouling self-repairing material

Material may be prevented from fouling the surface of biological, inorganic and organic substances attached, are widely used in many fields. According to the size of the surface energy of the anti-fouling material, it can be divided into low surface energy material (e.g., silicones and fluoropolymers) and a high surface energy material (e.g., PEG and zwitterionic polymers). The antifouling materials of different structures, may be divided into the following five categories: single layer polymer brush, coatings, gels, and liquid injection porous surface (SLIPS). any antifouling material properties will decline in the course, how to prolong the service life is important, so has the anti-fouling material (SHAF) self-healing function of widespread concern researchers. Mechanism of self-repairing material may antifouling divided into two categories:

① reversible interaction based on chemical / physical; ② the self-repairing material embedded in a matrix agent.

The results presented in

Sichuan University Wang Zhanhua , summer and Health and Wageningen University Han Zuilhof cooperation studied antifouling self-repairing material progress at home and abroad for a summary, according to the different self-repair mechanism, they will self repair fouling material is divided into three categories: surface-based antifouling material supply self-repairing, self-repairing material interaction based on dynamic antifouling covalent or non-covalent, self-repair mechanism of the two combined together antifouling materials. They then summed up potential applications antifouling self-healing material comprising an injectable hydrogel and oil / water separation. Finally, they looked to the future developments in the field that nine aspects of the design of new materials, multiscale research fouling processes and the preparation of anti-fouling material 3D printing technologies should be further studied. antifouling self-repairing material and self-healing mechanism antifouling

surface of the soil depends on a solid adsorption Gibbs adsorptionThe size of the free energy, when Gibbs free energy is less than zero, adsorption occurs: ΔGads = ΔHads-TΔSads < 0。

当防污材料与溶剂具有很强的相互作用时，材料表面牢固结合的溶剂层会大大降低表面与污物之间相互作用的焓增，因此ΔHads很小，甚至是正值。在这种情况下，吸附熵（ΔSads）起主导作用，被吸附的污物分子在表面上不稳定，会扩散回溶液中，表面从而具有防污性能。当防污材料在不良溶剂中使用时，由于溶剂与防污材料之间的相互作用较弱，污物的吸附焓（ΔHads）很小，ΔSads-sol也很小，不能补偿污染后熵（ΔSads-foul）的损失，吸附的污物在表面上不稳定，也具有防污的性能。

antifouling self-repairing material Category

[123 ] Figure 2. the three main types of self-healing anti-fouling materials. After the first type material (referred to as a surface Replenishment) good flexibility, small scratches may be repaired, repairing scratches:Researchers self-repair mechanism depending on surface material will be divided into three SHAF reinstate material antifouling properties; the second material (known as dynamic covalent or non-covalent interactions type) can repair damaged larger, then need to be fully restored by surface recombination of material; third category material (referred to as self-healing double) combines the advantages of both types of materials, not only repair scratches nm / [mu] m, can also repair large areas of material wear.

The first material (surface Replenishment) low surface energy material of the self-healing can be achieved in three ways: ① redirection, ② and ③ from the migration of low surface energy component moved to a new air interface.

FIG 3. (A) from the chemical supply mechanism and structure of the coating from the supply schematic; (B) from the supply of a schematic structure of a superhydrophobic surface of the coating.Esteves et al synthesized a low surface energy material having a self-healing function: crosslinked polyurethane film containing perfluoroalkyl side chains, then they will polyurethane coating is deposited on the SiO2 nanoparticles, superhydrophobic materials produced has excellent self-healing properties, after repair material 500 remains superhydrophobic properties, increasing F / C atomic ratio within the material slightly top 10 nm depth after repair, to fix a material thickness 30 nm . Fluoroalkyl side chains prepared Zhang et al., Self-repairing superhydrophobic 3D sol – gel network 1000 can be self-healing. The fluorine-containing polymer segment will be broken at the movement, giving superhydrophobic material excellent self-healing properties.

FIG 4. (A) through the secondary reaction of silane molecules embedded self-healing mechanism superhydrophobic coating; after (B) O2 plasma etching and self-healing, damage repetitive – repair process (a) in superhydrophobic coating (top) and superhydrophilic (bottom) state,And change in contact angle; (C) FAS and chemical structure of PVDF-HFP and fabric superhydrophobic coating process; (D) at a first inferior plasma treatment (upper) and inferior 100 ions and hot fix processing (under) after , the coated fabric colored liquid (water (blue), hexadecane (red) and soybean oil (transparent)) photographs, and water damage to the first 10 – change in contact angle in the repair process; (E) extended to 100 damaged – repair cycle changes.Li et al., The deposition of fluoroalkylsilane polyelectrolyte to the porous composite, developed a superhydrophobic coating of a self-repairing, O2 plasma after the coating is damaged, this material crosslinking at room temperature after 4 hours at 40% humidity can be restored superhydrophobic, contact angle 158 °, the sliding angle is less than 28 °. This is due to the material after the top layer is damaged, a fluoroalkyl chain binding present in the lower layer and polyacrylic acid (PAA) can be stably migrate to the surface, thereby restoring hydrophobicity. Researchers poly (vinylidene fluoride – hexafluoropropylene) (PVDF-HFP), coated with a mixture of fluoroalkyl silane (FAS) and silica nanoparticles on the surface of the fabric, to prepare a superhydrophobic fabric, the contact angle of water and oil are greater than 160 °. After destruction, the fabric was heated for 5 minutes at 130 ℃, can be fully restored superhydrophobic.

Fig 5. (A) surface functionalization, fixing initiator, a schematic configuration of a fluorine-containing polymer prepared in different brush; (B) the polymer brushes PMAF17 immersing the polymer solution, the original , antifouling properties schematic damage and repair material; (C) of the original, and repair damage PMAF17 AFM image of a polymer brush; (D) of the original, and repair damage PMAF17 PS- polymer brush dipped in a toluene solution for 12 hours AFM images; (E) polymer having a degree of offset of different thickness and molecular structure of the brush.Wang et al Zuilhof and the Si surface by atom transfer radical polymerization initiated surface (SI-ATRP) to prepare a 75 nm poly (meth acrylate, 2-perfluorooctyl methacrylate) (PMAF17) polymer brushes. This material is destroyed in harsh environments (high / low pH or UV), heat treated at 120 ℃ 2 hours to recover the antifouling property, which is due to the above polymerBrush Tg (40 ℃) temperature, segmental motion of the polymer chain increases, the reconstructed surface fluorinated material.

Figure 6 a schematic view of (A) forming a nanowire: producing nanowires, the initiator and the brush fixing fluoropolymer coated nanowires, the original, and repair damage adhesion protein-coated silicon nanowire acts polymer; (B) the original nanostructures, damage and repair PMAF17 static contact angle of the polymer brushes; PMAF17 polymer (C) nanostructures brush water static contact angle, advancing and receding contact angle after the change to repair the plasma damage and at 120 deg.] C; the increased thickness of soil BSA (D) of different surfaces, FFPB and NFPB represented flat and nanostructured fluoropolymer brushes.To further improve the investigators later antifouling property, the preparation of nanostructured PMAF17 fluoropolymer brushes. After we found that the fluorinated polymer grafted to the brush nanostructured silicon surface, which enhance the ability of anti-fouling, this is because the silicon surface roughness increases nanostructured material changes from hydrophobic to superhydrophobic. After air plasma damage, the water contact angle of the material is reduced from 152 ° to 135 °, after heat treatment for 30 minutes, the contact angle of full recovery, polymer brushes flat PMAF17 repair time is 2 hours, nanostructured, only need to 0.5 hours, which is the distance between the brush after structuring polymer increases, resulting in easier recombinant heated polymer segment. After the material is destroyed, a significant increase in protein adsorption, after heating the repair material against the protein adsorption performance can be restored to 90%.

FIG. 7. (A) SLIPS prepared schematic; (B) moving the droplets SLIPS pentane and superhydrophobic surface; (C) a quick fix damaged SLIPS surface (a typical hydrophobic comparison of the planar surface).Aizenberg et al., Low surface energy compound is dispersed into the porous material prepared two hydrophobic surface: the first one is perfluorinated liquid of low surface tension are incorporated into polyfluoroalkyl silane-modified of the nano-pillar array; the second is a liquid such as polytetrafluoroethylene incorporated into the nanofiber network. When these porous materials wear, performance degradation hydrophobic, porous material in capillary force, the liquid in the perfluorinated 150 ms at room temperaturePhysics can repair small scratches.

FIG. 8. (A) crosslinked PDMS is immersed in the oil, the oil molecules diffuse into the crosslinked network swelled PDMS; (B) a curing paraffin OG easily slide off the surface, but It is \”nailed\” on a solid PDMS; (C) PDMS organogel confocal fluorescence images over time.SLIPS materials discussed above, the interaction of the lubricant with the substrate is weak, easily lead to leakage of the lubricant. In order to reduce the leakage of the lubricant, the lubricant stored in advance researchers matrix material, and the like at a temperature of the lubricant or ultraviolet external stimulus will be released. When the organogel material is a self-repairing function (OG) prepared wang et al., At room temperature OG molten paraffin is deposited on the surface, paraffin exclusion, after 21 s, OG slightly inclined surface, the solidified paraffin began to move up, paraffin exhibits excellent repellency properties. This is due to the suppression of non-paraffin OG surface of homogeneous nucleation caused. Reversible breaking and Cui et al recombinant dynamic based on hydrogen bonding between the synthesis of a supramolecular organic gel, the gel when subjected to mechanical scraping, use of hydrogen bonds in the supramolecular polymer network can be achieved organogel self-repairing plastic.

FIG. 9. (A) on the surface and inside the membrane P2VP 3D graft polymer; (B) Wu et al., Self-repairing underwater superoleophobic / pollution works; (C ) induced underwater marine oil preparation schematic super hydrophobic coating.of the low surface energy material. Researchers poly (2-vinylpyridine) grafted membrane surface and an inner polyethylene oxide, an antifouling coating having synthesized pH responsive properties, its life increased four times, even if the coating is damaged large part, still has the self-healing function, which is due to internal graft segments may be supplemented by the movement of material damage to the surface, to make up for the loss of the coating. Wu et al prepared a self-repairing underwater and oleophobic anti-biofouling coating made of SiO2 microspheres of the coating by the ABC triblock polymer poly – (meth methacryloxypropyl-trimethoxy silane)-b- (poly – (acrylate-hydroxyethyl methacrylate) -b- (2- methyl-methacryloyloxyethyl phosphorylcholine), with the mixture self-assembled on a glass plate, then1,6-hexamethylene diisocyanate trimer crosslinking, when damage to the coating, 12 hours immersion in water can be fully restored and oleophobic anti-biofouling properties.

The second type of material (dynamic covalent or non-covalent interactions type)

FIG. 10. (A) by the HA and PEI-PEG Composition repairable damage and repair antifouling coatings; restored in (B) and cell adhesion PEI-PEG / HA film scratch (C); (D) (PDA / Alg-CAP @ CS-8 ) immersed in water to repair the multilayer film and the microscopic image 0,24 48 hours; (E) artificial seawater (PDA / Alg-CAP @ CS-8) ​​from a multilayer film schematic repair process; (F.) in Luria-Bertani medium after 18h, Pseudomonas aeruginosa and Staphylococcus aureus number; inhibition (G) PEM membrane of Staphylococcus aureus and Pseudomonas aeruginosa; (H) for the preparation of amphoteric ionic polymer network (ZPN) of the monolithic structure, and adhesion behavior on the original protein, the destruction and repair ZPN; ZPN coating an optical image of mechanical damage (I) and soaked in water for 1 min and dried for 1 minute the optical image; after immersion Alexa 488-BSA solution for 10 minutes, fluorescence image (L) ZPN coating (K) and the repair of damage.Sun et al., Based on electrostatic interactions synthesized from a PEI and PAA polyelectrolyte coating (PEM) repair, such coatings can be achieved self-repairing in water, since the coating which is water-swollen after easy movement, the fracture surface of the polyelectrolyte self-repair is achieved by interdiffusion. They subsequently by grafting on the PEG-modified PEI, manufactured PEI-PEG / HA-PEM coating which also has excellent self-healing properties, and the introduction of the PEG segments, but also has anti-biofilm coating adhesion characteristics. Chen et al adding chitosan capsaicin (CAP @ CS) nanocapsules to polydopamine / sodium alginate (PDA / Alg), the synthesis of a SHAF coating. Can be achieved under the effect of self-repair after pH coatings will release the CAP antifouling agent, and immersed in artificial seawater, Pseudomonas aeruginosa and Staphylococcus aureusMobilis has good inhibitory effect, after repeated self-healing, antibacterial effect of such coatings is only reduced by about 5%.

FIG. 11. (a) an epoxy microcapsule (ER-MC) and an epoxy curing underwater microcapsules (UEH-MC) structure; (b) mono methyl sulfobetaine body (SBMA), and zwitterionic sulfobetaine polymethyl methacrylate – glycidyl methacrylate ester synthesis route; schematic form (c) PSG / dual MCs / ER coating.Dong et al microcapsules and mixing the epoxy resin epoxy curing agent underwater microcapsules amine-cured epoxy paint system, and then the poly (sulfobetaine methacrylate – methacrylic acid glycidyl ester) (the PSG) was cast in the uncured epoxy coating surface, a coating having a synthesized underwater self-repair proteins and anti-adhesion function.

a schematic view of a multifunctional coating

The third type of material (double self-healing)

FIG. 12. (A1) Preparation of HDI microcapsules (the MC); (A2) a multifunctional coating upon self-repairing mechanical damage schematic; (A3) HDI-MC reversible hydrophilic coating – superhydrophobic transition mechanism; (B) the original zwitterionic polymer network, and repair the damage ( protein adhesion behavior on ZPNs); (C) microstructure (C1-C4) and macroscopic (C5-C8) destruction (C1, C2, C5, C1, C3, C5 and C7) optical (C1, C3, C5, and C7) and fluorescence (C2, C4, C6 and C8) image restoration after immersion in a solution of Alexa 488-BSA coated ZPN (C3, C4, C7 and C8); (D) PB-g-PFDT polymers and coatings synthetic route; under ambient conditions, prior self-repairing (E1), (E2) and after (F1), (F2), decane and the like droplets on the slide PB-g-PFDT coating ion etching; in ( G1) from before and after repair (G2), sliding on the cut PB-g-PFDT3 coating decane droplets picture.Yang et al resorcinol poly (urea – formaldehyde) (a PUF) microcapsules (of MCs) was modified, prepared by a simple one-pot having excellent against non-polar or weakly polar solvent adhesion and heat stabilityCoating containing hexamethylene diisocyanate (HDI) as a self-restorative microcapsules exhibit excellent superhydrophobic. Wan et al prepared a dual self-repairing anti bioadhesive coating, it can be self-repairing in the macro and nano / micrometer scale, and restore the surface wettability and anti bioadhesive properties. When coating a large area of ​​destruction, only needs to be immersed in saline, can achieve self-repairing, because it is the protonated ammonium group between the sulfonic acid groups may form ionic bonds broken by re saline solution, whereby realization damage repair. Li et al. To 1H, 1H, 2H, 2H- perfluoro decyl mercaptan (PFDT) grafted onto 1,2-polybutadiene (PB) was prepared as a clear antifouling coating having a heating repair capacity, O2 plasma after 5 seconds etch the coating, the coating will lose the ability to oleophobic, but after 48 hours, the coating can be restored oleophobic capacity, which is due to storage PFDT fluorochemical coating will migrate to the damaged area to achieve self-healing.

Application of the antifouling self-repairing material

FIG. 13. (A) preparation of MnO2 @ cotton fabric; (B) by thermal stimulation to restore the fabric superhydrophobic properties; (C) for an oil / water separation superhydrophobic MnO2 @ fabric; (D) the preparation of Co-PDMS @ PET fabric; freshly prepared (E1), damage (E2) and repair ( E3) Co-PDMS @ PET fabric oil / water separation process.Guo et al., In situ on the fabric surface cotton MnO2 nanoparticles grown and then modified stearate prepared a super-hydrophobic fabric having excellent self-healing, self-cleaning, oil / water separation and wear resistance. After the plasma treatment the fabric in air, exhibiting fully hydrophilic character, when the plasma treatment of the fabric was heated at 130 ℃ 10 minutes and the fabric exhibits surplus hydrophobic (contact angle of water of 153 °). After five consecutive etching – After heating, the fabric still retains 90% of the oil / water separation capacity. Liu et al prepared a polyethylene terephthalate (the PET) / Silicone fabric having a self-healing capabilities, crosslinking by coordinate bonds cobalt, the contact angle of such a fabric> 140 °, oil / water separation efficiency of 99%, having at room temperature for ultrafast selfCan repair fabric separation efficiency of a chloroform / water mixture after the fix is ​​still up to 98%.

FIG. 14. (A) ABA triblock copolymers DNODN chemical structure; (B) DNODN hydrogel structure; after exposure to Caco-2 cells for 48 hours uncoated (C1) and (C2) a microporous hydrogel fluorescent-microscopic image dish coated; (D) 10% of the hydrogel DNODN storage (G \’) and loss (G \”) modulus change temperature response; ( E) based on \”PFMNMF + PEI\” self-repairing injectable hydrogel, having an adjustable optical, mechanical and antibacterial properties; cyclic dynamic strain sweep measurements -9.5% (F) of the gel at 25 deg.] CZeng et al prepared: poly [(N-isopropyl acrylamide) -co- (N-3,4- dihydroxyphenyl ethyl acrylamide)] – b- polyethylene oxide -b- poly [(N-isopropyl acrylamide) -co- (N-3,4- dihydroxyphenyl ethyl acrylamide)], referred DNODN, based on hydrogen bonds and aromatic catechol aromatic interactions, this material has a fast self-healing and anti-adhesion Caco-2 cells. then they developed an injectable hydrogel ABA triblock copolymer, has excellent self-healing and antibacterial properties characteristics, and optical and mechanical properties change as the pH adjusted, the hydrogel exhibits a plurality of sol – gel transition, can effectively prevent the growth of Gram-negative and Gram-positive bacteria

[123. ] summary

progress of the self-healing anti-fouling materials at home and abroad are summarized, depending on the self-repair mechanism, they will be divided into three self-healing anti-fouling materials are described, which is based on supply of surface self-healing anti-fouling materials, self-repairing material interaction antifouling based on dynamic covalent and non-covalent mechanism will combine the two self-healing anti-fouling materials. they believe that the following nine aspects worthy of in-depth study : ① preparation of new molecular design based antifouling material; quantitative characterization of the degree of contamination ②; ③ original partial characterization, damage and repair area antifouling properties; ④ can be studied more contaminants resistant material; ⑤ since in saline repair materials; ⑦ offset process material scale -;; ⑥ ⑧ reduced to improve the mechanical strength of the material of the fluorine-containing compoundUse; ⑨ using 3D printing techniques for preparing antifouling self-repairing material. Original link: https: //onlinelibrary.wiley.com/doi/10.1002/adfm.201908098