Synergistic Aging Resistance and Autonomous Self-Healing in Trimethylolpropane Triglycidyl Ether-Based Anti-Icing Coatings

Abstract

Anti-icing materials have attracted considerable research interest due to their potential applications in preventing ice accretion and growth. However, a major challenge in the field is how to enhance durability while maintaining anti-icing performance. This study proposes a facile fabrication method for anti-icing coatings with anti-aging and self-healing abilities. A three-dimensionally cross-linked block copolymer, synthesized from polydimethylsiloxane, 4-aminophenyl disulfide, and trimethylolpropane triglycidyl ether, yielded a coating with excellent anti-icing/de-icing performance, including a low ice adhesion strength (29.2 kPa) and a high icing delay time (1389 s). The introduction of 4-aminophenyl disulfide enables dynamic disulfide bond reorganization and aromatic framework formation, synergistically conferring the icephobic coating with self-repair mechanisms and an anti-aging function. The coating exhibited a rapid self-healing capability (within 4 h), which is facilitated by the dynamic exchange of its hydrogen and disulfide bonds. Furthermore, the material demonstrated outstanding durability against physical wear and ultraviolet radiation. After being subjected to a 1000-cycle abrasion test and ultraviolet aging, the coating successfully retained more than 70% of its original performance in both icing delay time and ice adhesion strength. This paper proposes a facile strategy for developing self-healing and anti-aging anti-icing coatings and proposes innovative strategies for multifunctional anti-icing coatings.

1. Introduction

Anti-icing coatings have emerged as an effective strategy for diminishing ice-induced damage to power infrastructure components such as transmission lines and wind turbines [1,2,3]. Current research in this field primarily targets two categories of coatings: superhydrophobic surfaces and slippery liquid-infused porous surfaces (SLIPSs) [4].

Given that anti-icing materials need to operate stably under harsh environmental conditions such as sand abrasion and prolonged sunlight, their coatings must have excellent anti-aging properties, especially abrasion and UV resistance [5]. However, the anti-icing performance of superhydrophobic coatings and SLIPS (smooth liquid-infused porous surface) coatings is closely related to their surface morphology [6], and once the surface structure is degraded, the anti-icing effectiveness will be significantly reduced [7], thus showing poor anti-aging properties. In addition, anti-icing coatings in long-term outdoor service are often affected by wind and sand abrasion, which may lead to cracking or peeling of the coatings, so it is especially critical to develop coating systems with self-healing abilities [8,9,10,11,12]. Although superhydrophobic coatings and SLIPS coatings have outstanding performance in anti-icing, their performance in self-healing and anti-aging is still insufficient. In summary, only through the synergistic optimization of anti-icing, self-healing, and anti-aging properties can we provide a practical solution for anti-icing coatings for long-term outdoor applications [13,14,15].

Co-optimization using hydrogen bonding is a viable option due to the reversibility and directionality of hydrogen bonds; they can rapidly reorganize after fracture, endowing materials with self-healing capabilities. In related research, Zhuo et al. [16] designed a sponge-like structured transparent icephobic coating utilizing multiple hydrogen bonds within the polymer network, achieving an ice adhesion strength as low as 36.7 kPa. This coating could heal after heating at 100 °C for 6 h, although its self-healing capability remained limited. Therefore, the simultaneous introduction of non-covalent hydrogen bonds and reversible covalent bonds can significantly enhance the self-healing capacity of coatings. Zhao et al. [17] reported a self-healing network based on multiple hydrogen bonding interactions between urea groups, which can exhibit self-healing properties after 10–15 h of treatment at 60 °C, and the ice adhesion strength was still be maintained at about 50 kPa after 10 icing/de-icing cycles; however, the comprehensive balance between anti-icing efficiency, self-healing ability, and long-term aging resistance of this type of coating still needs to be further improved [18,19,20]. Therefore, this paper aims to develop an anti-icing coating with excellent synergistic optimization performance under a wide range of environmental conditions, aiming to achieve better anti-icing performance, a more efficient self-healing response, and more durable wear and aging resistance.

Based on the regulatory effect of hydrogen bonds on the water-freezing process and their intrinsic self-healing properties [21,22,23,24,25], we herein designed an anti-icing coating that is independent of surface structures, exhibits good self-healing performance, and possesses anti-aging capabilities. A block copolymer is synthesized from the precursors of glycerol ether, PDMS (bis(3-aminopropyl) terminated polydimethylsiloxane), and APD (4-aminophenyl disulfide). The coating demonstrates outstanding anti-icing performance, with an ice delay time reaching 1389 s and an ice adhesion strength as low as 16.3 kPa. After being scratched, it could self-heal upon heating at 60 °C for 4 h. Furthermore, it maintained relatively good anti-icing performance after 1000 abrasion cycles and showed no signs of blistering or powdering following 168 h of UV irradiation. Through the systematic analysis of these multifunctional materials, this work establishes a novel design paradigm for advanced anti-icing materials.

2. Materials and Methods

2.1. Materials

Trimethylolpropane triglycidyl ether (TMPTE, epoxy value = 0.68~0.74), 4-aminophenyl disulfide (APD, 98%), bis(3-aminopropyl) terminated polydimethylsiloxane (PDMS, Mn~5000 g/mol), and tetrahydrofuran (THF, 99.9%) are all purchased from Shanghai Taitan Technology Co. (Shanghai, China).

2.2. Preparation of Anti-Icing Coatings

PDMS, APD, and TMPTE are employed as base materials with an epoxy-to-amine equivalent ratio fixed at 1:1. By systematically increasing the molar ratio of PDMS functional groups to APD (1:1, 1:2, and 1:3), three anti-icing coating variants labeled PAT₁, PAT₂, and PAT₃ are developed. The components are dissolved in a controlled volume of THF solvent and subjected to continuous stirring at 60 °C under nitrogen protection for 20 h to achieve a homogeneous precursor solution. This solution is subsequently applied onto aluminum substrates using a coating knife, followed by ambient-temperature curing in air for 24 h to attain full cross-linking.

2.3. Characterization

2.3.1. Physical Characterization

The chemical composition of the coatings is analyzed using Fourier transform infrared spectroscopy (FTIR) with a Thermo Fisher Scientific Nicolet iS20 spectrometer (Waltham, MA, USA). Spectra are recorded for GTE, PDMS, APD, and PAT samples across the 4000–500 cm⁻¹ wavenumber range under standardized conditions: spectral resolution of 4 cm⁻¹ with 32 accumulated scans per measurement [26].

The ultraviolet (UV) shielding performance of PAT is evaluated using ultraviolet-visible (UV-Vis) spectroscopy and UV light aging techniques. The UV-Vis spectrum is measured across the 200–800 nm wavelength range using a UV-3600 Plus UV-Vis spectrophotometer (Kyoto, Japan) [27].

The surface free energy of the samples is quantified through the two-liquid contact angle method. Static contact angles are measured using 5 μL droplets of deionized water and diiodomethane, with surface energy values subsequently derived by applying Neumann’s equation of state to the experimental data obtained from these two probe liquids [28].

According to Young’s equation, the following relationship exists between the contact angle θ, the liquid surface tension σ_l, the liquid-solid interfacial tension σ_sl, and the solid surface free energy σ_s:

$${\sigma }_s={\sigma }_{sl}+{\sigma }_l\cdot \cos \theta$$

(1)

In order to calculate the surface free energy directly from the contact angle, Neumann proposed the following equation to calculate surface tension [29]:

$${\sigma }_{sl}={\sigma }_l+{\sigma }_s-2\sqrt{{\sigma }_l\cdot {\sigma }_s}\cdot e^{-\beta {\left({\sigma }_l-{\sigma }_s\right)}^2}$$

(2)

The gel fraction and swelling ratio of PAT were determined using the solvent immersion method [30]. One gram of the sample (W₀) was weighed and immersed in 25 mL of tetrahydrofuran for 3 days. After removal, the uncross-linked portion was completely dissolved to achieve swelling equilibrium. After three days, we blotted the sample surface with filter paper to remove residual solvent, weighed the sample, and recorded the swollen weight W₁. Subsequently, we dried the sample in an 80 °C oven for 24 h and recorded the final weight W₂.

The gel fraction of the sample is determined using the following equation:

$$G_f={\displaystyle \frac{W_2}{W_0}}\times 100\%$$

(3)

The swelling ratio of the sample is determined using the following equation:

$$S_r={\displaystyle \frac{W_1-W_0}{W_0}}\times 100\%$$

(4)

2.3.2. Anti-Icing Performance

(1)

Average icing temperature test

The coatings are placed on the cold stage and 4 μL of deionized water is added to their surface. The initial temperature of the deionized water is 26.18 ± 0.26 °C, while the freezing table is program-controlled to cool at a uniform rate of 5 °C/min. The temperature at which the water droplets transitioned from transparent to opaque within 1 s is observed and recorded. The average value of the 10 experimental data points is defined as the average freezing temperature (T_H) of the coating.

(2)

Icing delay time test

The time required for a water droplet to transition from liquid to fully frozen is defined as the icing delay time (IDT). To measure the IDT, a semiconductor cold stage is used to conduct experiments on bare aluminum sheets and PAT. The cold stage is first cooled from room temperature to −15 °C and samples are secured on its surface for 10 min to ensure thermal equilibrium. A 200 μL deionized water droplet is then deposited onto the sample surface using a syringe, with the moment of contact designated as the starting time (0 s). The duration until the droplet transitioned from transparent to fully opaque due to complete freezing is recorded. This procedure is repeated 10 times, and the average value is calculated as the coating’s icing delay time.

(3)

Ice adhesion strength test

The cooling table is precooled to −15 °C, upon which the coated aluminum sheet is placed. An ice cube mold (15 × 15 × 15 mm) is then positioned atop the coating and left undisturbed for 3 h to ensure complete freezing on the coating’s surface. Throughout the process, nitrogen gas is continuously circulated through the sample chamber at a controlled flow rate to simulate atmospheric flow conditions. A motorized translation stage connected to a force transducer advanced the ice at 0.1 mm/s, with the transducer recording the peak resistance force designated as Fmax during the pushing process; ice adhesion strength $\mathsf{\tau }$_ice is calculated as follows:

$${\tau }_{ice}={\displaystyle \frac{F_{\max }}{S}}$$

(5)

S is approximately 2.25 × 10⁻⁴ m². $\mathsf{\tau }$_ice is the average of the data from 10 experiments.

To analyze the stable operation of the PAT coating, the ice adhesion test described above is run 20 times through a constant icing/de-icing cycle and the ice adhesion is recorded to assess stability.

2.3.3. Self-Healing Performance Test

Three samples are first prepared by making standardized 10 mm scratches at identical positions using a blade. Following this, the samples are transferred to a forced-air drying oven where they are heated to 60 °C under maintained forced-air circulation. The duration required for complete visual disappearance of all scratches is systematically recorded as the self-healing time.

2.3.4. Aging Test

The abrasion resistance test was conducted according to the Chinese national standard GB/T 1689-2014, using a WML-76-type abrasion testing machine (Shandong Derrick Instrument Co., Ltd., Jinan, China), a rotary speed of 34 r/min, a grinding wheel using an abrasive for the alumina, and a particle size of No. 36; debris was removed between each cycle. Samples with a reference value of 700 mg were subjected to 1000 wear cycles with the grinding wheel at a load of 500 g, after which the wear mass was calculated.

UV aging was conducted in a LUYOR UCL-3500L UV cross-linking chamber (Shanghai, China). Coatings were positioned 20 cm directly beneath a 90-watt UV lamp (wavelength: 365 nm) for 168 h of continuous exposure.

3. Results and Discussion

3.1. Molecular Structure

The synthesis route of PAT anti-icing coatings is illustrated in Figure 1a. The amino groups of APD and PDMS both reacted with the epoxide groups of TMPTE, resulting in the formation of hydroxyl and secondary amine groups; the subsequent formation of linkages through these secondary amine groups led to a block copolymer with a three-dimensional network structure.

The chemical structure of PAT samples is examined by FTIR analysis. As shown in Figure 1b, all PAT samples exhibit C-H stretching vibration peaks of methyl and methylene groups at 2961 cm⁻¹. Additionally, the absorption peaks at 1010 cm⁻¹ and 1079 cm⁻¹ in the PAT spectrum correspond to the stretching vibration of Si-O bonds, which align with the absorption peak at 1062 cm⁻¹ in the PDMS spectrum. The absorption peak at 1258 cm⁻¹ in the PAT spectrum corresponds to the bending vibration of Si-CH₃, while the absorption peak at 788 cm⁻¹ belongs to the Si-C structure in PDMS. The weak absorption peak at 1409 cm⁻¹ primarily originates from the bending vibration modes of the methyl and methylene groups. As shown in Figure S1, PAT exhibits a characteristic peak at 1590 cm⁻¹, corresponding to the coupling of the C=C bond and N-H bond peaks at 1579 cm⁻¹ and 1488 cm⁻¹ in APD. As shown in Figure 1c, by comparing the peak intensities at 3362 cm⁻¹ in PAT₁, PAT₂, and PAT₃, it can be observed that the peak intensity of the hydroxyl group gradually increases with the increase in APD content. Due to the significant difference in molecular chain segment length between PDMS polymers and APD small molecules, when PDMS content decreases and APD content increases, the hydroxyl group density in the PAT samples correspondingly increases. By comparing the spectra of PAT samples and raw materials in Figure S2, it can be revealed that the disappearance of primary amine absorption is at 3419 cm⁻¹ for APD and the epoxy group peak is at 907 cm⁻¹ for TMPTE, indicating complete stoichiometric reactions. Based on the analysis of the FTIR spectra, these spectral matches validate the possibility of successful synthesis via the proposed route.

The test results of the solvent impregnation method are shown in Figure 2, where the gel fractions of PAT₁, PAT₂, and PAT₃ were 82.6%, 85.5%, and 91.1%, and the solubilization rates were 351%, 265%, and 143%, respectively. Since the higher the cross-linking density, the higher the gel fraction, the results of the solvent impregnation method showed that PAT3 had the highest cross-linking density, the largest polymer chain, and the least soluble material. Additionally, the dissolution rate is negatively correlated with the cross-linking density, indicating that PAT₃ is able to absorb the least amount of solvent. The experiments were able to prove that the reaction produced a three-dimensional cross-linked block copolymer with a good cross-link density.

3.2. Wettability and Surface Energy

The wettability of PAT coatings is quantified through static water contact angle (WCA) measurements [31]. As shown in Figure 3, all PAT coatings demonstrated apparent hydrophobic characteristics, with WCAs of 128.64° (PAT₁), 125.72° (PAT₂), and 123.79° (PAT₃). Since the main component of PAT block copolymers is PDMS, both its siloxane and methyl groups are hydrophobic, resulting in the overall hydrophobic nature of PAT samples. Since the ratio of amino groups to epoxy groups in the raw materials is always 1:1, as the APD content increases, the proportion of APD reacting with epoxy groups increases (while the proportion of PDMS reacting with epoxy groups decreases). This reduces the overall molecular weight of the block copolymer while increasing the density of the hydroxyl hydrophilic groups and hydrogen bonds, thereby reducing its hydrophobicity [32,33].

Complementing the WCA analysis, diiodomethane contact angles were measured (Figure S3). Based on Equation (2), surface energy calculations derived from these two-liquid measurements (Figure 2) yielded values of 21.44 mJ/m² (PAT₁), 24.64 mJ/m² (PAT₂), and 28.43 mJ/m² (PAT₃). The surface energy of these coatings is quite close to that of polytetrafluoroethylene (PTFE), a well-known low-surface-energy material, which has a surface energy of 18–22 mJ/m² [34]. The low surface energy of PAT coatings stems from abundant methyl groups in PDMS segments [35]. The methyl groups on PDMS chains suppress intermolecular interactions through three mechanisms: (1) reducing surface polarity, (2) providing steric hindrance, and (3) optimizing surface topology, collectively lowering the surface energy [36]. Consequently, the surface energy of coatings can be precisely tuned by controlling the PDMS concentration, thereby improving anti-icing performance. Notably, as the APD content gradually increases from PAT₁ to PAT₃, the density of hydroxyl groups and hydrogen bonds increases, and the interaction force with water molecules strengthens, significantly improving the surface energy of the material.

3.3. Anti-Icing Properties

The anti-icing performance is evaluated by measuring both the average freezing temperature and icing delay time of water droplets on the coatings. As shown in Figure 4a, the average freezing temperatures for PAT₁, PAT₂, and PAT₃ are −26.6 ± 1.0 °C, −24.64 −26.6 ± 1.1 °C, and −30.96 ± 1.2 °C, respectively, compared to −10.8 ± 0.8 °C for bare aluminum.

This enhanced performance originates from hydrogen bonding between hydrophilic groups and water molecules.

The cold stage is precooled to −15 °C to evaluate the icing delay time of water droplets on both bare aluminum surfaces and PAT surfaces. Specifically, the icing delay time is determined by tracking the time required for deionized water droplets to transition from transparent to opaque. The experimental results are shown in Figure 4b and the icing process for PAT₃ is shown in Figure 4c. The results show that, compared with icing delay time for bare aluminum (63 ± 34 s), PAT₁, PAT₂, and PAT₃ surfaces showed substantially prolonged icing delay times of 936 ± 70 s, 1132 ± 76 s, and 1389 ± 65 s, respectively. This phenomenon can be attributed to the gradual decrease in PDMS content and the corresponding increase in hydroxyl group density, as evidenced by the previous FTIR spectra analysis. Since hydrogen bond density is directly proportional to hydroxyl group density, PAT₃ exhibits the highest hydrogen bond density, which interacts most strongly with water molecules and consequently results in the longest icing delay.

Specifically, the epoxy groups in TMPTE underwent ring-opening reactions with amino groups from PDMS and APD, generating secondary amine groups and hydrophilic hydroxyl groups. Additionally, the intrinsic ether bonds in TMPTE contributed to the coating’s hydrophilicity. These structural components collectively form hydrogen bonds with water molecules. Icing is the process of ice nucleation through the orderly movement and directional arrangement of water molecules, which further develop into ice. Hydrogen bonding and water molecules between the force can effectively slow down the regulation of water molecules’ orderly movement and directional arrangement and then inhibit the aggregation of water molecules into the nucleus, in order to achieve the delay of icing [37].

Notably, the freezing temperatures of PAT₁~PAT₃ coatings decreased progressively with reduced PDMS content. This correlation aligns with the hydrogen bond density principle: a higher hydrogen bond density between the coating and water molecules corresponds to a lower surface freezing temperature [38]. The FTIR spectra revealed increasing hydroxyl group density with decreasing PDMS content, which intensifies water-coating interactions and thereby depresses freezing temperatures. Compared to other anti-icing material studies (summarized in

Table 1. Comparison of the performance of various types of anti-icing coatings.

Anti-Ice Coating	Surface Freezing Temperature	Delayed Icing Time	Ice Adhesion Strength
Laser-induced graphene silica sol coating [39]	−10 °C	840 s	30 kPa
Manipulating airflow superhydrophobic surfaces [36]	−20 °C	1381 s	50 kPa
Fluorinated resin/graphene composite coating [40]	−15.5 °C	958 s	30 kPa
This research	−30.96 °C	1389 s	<30 kPa

), it is indicated that the PAT coatings exhibit significantly lower freezing temperatures and prolonged icing delay times, demonstrating superior ice nucleation inhibition capability.

Simple molecular dynamics simulations were performed to verify the anti-icing properties of PAT by calculating the number of hydrogen bonds between water molecules in pure water (Figure S4a) and in water with added PAT molecules (Figure S4b), respectively. According to the simulation results (Figure S4), the number of hydrogen bonds between water molecules in the system with added PAT molecules was significantly reduced. This suggests that PAT weakens the hydrogen bonding network between water molecules by forming hydrogen bonding interactions with them. This mechanism both prevents water molecules from aggregating to form stable ice nuclei and inhibits them from arranging in specific orientations to form highly ordered hexagonal ice crystal structures. Based on molecular dynamics simulations, it can be inferred that PAT possesses a certain ability to lower the freezing point and delay ice formation.

As seen in Figure 5a, utilizing the ice shear strength platform, the ice adhesion strengths of PAT₁, PAT₂, and PAT₃ are measured at 16.3 ± 2.5 kPa, 24.7 ± 3.0 kPa, and 29.2 ± 3.4 kPa, respectively. In contrast, the bare aluminum surface exhibits significantly higher ice adhesion strength (212 ± 5.0 kPa) under identical conditions. The reduced ice adhesion strength observed in the prepared coatings compared to bare aluminum can be attributed to their lower surface energy, as calculated in Section 3.2 [41]. As the ratio of APD to PDMS increases, it leads to an increase in hydroxyl hydrophilic groups and hydrogen bond density, resulting in a deterioration in ice adhesion strength from PAT₁ to PAT₃. Results of ice adhesion strength after icing/de-icing cycles (Figure 5b) indicate that all samples maintain τice values similar to initial measurements even after 20 icing/de-icing cycles, demonstrating stable de-icing performance.

3.4. Self-Healing Properties

To evaluate the self-healing capability of PAT coatings, a standardized 10 mm scratch is created on all samples using a scalpel, followed by heat treatment in a forced-air oven at 60 °C. The scratch disappearance time is recorded during the healing process. As the ratio of APD to PDMS increased, the self-healing time decreased substantially, with PAT₁, PAT₂, and PAT₃ requiring 12 h, 8 h, and 4 h, respectively. These results indicate that an increase in the proportion of hydrogen bonds and disulfide bonds has a significant promoting effect on self-healing performance.

Figure 6a illustrates how reversible disulfide bonds facilitate dynamic molecular rearrangement within the coating matrix. The self-healing mechanism is primarily attributed to reversible disulfide bonds and dynamic hydrogen bonding in APD. When subjected to external stimuli, polymer chains undergo rearrangement that facilitates rapid reorganization of broken disulfide/hydrogen bonds and the formation of new polymer networks, thereby enabling material repair. Enhanced self-healing rates correlate with increased densities of exchangeable disulfide bonds and dynamic hydrogen bonds at higher APD concentrations. Using spray-UV polymerization, researchers developed a rosin-based self-healing superhydrophobic composite coating that delays icing for 728 s at −15 °C and fully repairs scratches within 4 h at 80 °C [42]. The PAT coating exhibits superior self-healing performance relative to the reference material, attributable to its dynamic hydrogen bonds and incorporated exchangeable disulfide bonds. Upon damage, hydrogen bonds, characterized by their low bond energy, undergo rapid rupture and reorganization at the fracture interface without requiring substantial external energy input [43]. This process effectively bridges micro-cracks even at room or relatively low temperatures, thereby creating close contact interfaces for subsequent disulfide bond exchanges. Once the molecules are repositioned under the guidance of hydrogen bonds, a higher energy input is necessary to overcome the relatively high energy barrier associated with disulfide exchange. Under moderate heating conditions, disulfide bonds undergo reversible cleavage and recombination. This rearrangement of covalent bonds fundamentally restores the material’s covalent network structure and mechanical strength [25].

To assess post-healing anti-icing performance, PAT₃ is selected as a representative sample for in situ observation of the healing process in the forced-air oven (Figure 6b). Post-repair evaluations included τ_ice measurements and IDT tests. Comparative analysis of anti-icing/de-icing performance before and after healing (Figure 6c and

Table 2. IDT and τice of PAT before and after self-healing.

Sample	Pristine IDT(s)	Post-Healing IDT(s)	Repair Efficiency	Pristine τice (kPa)	Post-Healing τice (kPa)	Repair Efficiency
PAT1	936	896	95.73%	16.3	17.1	95.32%
PAT2	1132	1098	96.99%	24.7	25.2	98.01%
PAT3	1389	1267	91.21%	29.2	29.4	99.31%

) revealed healing efficiencies defined as follows: ice nucleation delay time efficiency (post-healing/pre-healing ratio) and ice adhesion strength recovery efficiency (pre-healing/post-healing inverse ratio). The ice nucleation delay healing efficiencies reached 95.73%, 96.99%, and 91.21% for PAT₁, PAT₂, and PAT₃, respectively, while ice adhesion strength recovery efficiencies attained values of 95.32%, 98.01%, and 99.31%. These results confirm comparable performance between pristine and healed PAT coatings, demonstrating exceptional self-restoration capabilities across all samples. The self-healing effect in this paper is mainly in the visual representation of crack closure and the anti-icing function, rather than the complete restoration of mechanical properties.

3.5. Anti-Aging Performance

In order to evaluate the anti-aging performance of PAT samples, we selected two typical working conditions of wear and UV aging for research. Among them, UV radiation induces irreversible damage to the molecular structure, leading to surface crack and blister of coatings. Dust and sand continuously impact the coating’s surface, progressively thinning the protective layer and exposing the substrate. Therefore, UV aging and abrasion resistance abilities determine the durability of outdoor coatings [44].

The abrasion resistance of PAT coatings is evaluated using the Akron abrasion tester. Specimens are subjected to rolling friction against a grinding wheel under controlled conditions. After 1000 abrasion circles under a 500 g load, PAT₁, PAT₂, and PAT₃ exhibited mass losses of 6.7 mg, 3.7 mg, and 2.3 mg, respectively, confirming excellent abrasion resistance. This performance is attributed to the energy dissipation mechanism: when the material is subjected to stress generated by friction, hydrogen bonds, as “sacrificial bonds,” will preferentially undergo reversible fracture. This fracture process requires energy absorption, effectively dissipating the mechanical energy input from the outside and preventing energy from concentrating on the primary key, leading to its fracture [26].

Furthermore, anti-/de-icing performance has been evaluated after 1000 abrasion cycles, as shown in Figure 7a,b. This test structure demonstrates that the coating maintains effective anti-icing properties and exhibits notable abrasion resistance. The icing delay time and ice adhesion strength are 794 s and 24.6 kPa for PAT1, 989 s and 27.1 kPa for PAT₂, and 1156 s and 31.8 kPa for PAT₃, respectively. Compared to the unabraded samples, the PAT₁, PAT₂, and PAT₃ coatings exhibited high retention rates in their delayed icing time, measuring 84.8%, 87.4%, and 83.2%, respectively. Similarly, the retention rates for ice adhesion strength are 79.1%, 91.1%, and 91.2%. These results demonstrate that the anti-/de-icing performance of all PAT samples is effectively preserved following abrasion, highlighting their strong mechanical durability.

Other thicknesses were also considered, with thicker samples demonstrating superior anti-icing performance and no significant effect on abrasion resistance, but thickness did not influence the effect of raw material ratios on anti-icing performance, see Supplementary Material Table S1 for detailed performance.

It is evident that, when considered collectively, hydrogen bonding exerts a synergistic effect on the performance of anti-icing, the capacity for self-healing, and the anti-aging properties. The dynamic reversibility of hydrogen bonds has been demonstrated to regulate the oriented arrangement of water molecules, thereby inhibiting nucleation and enhancing the self-healing performance of materials by repairing damage. Furthermore, when the material is subjected to frictional stress, the hydrogen bond will preferentially undergo reversible fracture and act as a sacrificial bond. This fracture process consumes energy and effectively dissipates externally applied mechanical energy. This process functions to impede the accumulation of energy at the primary bond, thereby averting the occurrence of fracture and, consequently, enhancing the wear resistance of the material [45].

FTIR analysis has been conducted on the PAT coating that underwent a 168 h UV aging test. The results of this analysis are then compared with those of the original sample. As shown in Figure 8, the FTIR spectra of PAT changed significantly after UV irradiation because the UV irradiation catalyzed the chemical transformations and radical chain reactions of the photosensitive oxides and aromatic amine structures as the density of these functional groups increased, thus amplifying the changes in the characteristic peaks. The N-H/O-H stretching at 3354 cm⁻¹ indicated that the UV light triggered the photodegradation and oxidation of aromatic amine/epoxy residues, resulting in hydroxyl/amine derivatives. The enhanced C=C stretching vibrations at 1593 cm⁻¹ and 1492 cm⁻¹ indicate the presence of partial cross-linking, aromatic amine rearrangement, or cross-linking network disruption, which implies network disruption and the enrichment of aromatic structures. UV irradiation accelerated the oxidation/rearrangement of organic components in the cured network, and the magnitude of structural changes is proportional to the APD ratio.

For coatings subjected to prolonged outdoor exposure, UV-induced degradation significantly impacts service longevity. UV-vis spectroscopy analysis (Figure 9a) revealed outstanding UV shielding performance across all PAT samples. The spectral data demonstrate PAT’s broad-spectrum UV blocking (200–400 nm). Progressive reduction in transmittance with increasing APD content is observed, culminating in PAT3’s complete opacity (0% transmittance) within 400–413 nm. This trend correlates with the enhanced benzene ring density at higher APD concentrations, which strengthens UV attenuation through π-π electronic transitions [46].

Following 168 h of UV irradiation, the coating exhibited slight color deepening without observable blistering or chalking (Figure 9b). As summarized in Figure 9c,d and

Table 3. Comparison of IDT and τ_ice between original and abraded UV-aged samples.

Sample	Original Sample		Samples After Abrasion				Sample After UV Aging
	IDT(s)	τice (kPa)	IDT(s)	Retention Rates	τice (kPa)	Retention Rates	IDT(s)	Retention Rates	τice (kPa)	Retention Rates
PAT1	936	16.3	794	84.8%	20.6	79.1%	658	70.2%	23.4	69.7%
PAT2	1132	24.7	989	87.4%	27.1	91.1%	879	77.6%	29.6	83.4%
PAT3	1389	29.2	1156	83.2%	31.8	91.2%	994	71.6%	34.7	84.1%

, following UV aging, the retention rates of the freezing delay times for PAT₁, PAT₂, and PAT₃ are 70.2%, 77.6%, and 71.6%, respectively, while the corresponding retention rates of ice adhesion strength are 69.7%, 83.4%, and 84.1%, respectively. The coating’s UV resistance is primarily attributable to the absence of free radicals in PDMS and copolymer polymer chains, which prevent photochemical degradation. Additionally, UV attenuation is enhanced through π→π* electron transitions in the aromatic ring system, where increased benzene ring density improves radiation absorption [47].

A previous study documented that a polyurea icephobic coating, following 72 h of continuous exposure to 6 W UV irradiation, exhibited an ice adhesion strength of approximately 31.0 ± 6.1 kPa, representing an increase of 7.3 kPa from its initial value of 23.7 kPa [48]. In contrast, the PAT coatings demonstrated superior resistance to UV aging.

4. Conclusions

This study presents a straightforward synthesis method for icephobic coatings using TMPTE, PDMS, and APD as precursors. The optimized coating combines exceptional anti-icing performance with an integrated UV-shielding capability and autonomous self-healing properties. Demonstrated through comprehensive characterization, this multifunctional system establishes a new design framework for durable anti-icing solutions capable of withstanding outdoor environmental conditions.

(1)

In terms of anti-icing performance, PAT₃ exhibited the lowest freezing temperature (−30.96 ℃) and the longest anti-icing delay time (1389 s). These anti-icing properties stem from hydrogen bonding interactions between hydrophilic groups and water molecules, effectively hindering ice crystal nucleation through kinetic delay and thermodynamic inhibition. However, due to hydrogen bonding interactions with water molecules, PAT₃ exhibits an ice adhesion strength of 29.2 kPa, slightly higher than PAT₁ and PAT₂.

(2)

PAT coatings offer excellent self-healing and aging resistance, with a self-healing efficiency of 99.31% at 60 °C, as well as outstanding abrasion and UV resistance. These multifunctional properties result from the supramolecular network structure formed by PDMS and APD. A synergistic combination of dynamic disulfide exchange and hydrogen bonding interactions promotes autonomous damage recovery.

(3)

The PAT coatings exhibited outstanding durability, with the highest retention rates reaching 91.2% for abrasive wear and 84.1% for UV aging resistance. The entanglement of long molecular chains dissipates impact forces through elastic deformation and reduces wear and tear. The π → π* electron leaps in the aromatic ring system enhance UV attenuation, and the increase in benzene ring density improves radiation absorption.