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Marine antifouling coating based on fluorescent-modified poly(ethylene-co-tetrafluoroethylene) resin

  • Ze Wang , Yu Li , Jiahao Ren , Yangkai Xiong , Zheng Li and Guoqing Wang EMAIL logo
Published/Copyright: March 13, 2024
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e-Polymers
From the journal e-Polymers Volume 24 Issue 1

Abstract

The growth of marine economy urgently needs non-toxic coatings. This study provides a novel and green coating that obtains outstanding antifouling performance by combining the low surface energy effect and the fluorescent effect. The coating was synthesized by reacting tetraphenylethylene (TPE) as the fluorescent component with poly(ethylene-co-tetrafluoroethylene) resin. The introduction of TPE provided the resin coating with lower surface energy and fluorescent properties, leading to improve the antifouling performance. This study indicates fluorescent TPE polymers for marine antifouling and opens new horizons for the exploitation of fluorescent antifouling coatings.

Keywords: antifouling coating; fluorescent effect; low surface energy; poly(ethylene-co-tetrafluoroethylene); TPE derivatives

1 Introduction

Marine fouling organisms, which are abundantly present in the marine environment (1,2), cause significant harm to ships, marine facilities, offshore oil platforms, offshore wind power generators, marine transportation pipelines, etc., hence seriously hindering the development of the marine economy (1,2,3). The conventional antifouling coatings usually employ toxic fungicides or heavy metals to inhibit the growth of marine organisms (4,5,6). However, these fillers also lead to further pollution in the marine environment (7,8). Thus, it is vital to develop non-toxic and environment-friendly marine antifouling coatings. Low surface energy coatings, which can prevent the adhesion of marine fouling organisms, are one of the candidates (9,10). For low surface energy coatings, such as poly(ethylene-co-tetrafluoroethylene) (EFTE), the low surface energy normally comes from the existence of F atoms. Moreover, the organic fluorine coatings exhibit excellent chemical stability, weather resistance, and stain resistance (11,12,13).

However, the marine antifouling performance solely resulting from the low surface energy coating is limited under static situations (14,15). To further improve the antifouling performance under static conditions, the fluorescent effect may provide a promising method for the low surface energy coating. The fluorescent effect in microorganisms, which has been reported by Guo et al. and Jin et al., states that the attachment degree of diatoms decreases significantly under fluorescence (16,17). Cohn et al. and Cao et al. verify that the light can directly reduce the activity of diatoms and inhibit their deposition on the substrates (18,19,20). In the fouling processes, diatoms work as pioneer microorganisms that determine the formation of biofilms on the substrates and secondary adhesion of microorganisms (21,22). Therefore, the fluorescent coatings that inhibit the deposition of diatoms can further minimize the formation of biofilms and secondary adhesion of other marine organisms.

Here, we are aiming to prepare a green and underwater curing composite coating for the marine antifouling. EFTE, chosen as the building block of organic fluorine resin, is a versatile polymer with poor roughness, small elastic modulus, and non-toxic to the marine (23,24). Tetraphenylethylene (TPE) derivatives, which show significant fluorescence emission in the aggregated or solid-state due to the restriction of intramolecular rotation, are available to be applied as fluorescent dyes to resin coatings (22,23,24,25,26). In highly transparent seawater, the UV radiation from sunlight can penetrate 20 m below the water surface (27), thus allowing the photochemical processes to occur and trigger the fluorescent anti-fouling mechanism. Moreover, the TPE derivatives have good hydrophobicity, simple synthesis procedures, and good processability of purification and modification (28,29). These advantages make them easy to combine with resins and fabricate coatings. For antifouling coatings, the introduction of TPE derivatives can improve the hydrophobicity of the coatings, which is also beneficial to the antifouling performance.

In this study, we have fabricated TPE-EFTE fluorescent anti-fouling painting by introduced TPE-COOH into the EFTE resin. The synergy of the low surface energy antifouling mechanism and fluorescent antifouling mechanism enhances the antifouling performance of the coating. The environment-friendly antifouling coating exhibits outstanding antifouling performance and the water-insoluble EFTE resins and TPE fluorescent make them promising for use as underwater curing coatings for the rehabilitation of submarine or underwater facilities.

2 Materials and methods

2.1 Materials

Triphenylbromoethylene (TPBE), 4-ethoxycarbonylphenylboronic acid (EPBA), tetrakis(triphenylphosphine)palladium [pd(pph3)4], tetrabutylammonium bromide (TBAB), potassium carbonate (K2CO3), sodium sulfate (Na2SO4), sodium hydroxide (NaOH), tetrahydrofuran (THF), petroleum ether (PET), ethyl acetate (EA), dichloromethane (DCM), hydrochloric acid (HCl), and methanol (MeOH) were obtained from Aladdin (Shanghai, China). 4-Dimethylamiopyridine (DMAP), N,N′-dicyclohexylcarbodiimide (DCC), phosphate-buffered saline (PBS), and butyl acetate were purchased from Macklin (Shanghai, China). All these chemicals above were used as received. The poly(ethylene-co-tetrafluoroethylene) resin (EFTE (Zeffle GK-570)) used in this study was obtained from Daikin (Shanghai, China) and dried in a vacuum in advance. Aliphatic polyisocyanate (Wannate HT-100) was used as a curing agent for polyurethane and acquired from Wanhua (Shandong, China). LB liquid medium contains tryptone, yeast extract, and sodium chloride, while PBS contains sodium chloride, potassium chloride, sodium phosphate dibasic, and potassium phosphate monobasic.

2.2 Synthesis of TPE-EFTE

The synthesis procedures of TPE-EFTE are shown in Figure 1. Ethyl 4-(triphenylethenyl)benzoate (TPE-COOEt) was synthesized according to the previous report by Huang (30). EPBA (1.09 g, 5 mmol), TPBE (1.35 g, 4 mmol), TBAB (0.01 g, 0.03 mmol), pd(pph3)4 (0.12 g, 0.1 mmol), and K2CO3 (1.38 g, 10 mmol) were added to a 250 mL three-necked flask with THF (40 mL) and deionized water (5 mL). The mixture was stirred and refluxed at 80°C in nitrogen for 24 h. When cooled down, it was extracted three times with DCM, dehydrated by adding an appropriate amount of Na2SO4 to remove excess water, and concentrated by rotary evaporation. Then, the crude product was purified through silica gel (300–400 mesh) with a mixture of PET and EA (10:1, v/v) and pure TPE-COOEt was obtained subsequently.

Figure 1 Schematic representation of the synthesis of TPE-EFTE resin.
Figure 1

Schematic representation of the synthesis of TPE-EFTE resin.

Then, the prepared TPE-COOEt (0.40 g, 1 mmol), NaOH (0.40 g, 10 mmol), MeOH (40 mL), THF (40 mL), and deionized water (40 mL) were mixed and stirred at 60°C for 10 h for the synthesis of TPE-COOH. After the solvent was removed through vacuum rotary evaporation and the pH value of the mixture was adjusted to 6.0 by adding HCl (1.0 mol·L−1) slowly within an ice bath, a large amount of precipitates appeared. The solvent was removed through filtration and the precipitates were washed with 20 mL of deionized water three times. After drying in an oven, the pure TPE-COOH was obtained.

For the synthesis of TPE-EFTE, the TPE-COOH (0.38 g, 1.0 mmol), DMAP (0.08 g, 0.6 mmol), and DCC (0.46 g, 0.2 mmol) were well dissolved in THF (50 mL) with EFTE (8.89 g, 10 mmol) and the mixture was kept stirring for 24 h (31). A thin layer of chromatographic (TLC) was used to monitor the consumption of TPE-COOH. When the reaction was completed, THF was removed by rotary evaporation and EA was added. The mixture was placed in a refrigerator overnight. The solution was purified by adding deionized water and separated through a funnel. Na2SO4 was added to remove the residual water and removed through filtration. Finally, yellow TPE-EFTE was obtained after the removal of EA through rotary evaporation. By adjusting the formulation, TPE-EFTE samples with various amounts of TPE-COOH were prepared, as shown in Table 1.

Table 1

The TPE-EFTE samples synthesized from different formulations

Sample name TPE-COOH (mmol) EFTE (mmol)
TPE-EFTE-1 0.2 10
TPE-EFTE-2 0.3 10
TPE-EFTE-3 0.5 10
TPE-EFTE-4 1.0 10

2.3 The fabrication of coatings

To fabricate the paint of TPE-EFTE coating, the TPE-EFTE resin (14.0 g) and the curing agent (4 g) were added into EA (6 mL) and completely blended through ultrasonic dispersion and stirring. The paint was sprayed on smooth or wrinkled/corrugated substrate and dried at room temperature until fully curing. Glass slides were selected as substrates for small samples used in some lab tests. The carbon steel plate was another type of substrate used for real-sea teats. The carbon steel plates with a size of 150 mm × 70 mm × 5 mm were sandblasted and washed with de-ionized water and acetone in advance. Before coating the above paints for steel plates, iron oxide epoxy resin coatings were used for anti-corrosion. The thickness of TPE-EFTE coatings determined by 3D surface profiler was 100 μm. In addition, EFTE coating was also prepared as a control.

2.4 Characterizations

To test the structure and properties of the prepared samples, various characterizations were conducted. FT-IR spectra were performed on a Fourier transform spectrometer (Bruker Tensor-27) through the KBr pellet method with a wavenumber range of 400–4,000 cm−1. 1H NMR spectra were carried out by spectrometer (Bruker Avance neo 400) with deuterated dimethyl sulfoxide (DMSO-d6) or deuterated chloroform (CDCl3) as solvents. The fluorescence spectra were recorded by a fluorescence spectrometer (Hitachi F-7000). The hydrophobicity of the coatings is determined by a contact angle analyzer (Dataphysics OCA25). The droplet volume was approximately 20 μL and the measurement was conducted under room temperature. The contact angle was tested 10 times and averaged.

2.5 Antibacterial adhesion test

An antibacterial adhesion test was conducted to estimate the antifouling performance of coatings. Escherichia coli is used as the bacteria for the testing and the attachment of E. coli on the surface of samples was observed through the fluorescence microscope.

E. coli strains were provided by the State Key Laboratory of Marine Resource Utilization in the South China Sea. The E. coli was inoculated on Luria–Bertani (LB) solid medium by an inoculation ring and then placed in an incubator at a constant temperature of 37°C for 24 h. The obtained single strain was transferred to 60 mL LB liquid medium and then placed in a shaker with a speed of 140 rpm at 37°C for 12 h. The strains were dispersed into the LB liquid medium at a ratio of 1:500 and placed in the shaker at 37°C for 24 h. After the bacterial liquid was centrifuged (3,000 rpm, 15 min), the supernatant was removed. The final solution with an E. coli concentration of 105 CFU·mL−1 was obtained by redispersing the E. coli in PBS (32) and determined by the plate count method.

Then, a blank slide, EFTE-coated slide, and TPE-EFTE-coated slides were added into a Petri dish containing 5 mL E. coli solution, respectively. These slides were immersed in E. coli solution and incubated in an incubator at 37°C for 24 h. After the samples were moved out from the E. coli solution, they were stained with 0.01% acridine orange solution. The E. coli on the samples was recorded through the fluorescence microscope and the number of bacteria is counted by plate count method.

2.6 Real-sea tests of the coatings

To further study the antifouling performance, the real-sea tests were conducted in Haikou Port (Hainan, China) of the South China Sea according to the method for testing antifouling panels in shallow submergence (GB/T 5370-2007). The prepared samples were placed into the sea with a depth of 1 m from the water surface. After being immersed in the water for 30 and 90 days, the plates were taken out to observe the growth of fouling on the surface, and photographs were taken for further analysis, respectively.

3 Results and discussion

3.1 Structure of the TPE-EFTE resin

As shown in Figure 1, there are several steps to synthesize the TPE-ETFE. One important intermediate product is TPE-COOEt. The TPE-COOEt was synthesized through the Suzuki coupling reaction between EPBA and TPBE in the presence of pd(pph3)4 as the catalyst. The structure of TPE-COOEt was determined by 1H NMR spectrum (CDCl3 is used as the solvent). As shown in Figure 2a, the peaks at about 7.83–7.74 and 7.28–7.02 ppm are the protons of benzene rings. The peaks’ assignments of –CH2 were observed at 4.34–4.28 ppm, and the peaks at 1.43–1.30 ppm belong to –CH3.

Figure 2 NMR spectra of TPE-COOEt (a) and TPE-COOH (b).
Figure 2

NMR spectra of TPE-COOEt (a) and TPE-COOH (b).

TPE-COOH is prepared by alkaline hydrolysis of TPE-COOEt, as shown in Figure 1. The structure of TPE-COOH was confirmed by 1H NMR (DMSO-d6 was used as the solvent) and the 1H NMR spectrum was shown in Figure 2b. Compared to the spectrum of the TPE-COOEt, the 1H NMR spectrum of TPE-COOH has similar peaks which correspond to the benzene rings at about 7.96–6.96 ppm. However, the new emerging carboxyl peak at 12.85 ppm and the disappearance of –CH2 and −CH3 peaks indicate the successful synthesis of TPE-COOH.

TPE-EFTE was prepared through the esterification reaction between TPE-COOH and EFTE with DCC/DMAP as the catalyst, as shown in Figure 1. The 1H NMR spectra (CDCl3 was used as the solvent) of EFTE resin and TPE-EFTE resin are displayed in Figure 3. Compared to the spectrum of the original EFTE resin, the 1H NMR spectrum of TPE-EFTE has similar peaks that correspond to the main chain of polymers. However, the carboxyl peak of TPE-COOH disappears and the new emerging peaks at 8.19–6.99 ppm of benzene rings can be observed, which indicates that the TPE segment was successfully introduced into the EFTE resin through reaction.

Figure 3 NMR spectra of EFTE resin (a) and TPE-EFTE resin (b).
Figure 3

NMR spectra of EFTE resin (a) and TPE-EFTE resin (b).

Moreover, the structure of TPE-EFTE resin was further confirmed through FT-IR spectra (Figure 4). Compared to the FT-IR spectrum of the original EFTE resin, the newly stretching vibration peaks of Ar-H at about 3,058.29 cm−1 and the peaks of benzene ring vibration at 1,607.66–1,519.06 cm−1 appear in the spectrum of TPE-EFTE. Meanwhile, the peaks at 1,739.07 and 1,243.25 cm−1 correspond to the strong bending vibration of C═O and the characteristic peak of –C–O–, which demonstrate that TPE-EFTE was synthesized.

Figure 4 FT-IR spectra of TPE-COOH, EFTE resin, and TPE-EFTE resin.
Figure 4

FT-IR spectra of TPE-COOH, EFTE resin, and TPE-EFTE resin.

3.2 Fluorescence properties of TPE-EFTE resin and coating

There are few studies focusing on the application of fluorescent materials to coatings. However, the possibility of using fluorescent components to enhance the antifouling performance is valuable for organic coatings. In this study, the effect of the link between fluorescent segment (TPE-COOH) and polymer chain (EFTE resin) on the photophysical properties was evaluated through PL-spectrum. Figure 5a shows that the fluorescent intensity of TPE-EFTE resin in THF is much stronger than that of the mixture of TPE-COOH and EFTE resins. After the covalently linking between TPE-COOH and EFTE resins through esterification reaction, the EFTE segment limits the intramolecular rotation of TPE chains, thus releasing energy through the form of fluorescence, and exhibits a good fluorescence performance even in a dilute solution state (33). Moreover, the intensity improvement confirms the reaction between the TPE-COOH and EFTE resins, which is consistent with the results of FTIR and 1H NMR spectra.

Figure 5 (a) PL-spectra of the TPE-EFTE resin and the mixture of TPE-COOH and EFTE resin. (b) PL-spectra of TPE-EFTE resin with different water/THF ratios. (c) PL-spectra of TPE-EFTE resin after different curing time.
Figure 5

(a) PL-spectra of the TPE-EFTE resin and the mixture of TPE-COOH and EFTE resin. (b) PL-spectra of TPE-EFTE resin with different water/THF ratios. (c) PL-spectra of TPE-EFTE resin after different curing time.

Here, all TPE-COOH, ETFE, and TPE-EFTE are soluble in THF. However, the resins are insoluble in water and the coatings will be used in water conditions. Thus, understanding the fluorescent behavior in water is very important to evaluate the possibility of using in antifouling coatings. The samples were dissolved in THF first, and water was subsequently injected to observe the variation in the fluorescence intensity, as shown in Figure 5b. With an increase in water content in the mixture, the fluorescence intensity of the TPE-EFTE resin increases gradually. The improvement is due to the aggregation-enhanced emission effect caused by the molecular chain conformation changes from the stretch confirmation to the curled conformation (34). The high fluorescent intensity means that this obtained resin is available to be used as coatings in underwater conditions.

In addition to the solvent and condition, the curing process that involves cross-linking between the curing agent and resin may also affect the fluorescent characteristics. Therefore, the fluorescence intensity of the coating during the curing process was also monitored and the fluorescence spectra are exhibited in Figure 5c. The results show that the fluorescence intensity of TPE-EFTE resin increases with the increase of the curing time. The higher intensity is due to the cross-link between resin and curing agent and the volatilization of the solvent which leads to a denser internal structure of the coating, reduces the movement space of fluorescent segments, and limits the rotation of molecular chains. Thus, more energy is consumed in the form of fluorescence and higher fluorescent intensity is obtained with a longer curing time.

3.3 Contact angle of the TPE-EFTE coatings

ETFE is a copolymer of tetrafluoroethylene and ethylene. Due to the presence of fluorine atoms, the groups of ETFE are difficult to Van der Waals interaction with other molecules, which leads to the low surface energy of the coating and high hydrophobicity. TPE derivatives also have good hydrophobicity due to the existence of the benzene ring structure. Therefore, the induction of TPE is possible to improve the hydrophobicity of ETFE resin. To understand the hydrophobicity effect, the static contact angle of the EFTE and TPE-EFTE coatings were measured and summarized. Figure 6 reveals that the contact angle of ETFE increased from 85.19 ± 0.54 to 94.76 ± 1.42° with the introduction and increase of TPE groups, which suggests that the existence of TPE reduces the surface energy of the resin coatings. The low surface energy would be also beneficial to the antifouling performance of the coatings.

Figure 6 The water contact angle of the coatings.
Figure 6

The water contact angle of the coatings.

3.4 Antibacterial adhesion test

To estimate the antifouling performance of obtained samples, an antibacterial adhesion test is performed. The coatings were immersed in the bacterial solutions and later counted the number of bacteria on the surface of the coatings. A smaller number means a better antibacterial adhesion performance. Figure 7 shows the fluorescence microscope images (a–f) and the numbers (g) of E. coli attached to the surface of the samples. The results reveal that TPE-EFTE coatings exhibit improved antibacterial adhesion performance compared to the blank sample and EFTE coating. Meanwhile, with increasing the concentration of TPE segments in the resin, the antibacterial adhesion of the coating keeps improving. The improvement results from the synergistic effect of the low surface energy and fluorescent property of the coatings.

Figure 7 Antibacterial adhesion performance of different coatings. Fluorescence microscope images of (a) Blank; (b) EFTE coating; (c) TPE-EFTE-1 coating; (d) TPE-EFTE-2 coating; (e) TPE-EFTE-3 coating; and (f) TPE-EFTE-4 coating. (g) Number of bacteria adhering on the different coatings.
Figure 7

Antibacterial adhesion performance of different coatings. Fluorescence microscope images of (a) Blank; (b) EFTE coating; (c) TPE-EFTE-1 coating; (d) TPE-EFTE-2 coating; (e) TPE-EFTE-3 coating; and (f) TPE-EFTE-4 coating. (g) Number of bacteria adhering on the different coatings.

3.5 Real-sea antifouling tests

To better understand the antifouling performance of the coatings, the coated steel plates were immersed in the South China Sea. The surfaces of coatings were recorded before soaking, after 30 days of soaking, and after 90 days of soaking, respectively, as shown in Figure 8. These photos show that, after 30 days, a lot of marine fouling organisms have already adhered to the blank plate. There are fewer organisms on EFTE coating than that of the blank plate, meanwhile, the surface of TPE-EFTE coating is almost clean. After 90 days of immersion, more fouling organisms have adhered to the surfaces of coatings. The blank plate is almost completely covered by fouling organisms. However, the TPE-EFTE coating still shows the best antifouling performance with only some aquatic plants. As we know, the barnacle is one fouling organism that normally sticks to the bottom of boats and is very hard to remove. The aquatic plants reproduce and grow rapidly but the adhesion is not strong and easy to take away by the water flow. No barnacle found on the surface after 90 days of soaking indicates the good antifouling performance of TPE-EFTE coating.

Figure 8 Photographs of blank, ETFE, and TPE-ETFE coatings in real-sea anti-fouling tests.
Figure 8

Photographs of blank, ETFE, and TPE-ETFE coatings in real-sea anti-fouling tests.

4 Conclusions

In summary, we have produced a novel TPE-EFTE anti-fouling coating with low surface energy and fluorescent properties. Furthermore, the TPE not only provides fluorescent behavior but also improves the hydrophobicity of the coating. The antibacterial adhesion results of TPE-EFTE coating demonstrate a 23% reduction of attached E. coli compared to the EFTE coating. After immersing the coatings in seawater for 90 days, TPE-EFTE coating still kept surface clean and showed better anti-fouling performance. Overall, this study explores the synergistic effect of two antifouling mechanisms by introduced fluorescent dyes to resin and provides a new perspective for developing high-effective and non-toxic antifouling coatings.

  1. Funding information: This research was funded by the National Natural Science Foundation of China (grant number 51963008), the horizontal project (grant number zzzz002023451), and the Natural Science Foundation of Hainan Province (grant number 520MS015).

  2. Author contributions: Ze Wang: writing – original draft, writing – review and editing, methodology, formal analysis; Yu Li: writing – resources; Jiahao Ren: original draft, formal analysis; Yangkai Xiong: original draft, formal analysis; Zheng Li: writing – review and editing; Guoqing Wang: writing – review and editing, resources, project administration.

  3. Conflict of interest: Authors state no conflict of interest.

  4. Data availability statement: All data generated or analyzed during this study are included in this published article.

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Received: 2023-08-21
Revised: 2023-10-30
Accepted: 2023-12-06
Published Online: 2024-03-13

© 2024 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/epoly-2023-0130
Keywords for this article
antifouling coating; fluorescent effect; low surface energy; poly(ethylene-co-tetrafluoroethylene); TPE derivatives
Creative Commons
BY 4.0

Articles in the same Issue

  1. Research Articles
  2. Flame-retardant thermoelectric responsive coating based on poly(3,4-ethylenedioxythiphene) modified metal–organic frameworks
  3. Highly stretchable, durable, and reversibly thermochromic wrapped yarns induced by Joule heating: With an emphasis on parametric study of elastane drafts
  4. Molecular dynamics simulation and experimental study on the mechanical properties of PET nanocomposites filled with CaCO3, SiO2, and POE-g-GMA
  5. Multifunctional hydrogel based on silk fibroin/thermosensitive polymers supporting implant biomaterials in osteomyelitis
  6. Marine antifouling coating based on fluorescent-modified poly(ethylene-co-tetrafluoroethylene) resin
  7. Preparation and application of profiled luminescent polyester fiber with reversible photochromism materials
  8. Determination of pesticide residue in soil samples by molecularly imprinted solid-phase extraction method
  9. The die swell eliminating mechanism of hot air assisted 3D printing of GF/PP and its influence on the product performance
  10. Rheological behavior of particle-filled polymer suspensions and its influence on surface structure of the coated electrodes
  11. The effects of property variation on the dripping behaviour of polymers during UL94 test simulated by particle finite element method
  12. Experimental evaluation on compression-after-impact behavior of perforated sandwich panel comprised of foam core and glass fiber reinforced epoxy hybrid facesheets
  13. Synthesis, characterization and evaluation of a pH-responsive molecular imprinted polymer for Matrine as an intelligent drug delivery system
  14. Twist-related parametric optimization of Joule heating-triggered highly stretchable thermochromic wrapped yarns using technique for order preference by similarity to ideal solution
  15. Comparative analysis of flow factors and crystallinity in conventional extrusion and gas-assisted extrusion
  16. Simulation approach to study kinetic heterogeneity of gadolinium catalytic system in the 1,4-cis-polyisoprene production
  17. Properties of kenaf fiber-reinforced polyamide 6 composites
  18. Cellulose acetate filter rods tuned by surface engineering modification for typical smoke components adsorption
  19. A blue fluorescent waterborne polyurethane-based Zn(ii) complex with antibacterial activity
  20. Experimental investigation on damage mechanism of GFRP laminates embedded with/without steel wire mesh under low-velocity-impact and post-impact tensile loading
  21. Preparation and application research of composites with low vacuum outgassing and excellent electromagnetic sealing performance
  22. Assessing the recycling potential of thermosetting polymer waste in high-density polyethylene composites for safety helmet applications
  23. Mesoscale mechanics investigation of multi-component solid propellant systems
  24. Preparation of HTV silicone rubber with hydrophobic–uvioresistant composite coating and the aging research
  25. Experimental investigation on tensile behavior of CFRP bolted joints subjected to hydrothermal aging
  26. Structure and transition behavior of crosslinked poly(2-(2-methoxyethoxy) ethylmethacrylate-co-(ethyleneglycol) methacrylate) gel film on cellulosic-based flat substrate
  27. Mechanical properties and thermal stability of high-temperature (cooking temperature)-resistant PP/HDPE/POE composites
  28. Preparation of itaconic acid-modified epoxy resins and comparative study on the properties of it and epoxy acrylates
  29. Synthesis and properties of novel degradable polyglycolide-based polyurethanes
  30. Fatigue life prediction method of carbon fiber-reinforced composites
  31. Thermal, morphological, and structural characterization of starch-based bio-polymers for melt spinnability
  32. Robust biaxially stretchable polylactic acid films based on the highly oriented chain network and “nano-walls” containing zinc phenylphosphonate and calcium sulfate whisker: Superior mechanical, barrier, and optical properties
  33. ARGET ATRP of styrene with low catalyst usage in bio-based solvent γ-valerolactone
  34. New PMMA-InP/ZnS nanohybrid coatings for improving the performance of c-Si photovoltaic cells
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  36. Preparation of cardanol-based curing agent for underwater drainage pipeline repairs
  37. Preparation of lightweight PBS foams with high ductility and impact toughness by foam injection molding
  38. Gamma-ray shielding investigation of nano- and microstructures of SnO on polyester resin composites: Experimental and theoretical study
  39. Experimental study on impact and flexural behaviors of CFRP/aluminum-honeycomb sandwich panel
  40. Normal-hexane treatment on PET-based waste fiber depolymerization process
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  42. Design, synthesis, and characterization of novel copolymer gel particles for water-plugging applications
  43. Influence of 1,1′-Azobis(cyclohexanezonitrile) on the thermo-oxidative aging performance of diolefin elastomers
  44. Characteristics of cellulose nanofibril films prepared by liquid- and gas-phase esterification processes
  45. Investigation on the biaxial stretching deformation mechanism of PA6 film based on finite element method
  46. Simultaneous effects of temperature and backbone length on static and dynamic properties of high-density polyethylene-1-butene copolymer melt: Equilibrium molecular dynamics approach
  47. Research on microscopic structure–activity relationship of AP particle–matrix interface in HTPB propellant
  48. Three-layered films enable efficient passive radiation cooling of buildings
  49. Electrospun nanofibers membranes of La(OH)3/PAN as a versatile adsorbent for fluoride remediation: Performance and mechanisms
  50. Preparation and characterization of biodegradable polyester fibers enhanced with antibacterial and antiviral organic composites
  51. Preparation of hydrophobic silicone rubber composite insulators and the research of anti-aging performance
  52. Surface modification of sepiolite and its application in one-component silicone potting adhesive
  53. Study on hydrophobicity and aging characteristics of epoxy resin modified with nano-MgO
  54. Optimization of baffle’s height in an asymmetric twin-screw extruder using the response surface model
  55. Effect of surface treatment of nickel-coated graphite on conductive rubber
  56. Experimental investigation on low-velocity impact and compression after impact behaviors of GFRP laminates with steel mesh reinforced
  57. Development and characterization of acetylated and acetylated surface-modified tapioca starches as a carrier material for linalool
  58. Investigation of the compaction density of electromagnetic moulding of poly(ether-ketone-ketone) polymer powder
  59. Experimental investigation on low-velocity-impact and post-impact-tension behaviors of GFRP T-joints after hydrothermal aging
  60. The repeated low-velocity impact response and damage accumulation of shape memory alloy hybrid composite laminates
  61. Exploring a new method for high-performance TPSiV preparation through innovative Si–H/Pt curing system in VSR/TPU blends
  62. Large-scale production of highly responsive, stretchable, and conductive wrapped yarns for wearable strain sensors
  63. Preparation of natural raw rubber and silica/NR composites with low generation heat through aqueous silane flocculation
  64. Molecular dynamics simulation of the interaction between polybutylene terephthalate and A3 during thermal-oxidative aging
  65. Crashworthiness of GFRP/aluminum hybrid square tubes under quasi-static compression and single/repeated impact
  66. Review Articles
  67. Recent advancements in multinuclear early transition metal catalysts for olefin polymerization through cooperative effects
  68. Impact of ionic liquids on the thermal properties of polymer composites
  69. Recent progress in properties and application of antibacterial food packaging materials based on polyvinyl alcohol
  70. Additive manufacturing (3D printing) technologies for fiber-reinforced polymer composite materials: A review on fabrication methods and process parameters
  71. Rapid Communication
  72. Design, synthesis, characterization, and adsorption capacities of novel superabsorbent polymers derived from poly (potato starch xanthate-graft-acrylamide)
  73. Special Issue: Biodegradable and bio-based polymers: Green approaches (Guest Editors: Kumaran Subramanian, A. Wilson Santhosh Kumar, and Venkatajothi Ramarao)
  74. Development of smart core–shell nanoparticles-based sensors for diagnostics of salivary alpha-amylase in biomedical and forensics
  75. Thermoplastic-polymer matrix composite of banana/betel nut husk fiber reinforcement: Physico-mechanical properties evaluation
  76. Special Issue: Electrospun Functional Materials
  77. Electrospun polyacrylonitrile/regenerated cellulose/citral nanofibers as active food packagings
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