Simultaneous radical and condensation polymerization for the fabrication of cost-effective, transparent, and underwater oil-repellent hybrid films

Abstract

Underwater oil-repellent surfaces are crucial for various applications that require protection against oil-based contaminants in aquatic environments, yet producing cost-effective, crack-free, and transparent coatings with such properties remains a major challenge. In this study, a one-pot, two-step synthesis approach was used to fabricate transparent, underwater oil-repellent coatings by synthesizing a hybrid organic–inorganic copolymer (PAA–TEOS) through simultaneous radical and condensation polymerization of acrylic acid (AA) and TEOS alkoxysilane. The AA/TEOS molar ratio and TEOS addition timing were optimized to obtain crack-free films, and wettability was evaluated by measuring water contact angles in air and hexadecane contact angles underwater. Surface morphology and roughness were characterized using SEM and AFM. The optimized hybrid coatings exhibited high transparency, superhydrophilicity in air (water contact angle ≤10°), and superoleophobicity underwater (hexadecane contact angle >160°), while resisting cracking and maintaining structural integrity in aqueous environments. These characteristics make them highly suitable for marine antifouling, underwater sensors, and oil–water separation applications, offering a scalable and eco-friendly alternative to conventional coatings.

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1. Introduction

Superoleophobic surfaces are characterized by exhibiting an oil contact angle (CA) of 150° or higher, along with a contact angle hysteresis (CAH) or sliding angle of 10° or lower.^1–4 However, due to variations in the surface tensions of different oils, the terminology of superoleophobicity emphasizes a minimum requirement of a 140° contact angle with hexadecane for a surface to be classified as superoleophobic.² A comparable criterion has not been strictly established for underwater oil repellency; nevertheless, the widespread use of hexadecane as a test liquid in air suggests its applicability underwater as well. Given hexadecane's moderate surface tension, its use in underwater systems is considered a realistic and practical approach.^5,6 The underwater oil-repellent property of a surface is directly related to its hydrophilic character in air. In addition to hydrophilicity, increased surface roughness facilitates water penetration into the surface textures, which contributes to the repulsion of oil droplets underwater. This behavior is consistent with the underwater Cassie state model.^7,8 A superhydrophilic surface is defined as one exhibiting a water contact angle of 10° or less.⁹

Underwater oil-repellent surfaces play a pivotal role in safeguarding materials and devices against oil-based contaminants in aquatic environments.^10–13 They have emerged as critical in a range of applications, including antifouling coatings in marine industries,^4,8,14–18 underwater sensors,^4,15 microfluidic devices,⁴ fuel transportation systems,¹⁴ oil–water separation technologies,^{8,13,15,19–22} oil spill remediation strategies,^{7,8,16,17,19,23} wastewater treatment processes^{13,17,19,20,24,25} and self-cleaning protective coatings.^14,15,26 Despite these advances, developing coatings that combine high mechanical durability, cost-effectiveness, and environmental compatibility for underwater use remains a substantial research challenge.^16,17 Recent developments in functional nanostructures also highlight the growing interest in multifunctional surfaces for sensing, catalysis, and oil–water interfacial engineering. For instance, nanozyme-integrated sensing platforms have enabled ultralow-cost and highly sensitive detection of gaseous biomarkers such as H₂S.²⁷ Similarly, hollow metal-oxide and metal–sulfide architectures have shown great potential in advanced signal-transduction mechanisms and photocatalytic interfacial reactions.^28,29 These advances underscore the expanding application space for hybrid material systems and further motivate the development of robust, optically transparent, and underwater oil-repellent coatings capable of operating in complex environments. Among the various material systems explored to address these challenges, organic–inorganic hybrids—particularly those combining polyvinyl alcohol (PVA) and alkoxysilanes (such as TEOS and APTES)—have demonstrated considerable promise. PVA offers excellent film-forming capability and inherent hydrophilicity, while TEOS contributes rigidity and chemical stability, resulting in hybrid coatings with superior performance characteristics.^13,30 Consequently, alkoxysilane-modified PVA systems have gained prominence in the pursuit of advanced functional surfaces. Notably, Georgieva et al. reported the fabrication of PVA–TEOS hybrid films via a sol–gel process, observing underwater superoleophobicity coupled with air superhydrophilicity and suggesting their use as tissue engineering scaffolds.³¹ Similarly, Bryaskova et al. introduced silver nanoparticles (AgNPs) into such hybrid systems to impart antibacterial properties, thereby creating promising candidates for biomedical coatings.³² Composite structures integrating APTES-functionalized SiO₂ nanoparticles within PVA matrices, prepared via freeze–thaw methods, have also been shown to exhibit underwater oil repellency, low-temperature resilience, and self-healing behavior.¹⁷ In biomedical applications, membranes produced from PVA/chitosan blends crosslinked with TEOS were found to remove over 90% of copper ions from aqueous solutions.³⁰ For optical applications, Okkay et al. (2021) developed transparent, mechanically robust, and superhydrophilic films using PVA and TMOS through a microwave-assisted sol–gel method. The incorporation of silica nanoparticles further enhanced performance, enabling the creation of anti-fog surfaces with water contact angles as low as 5°.³³ Biomimetic approaches utilizing alkoxysilane-modified PVA composites have also gained attention for their potential in multifunctional applications.^15,34,35 Nevertheless, many existing studies rely on multi-step processing routes or costly reagents, which hinder scalability and industrial implementation. This underscores the pressing need for developing durable, transparent, and environmentally benign coatings suitable for underwater environments. Acrylic-acid-based hybrid systems provide stronger covalent bonding with TEOS, leading to a more homogeneous and mechanically robust hybrid network.³⁶ Chen et al. reported that the carboxyl groups of PAA actively participate in TEOS hydrolysis and condensation, forming stable Si–O–C linkages that suppress phase separation and ensure uniform silica distribution. Their findings further demonstrated that the presence of PAA regulates silica growth and prevents siloxane aggregation, resulting in transparent and crack-free hybrid films.³⁶ PAA exhibits stronger intrinsic hydrophilicity, enabling the formation of a more stable hydration layer under water, which is essential for achieving high underwater oil repellency. Moreover, the abundance of carboxyl groups in PAA allows more regular and stronger covalent bonding with TEOS compared with hydroxyl-rich PVA, leading to a more homogeneous hybrid network.³⁷ This difference arises because –COOH groups exhibit a much higher affinity for silanol species generated during TEOS hydrolysis, forming stronger hydrogen-bonding and electrostatic interactions, which promote uniform Si–O–C link formation and suppress siloxane aggregation.³⁷ These structural features contribute to improved transparency, reduced cracking, and enhanced mechanical durability. In this study, the one-pot, two-step simultaneous radical–condensation polymerization strategy further enhances these benefits by eliminating the heterogeneous network formation typically observed in multi-step AA/TEOS processes. This approach shortens processing time, reduces cost, and enables the fabrication of uniform, stable, and underwater oil-repellent hybrid films.

In previous studies, acrylic acid has mainly been combined with TEOS or other alkoxysilanes through multi-step routes, where PAA is first deposited or grafted and TEOS is subsequently hydrolysed and condensed to build rough or functional surfaces. For example, Du et al. consecutively treated nylon with PAA, TEOS and octadecylamine to enhance hydrophobicity, reaching a water contact angle of about 125°, but only after multiple immersion, curing and washing steps.³⁸ Shen and co-workers used PAA as a blocking polymer in a sol–gel TEOS/iso-BTMS system to suppress siloxane aggregation and improve film homogeneity, achieving a maximum water contact angle of 147° in air, yet the process still relied on sol aging, careful factor screening and post-addition of PAA.³⁹ Yao et al. reported an acrylate prepolymer that was first synthesized by radical polymerization and then crosslinked with TEOS in a separate curing step, where increasing TEOS improved hardness and water resistance but gradually compromised transparency.⁴⁰ Other AA/TEOS systems based on plasma-deposited dual layers⁴¹ or PAA-functionalized particles assembled during TEOS hydrolysis⁴² also require distinct deposition and condensation stages and often additional post-modification to obtain the desired wettability. In contrast to these sequential or post-addition strategies, our one-pot, two-step approach combines the radical polymerization of AA with its concurrent condensation with TEOS in a single bath. This simultaneous polymerization route not only reduces the number of processing steps and associated cost but also promotes a more regular and homogeneous covalent linkage between the growing PAA chains and the forming siloxane network, which is crucial for obtaining crack-free, transparent hybrid films with high underwater oil contact angles and long-term stability in aqueous environments. Compared with conventional multi-step AA/TEOS processes, such as preformed PAA deposition followed by sol–gel condensation or sequential TEOS crosslinking, the simultaneous radical and condensation polymerization route offers several advantages. The one-pot configuration significantly reduces processing time and cost, while enabling a more homogeneous covalent integration between the growing PAA chains and the developing siloxane network. This structural uniformity is critical for obtaining crack-free and transparent hybrid films. In addition, the method provides superior underwater oil repellency due to the balanced distribution of hydrophilic groups and inorganic domains. However, this approach also presents certain limitations: the optimal TEOS concentration window is relatively narrow, and the simultaneous reaction requires precise timing to prevent excessive sol–gel contraction. Despite these constraints, the combined radical–condensation route provides a practical and efficient pathway for fabricating stable oil-repellent hybrid coatings.

In this study, TEOS-modified PAA composite films were synthesized through this one-pot, two-step strategy. The process integrates simultaneous radical polymerization of AA and controlled condensation with TEOS. Initially, radical polymerization of PAA was allowed to proceed for a predetermined period, after which the alkoxysilane crosslinker was added dropwise. This controlled addition enables the growing PAA chains to crosslink through their hydroxyl termini with TEOS ethoxy groups, completing a more uniform hybrid network. By systematically optimizing the TEOS content, we evaluated the resulting changes in surface chemistry, morphology and wettability, and successfully developed crack-free, transparent and underwater oil-repellent hybrid films with enhanced mechanical durability.

2. Experimental

2.1. Materials

Tetraethyl orthosilicate (TEOS, 98%), ethyl alcohol, (ETOH, 99,8%) and ammonium persulfate (APS, >98%) were purchased from Sigma-Aldrich. acrylic acid (AA, 98%) was supplied with Acros Organics. Sodium hydroxide (NaOH, 99%) pellet and glass slides (76 × 26 mm, Isolab, Turkey) were used as substrates.

2.2. Design and fabrication of crosslinked pAA–TEOS hybrid networks

Hybrid pAA–TEOS copolymers were synthesized through a one-pot, two-step approach involving the simultaneous radical polymerization of acrylic acid (AA) and the condensation reaction between hydroxyl groups of AA and ethoxy groups of tetraethyl orthosilicate (TEOS), as schematically illustrated in Fig. 1. This concurrent polymerization strategy enables both radical and condensation reactions to occur simultaneously during chain growth.^43,44 In this process, the vinyl groups of AA undergo free-radical polymerization initiated by APS, while the ethoxy groups of TEOS react with hydroxyl groups from AA to form Si–O–C crosslinks. This design aimed to enhance the underwater mechanical stability of the films through TEOS-induced crosslinking, while maintaining sufficient surface hydroxyl functionalities to preserve underwater oil repellency.

Fig. 1 Schematic illustration of the simultaneous radical polymerization of AA and the condensation reaction with TEOS.

The reaction temperature was maintained at 75 °C. First, 15 mL of deionized water and 15 mL of ethanol were mixed with APS and transferred into a round-bottom flask equipped with a reflux condenser and magnetic stirrer (Fig. 1). After reaching thermal equilibrium, the AA solution (prepared in a water–ethanol mixture) was added dropwise into the reactor. Polymerization was carried out at 75 °C under continuous stirring (200 rpm) for 4 hours. Subsequently, 0.1 g of NaOH (added as 1 M solution) and TEOS were introduced into the reaction mixture, and the reaction was continued for an additional 2 hours under the same conditions.

The polymer codes, monomer compositions, and wettability results of the synthesized copolymers with varying AA and TEOS ratios are presented in Table 1. At the end of the reaction, the resulting hybrid solutions were deposited onto pre-cleaned glass slides (26 × 76 mm) using a Laurell WS-400 BZ-6NPP/LITE spin coater. The spin-coating process was conducted at 1500 rpm for 1 minute. The coated samples were then cured in an oven at 60 °C for 1 hour and subsequently stored in a desiccator for 24 hours prior to surface characterization. In addition to the AA–TEOS hybrid formulations, pure PAA films (AA2–AA8 in Table 1), prepared without TEOS, and a pure TEOS-derived coating were synthesized under identical conditions (Table 1). These samples served as control formulations to independently evaluate the roles of AA radical polymerization and TEOS condensation in the film formation process.

Table 1 Composition table of synthesized copolymers with varying monomer ratios and wettability results

Code	AA (mole)	TEOS (mole)
All reactions were conducted using a molar ratio of APS : ethanol : water of 1 : 240 : 776, with 0.025 mol of APS utilized per reaction.
AA2	0.2	—	22	104
AA4	0.4	—	24	152
AA6	0.6	—	5	160
AA8	0.8	—	6	170
TEOS	—	0.3	70	85
AA2–TEOS0.15	0.2	0.015	58	145
AA4–TEOS0.15	0.4	0.015	29	152
AA6–TEOS0.15	0.6	0.015	11	164
AA8–TEOS0.15	0.8	0.015	13	170
AA8–TEOS0.2	0.8	0.02	10	170
AA8–TEOS0.4	0.8	0.04	11	163
AA8–TEOS0.6	0.8	0.06	23	156
AA8–TEOS0.8	0.8	0.08	25	158

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2.3. Characterization

The optical transmittance of the thin films was measured using UV-Vis spectroscopy in the wavelength range of 300–900 nm with a PerkinElmer Lambda 950 spectrophotometer. The water contact angle (WCA) of the hybrid films in air was measured using a Data Physics GmbH OCA-15EC contact angle goniometer with a precision of ±0.1°. For each sample, static WCA values were recorded at five different positions, and the reported values correspond to the average ± standard deviation.⁴⁵ Underwater hexadecane contact angles were measured using a custom-built setup, where droplet images were captured with an Imaging Source DFK 27AUP006 camera and subsequently analyzed using ImageJ software; these underwater measurements were obtained from three different surface positions with an overall measurement precision of ±1°.⁴⁶ The surface morphology and microstructure of the samples were examined via scanning electron microscopy (SEM) using a JEOL SEM-7100-EDX model. Additionally, surface roughness and root mean square (RMS) values were measured with a Witec Alpha 300 RS atomic force microscope (AFM) operating in non-contact mode over a scan area of 100 × 100 µm.

3. Results and discussion

As shown in Table 1, the AA2–AA8 formulations (no TEOS) and the TEOS-only coating serve as negative controls for TEOS condensation and AA radical polymerization, respectively. These control samples were used to evaluate the individual contributions of each component to surface wettability and underwater stability. The thin-film contact angle measurements of the pure PAA homopolymers (AA2–AA8) show that increasing the AA molar content markedly decreases the water contact angle, rendering the surfaces superhydrophilic. At the same time, the underwater hexadecane contact angle increases significantly from 104° to 170°, indicating that PAA networks inherently provide strong underwater oil repellency. However, these PAA films deteriorate rapidly during underwater measurements, demonstrating their insufficient mechanical stability in aqueous environments. Therefore, as also summarized in Table 1, AA–TEOS hybrid films were subsequently fabricated to introduce inorganic crosslinking. By systematically varying the TEOS content, the compositions were optimized to obtain coatings that combine high underwater oil repellency with robust mechanical durability.

To this end, the variations in water contact angle and underwater hexadecane contact angle . were first examined as a function of increasing AA content at a constant TEOS concentration (Fig. 2). The results indicate that as the AA content increases, the water contact angle decreases from 58° to 11°, ultimately reaching the threshold for superhydrophilicity (Fig. 2(a)). Specifically, the AA₂–TEOS_0.15 copolymer exhibited a water contact angle of 58°, whereas the angle decreased dramatically to 11° for AA₆–TEOS_0.15 when the AA concentration reached 1.5 M. This trend is attributed to the increasing density of hydroxyl (–OH) groups on the surface.

Fig. 2 Variation of (a) water contact angle in air and (b) underwater hexadecane contact angle as a function of acrylic acid (AA) content for films prepared with and without TEOS.

In parallel, the underwater hexadecane contact angle increases significantly, reaching up to 170° with higher AA content (Fig. 2(b)). The inverse relationship between water contact angle and underwater oil contact angle, both governed by the surface –OH concentration, aligns well with previous literature findings. Similarly, when the AA molar ratio was held constant, increasing the TEOS content from 40 wt% to 75 wt% resulted in an increase in the water contact angle from 10° to 25°, while the underwater hexadecane contact angle decreased from 170° to 155° (Fig. 3). This behavior can be attributed to the condensation reactions between TEOS and –OH groups from AA, which reduce the surface hydroxyl content.

Fig. 3 Variation of water and underwater hexadecane contact angles with increasing TEOS content.

Interestingly, beyond 70 wt% TEOS, the slight reversal in the water contact angle—first decreasing and then increasing—may be related to the preferential self-condensation of ethoxy groups over their reaction with hydroxyl groups. When examining the surface behavior against dichloromethane (DCM), it was observed that the underwater oil contact angle decreased from 156° to 131° with increasing TEOS content. This decrease is likely due to DCM's inherently high surface tension (Fig. 4).

Fig. 4 Variation of underwater hexadecane and DCM contact angles with increasing TEOS content.

The greater decrease in underwater contact angle for DCM compared to hexadecane is attributed to its higher polarity and stronger interfacial interaction with the hydrated surface, leading to enhanced spreading (Fig. 4).

SEM analysis revealed that the surface morphology strongly depends on the AA/TEOS ratio. At low TEOS contents (AA₈–TEOS_0.2 and AA₈–TEOS_0.4), the films exhibited smooth and uniform textures with no signs of structural defects. As the TEOS fraction increased, however, the sol–gel network became denser and shrinkage-induced surface patterns appeared (AA₈–TEOS_0.6 and AA₈–TEOS_0.8). While these features resemble cracking at first glance, they are more accurately interpreted as contraction lines generated during silica condensation and drying—a phenomenon that intensifies at higher TEOS ratios due to volumetric shrinkage of the inorganic-rich domains. The homopolymer p(TEOS) sample further supports this interpretation by displaying a characteristic aggregated spherical morphology arising from TEOS-rich sol–gel domains. AFM images corroborate the SEM observations: RMS roughness values increase moderately with TEOS content, yet the surface topography remains continuous and well-integrated, indicating that the hybrid network preserves its structural integrity even at elevated inorganic fractions. The fact that all RMS values remain below 100 nm is consistent with the retained optical transparency of the composite films.

As shown in Fig. 5, the surfaces exhibit light transmittance comparable to that of a clean glass slide, confirming that all composite coatings remain optically transparent. A slight increase in RMS values was observed with increasing TEOS content, indicating that enhanced inorganic crosslinking leads to a moderate rise in surface roughness. Notably, the decrease in underwater oil contact angles (Fig. 4) correlates closely with the increase in RMS values. Higher surface roughness combined with reduced hydroxyl density facilitates the penetration of oil droplets into the surface texture. The weakened hydration layer becomes less effective at resisting interfacial wetting, and nanoscale topographical features formed at higher TEOS contents promote partial oil infiltration and pinning, leading to a transition toward the Wenzel-like wetting state. Consequently, oil droplets become more strongly pinned on TEOS-rich surfaces (as in the AA₈–TEOS_0.8 sample) under water.

Fig. 5 Light transmittance of AA–TEOS hybrid films.

AFM and SEM analyses clearly demonstrate that surface morphology plays a decisive role in establishing the energy barrier governing underwater oil wettability. However, when the data in Tables 1 and 2 are considered together, it becomes evident that the increase in RMS roughness occurs simultaneously with an increase in water contact angle in air and a decrease in underwater oil contact angle. This indicates that not only the surface roughness but also the surface chemistry is changing. In the literature, for hydrophilic coatings with constant surface chemistry, an increase in roughness is expected to decrease the water contact angle in air and increase the underwater oil contact angle.⁵ Indeed, previous studies have reported that, on hydrophilic surfaces, higher RMS values allow deeper penetration of water into the surface texture, leading to a fully wetted state and the formation of a more stable underwater Cassie state for oil droplets.^5,8,47 In such cases, the trapped water layer becomes more stable, increasing the energy barrier required for oil to contact the surface, thereby raising the underwater oil contact angle and reducing oil adhesion forces. In contrast, in the present study, increasing the TEOS content consumes a portion of the –OH groups originating from PAA due to sol–gel condensation reactions between AA and TEOS, thereby reducing the hydroxyl density on the surface. As a result, despite the increase in RMS roughness, the surface becomes less hydrophilic in air (leading to higher water contact angles), while the weakened hydration layer results in lower underwater oil contact angles. Therefore, the underwater oleophobic performance of the hybrid films is governed not only by the morphological Cassie–Wenzel energy barrier but also by variations in hydroxyl group density—and consequently surface free energy—arising from changes in TEOS content.

Table 2 SEM and AFM images of the AA–TEOS composite polymer

Code	500×	5000×	10 000×	50 000×	AFM images
AA8–TEOS0.2
AA8–TEOS0.4
AA8–TEOS0.6
AA8–TEOS0.8
p(TEOS)

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This phenomenon signifies a transition from the underwater Cassie state to the Wenzel state, suggesting that the surface enters an intermediate transitional wetting regime. On the p(TEOS) surface, complete pinning is observed underwater, representing a fully developed underwater Wenzel state (Video S1). In contrast, the AA₈–TEOS_0.2 surface maintains a stable underwater Cassie state, as illustrated in Video S1. Such observations highlight the intrinsic complexity of underwater wetting, where the coexistence of water, oil, and trapped air leads to a multiphase interface that cannot be fully described by classical wetting models.⁸ The underwater Cassie state, stabilized by water-filled micro/nanostructures, plays a key role in achieving low oil adhesion and high underwater oil repellency.^7,8 This behavior is further reflected in the oil adhesion characteristics (Video S2). On TEOS-rich surfaces, a hexadecane droplet deposited underwater adheres strongly and remains pinned due to increased oil–surface interactions. In contrast, on the AA₈–TEOS_0.2 surface, the oil droplet easily detaches without leaving any residue, propelled by buoyant forces. Importantly, repeated underwater experiments demonstrated that the AA₈–TEOS_0.2 coating preserves this low-adhesion Cassie state and maintains its oil-repellent behavior throughout extended immersion periods, indicating that the hybrid network exhibits good mechanical and interfacial stability under prolonged underwater conditions.

The combined transparency, strong underwater oil repellency, and mechanically integrated hybrid network of the AA–TEOS coatings highlight their suitability for practical underwater applications. Their high optical transmittance enables use in underwater sensing and optical devices where minimal light scattering is essential. Meanwhile, the excellent underwater oil repellency—particularly at low TEOS ratios—supports applications in marine antifouling and oil–water separation systems, in which stable hydration layers help prevent oil adhesion. These features together suggest that the AA–TEOS hybrid films offer a promising platform for multifunctional underwater coatings.

4. Conclusion

This study evaluated the wettability performance of acrylic acid–TEOS hybrid copolymers synthesized via a one-pot, two-step simultaneous polymerization technique, both in air and under water. During the process, acrylic acid undergoes radical polymerization while condensation reactions occur between the hydroxyl groups of acrylic acid and the ethoxy groups of TEOS. The results revealed that both the TEOS content and the timing of its addition significantly influence the underwater oil-repellent behaviors of the coatings.

PAA homopolymer films (AA₂–AA₈) are superhydrophilic in air and exhibit very high underwater hexadecane contact angles but suffer from poor stability in aqueous environments. Incorporation of TEOS into the network improves the integrity of the hybrid films while preserving high underwater oil repellency at low to moderate TEOS loadings. Formulations containing 0.015–0.020 mol of TEOS (AA₈–TEOS_0.15 and AA₈–TEOS_0.20) provide the highest underwater hexadecane contact angles (170°) together with very low water contact angles in air (10°), indicating a favorable balance between hydrophilicity and underwater superoleophobicity. Further increases in TEOS content lead to higher water contact angles in air and a progressive decrease in underwater oil contact angles, consistent with partial loss of the hydrated Cassie state.

Surface characterization showed that all hybrid coatings possess root mean square (RMS) roughness values below 100 nm, which is critical for maintaining optical transparency, while SEM and AFM images confirm a continuous, well-integrated hybrid network. The combined transparency, underwater oil repellency and integrated organic–inorganic structure highlight the potential of these AA–TEOS coatings for practical underwater applications such as marine antifouling surfaces, underwater sensing platforms, microfluidic devices and oil–water separation systems.

Author contributions

Conceptualization: U. Cengiz, methodology: E. Eroglu, U. Cengiz, investigation: E. Eroglu, S. N. Belen, C. Cengiz, data curation: E. Eroglu, validation: S. N. Belen, C. Cengiz, visualization: C. Cengiz, writing – original draft: C. Cengiz, writing – review & editing: U. U. Cengiz, supervision: U. U. Cengiz.

Conflicts of interest

There is no conflict of interest between the authors.

Data availability

The data that support the findings of this study are available from the corresponding authors from reasonable requests.

Supplementary information is available. See DOI: https://doi.org/10.1039/d5nj04270d.

Acknowledgements

This work was supported by Canakkale Onsekiz Mart University, The Scientific Research Coordination Unit, Project number: FYL-2021-3754. The authors would like to thank Central Laboratory of Çanakkale Onsekiz Mart University for providing SEM, and AFM. The authors also acknowledge the assistance of an AI-based language tool for improving the English clarity and readability of the manuscript.

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