Facile fabrication of ultraviolet-protective silk fabrics via atomic layer deposition of TiO 2 with subsequent polyvinylsilsesquioxane modification

Abstract

To develop ultraviolet (UV) light-protective silk fabrics (SFs), a conformal nanoscale TiO₂ coating was deposited using an atomic layer deposition (ALD) method, and polyvinylsilsesquioxanes (PVSs) were further coated onto the SFs to enhance their hydrophobicity and UV light-resistance. Scanning electron microscopy and atomic force microscopy revealed hierarchical microstructures and nanostructures of the TiO₂ coatings, which were primarily responsible for the increase of the water contact angle from approximately 0 to 120° after the ALD process. A high mean square surface roughness of 76.325 nm also accounted for this improved water contact angle. Furthermore, TiO₂-coated SFs modified with low surface energy PVSs exhibited enhanced hydrophobic properties. More importantly, both the UV-blocking and yellowing-resistance of the SFs were improved without any significant change to the luster of the SFs. The ease and simplicity of this fabrication method makes it applicable to the preparation of multifunctional textiles with both good water repellency and UV-resistance.

Keywords

atomic layer deposition silk fabrics polyvinylsilsesquioxanes UV-protective

Silk is a natural protein filament fiber produced by the silkworm (Bombyx mori). It has been applied in the textile industry for thousands of years due to its softness, skin-affinity, flexibility and mechanical strength.^1–2 However, its shortcomings, such as microbe adherence, flammability, wrinkling and, in particular, ultraviolet (UV)-induced aging and yellowing of silk fibers, are still to be overcome to make it more popular.^3–10

Nanostructured metal oxides can be used to impart desired properties to silk fibers,^9–11 and approaches involving precipitation, thermal decomposition, in situ hydrothermal deposition, microemulsion and sol–gel techniques have been adopted to attach nanomaterials onto the surfaces of SFs. Zhang et al.¹¹ reported the improvement of the anti-UV properties of SFs by treating the surfaces of SFs with nano-TiO₂ via a sol-hydrothermal method. TiO₂/La (III) composite nanoparticles were also coated onto the surfaces of SFs to enhance their anti-yellowing and UV-blocking properties by Wang et al.¹² Directly dip-coating silica nanoparticles onto the surface of silk fibers was proved to be effective in enhancing their water repellency.¹³ However, the inherent uncontrollability and uneven distribution of the nanoparticles via these traditional methods severely limits their further application.^14–15 One method that helps to overcome these restrictions is atomic layer deposition (ALD). ALD is a low-temperature vapor deposition method, bearing excellent three-dimensional conformity and thickness controllability due to the self-limiting reaction, making it suitable for surface modification, especially for elastic fiber materials.^16–17

Previous work confirmed that the hydrophobicity of SFs was improved by coating TiO₂ films onto their surfaces via ALD.¹⁸ Notably, UVB-activated TiO₂ on the surface of SFs accelerates the aging and yellowing of SFs by promoting protein decomposition. To further enhance the multifunctional feathers, including the hydrophobicity, anti-UV properties and anti-yellowing characteristics of SFs, a low-surface energy polyvinylsilsesquioxane (PVS) layer was further dip-coated onto TiO₂-coated SFs by solution impregnation to weaken the activity of TiO₂. An ALD process was employed to fabricate the TiO₂ layer, instead of any other inorganic coating methods, because of its excellent three-dimensional conformality, precise and controllable film thickness, and uniformity over a large area.^19–24 Furthermore, the chemical bonding between the ALD TiO₂ coating and the SFs effectively extends the life of the functional coating. A sub-nanoscale film growth rate also greatly increases the surface area of TiO₂ and fully utilizes the physicochemical properties of TiO₂.^25–27 By adopting this approach, the surface topography and functional characteristics of SFs can be precisely controlled. In turn, the surface curvature, surface roughness and surface energy can be tailored. Meanwhile, laundering durability could be guaranteed by the chemical bond reaction between SFs and the TiO₂ coating, and affluent hydroxyl groups (-OH) provide the possibility of further surface modification by PVS. Furthermore, the PVS introduced as a surface modification layer can maintain the UV-blocking property of TiO₂, and improve both the anti-yellowing and hydrophobicity properties of SF.

Experimental methods

Material

Plain-weave SFs (63.3 g/m²), purchased from a local textile store, were used as a control sample. Prior to ALD, the SFs were degummed as follows: known weights of SFs were first immersed in 0.05 M Na₂CO₃ aqueous solution at a weight ratio of 1:100 and then boiled at 98℃ for 30 min. The treated SFs were rinsed with warm (∼40℃) deionized water. The above-mentioned procedure was repeated at least three times and the thoroughly degummed SFs were then dried at 45℃ for 12 h. Finally, the SFs thus prepared were stored in a closed bag until further study. Titanium (IV) isopropoxide (TIP) (99.999% metals basis) was purchased from Aladdin Industrial Co., Ltd. The silicon wafers (diameter of 150 ± 0.4 mm, resistivity of 0.01–1 Ω cm and thickness of 650 ± 20 µm) were purchased from Hefei/Kejing Materials Technology Co., Ltd. Vinyltrimethoxysilane (97.9%) was obtained from Silicone New Material Co., Ltd of Wuhan University. CaCO₃, Na₂CO₃, anhydrous ethanol, hydrochloric acid (37 wt%) and toluene of analytical reagent grade were purchased from Sinopharm Chemical Reagent Co., Ltd. Deionized water was generated by a Milli-Q Plus 185 water purification system (Millipore, Bedford, MA) with a resistivity of 18.2 MΩ·cm at 25℃. All chemicals were used as received without further purification.

Synthesis of the PVS

PVSs was synthesized according to a modified method as reported by our previous work.^28–30 Briefly, 10 mL of anhydrous ethanol, 250 mL of toluene and 151.35 g vinyltrimethoxysilane were added into a 1 L round-bottomed flask and magnetically stirred for 10 min in an ice bath. Then, a mixed solution with 47.48 g deionized water and 10.35 g of concentrated hydrochloric acid was added dropwise into the round-bottomed flask. Sequentially, the mixed solution was stirred at room temperature for 10 min and condensed at 85℃ for 3 hours, then was cooled to room temperature. Next, 3 mL saturated Na₂CO₃ solution and 25 mL deionized water were successively used to clean the upper layer liquid. Finally, the collected upper solution was dehydrated by adding 10.35 g anhydrous CaCO₃ under magnetic stirring for 30 min. After filtration, the filtrate was distilled at room temperature until a final colorless oil-like PVS was obtained. The prepared PVS has the following characteristics: Mn = 5655 g/mol and M_w/M_n = 1.38 (measured by gel permeation chromatography), ¹H NMR (CDCl₃): δ 5.96–6.07 (m, H₂C = CH–Si), δ 3.48 (s, Si-OCH₃) and δ 2.36 (s, Si-OH); ¹³C NMR (CDCl₃, ppm): δ = 50.6 (SiOCH₃), δ = 129.23 (CH = CH₂) and δ = 137.18 (CH=CH₂); and ²⁹Si NMR (CDCl₃, ppm): δ = −70.22 (H₂C = CHSiO(OCH₃)), δ = −77.84 (H₂C = CHSiO(OH)) and δ = −79.26 (H₂C = CHSiO_1.5). The prepared PVS was used in subsequent experiments without further purification.

Preparation of TiO₂-deposited SFs via ALD

TiO₂-coated SFs were prepared based on our previous reports.^3,16,31–33 Briefly, a self-made ALD reaction chamber containing degummed SF was vacuumed to ∼ 0.5 Torr at 150℃. Titanium (IV) isopropoxide and deionized water, used as precursors, were alternately pumped into the reaction chamber. A typical ALD cycle was run as follows. Firstly, TIP was purged into the reaction chamber and chemisorbed onto the surface of SFs. After the adsorption saturated, nitrogen (99.99%) was purged to remove residual reagent and resultant. Subsequently, water was purged into the reaction chamber and then reacted with TIP on the surface of SF. Finally, nitrogen was used as the purging gas again. The acting times for each step of the four-step cycle (TIP/N₂/H₂O/N₂) were 0.2, 35, 0.05, and 35 s, respectively. The detailed ALD reaction mechanism is listed below:

\begin{matrix} Ti (OCH ({CH}_{3})_{2})_{4} + Silk (- {OH}^{*})_{n} \to Silk (- O -)_{n} Ti \\ - (OCH ({CH}_{3})_{2} *)_{4 - n} + n ({CH}_{3})_{2} CHOH \end{matrix}

(1)

\begin{matrix} Silk (- O -)_{n} Ti - (OCH ({CH}_{3})_{2} *)_{4 - n} \\ + (4 - n) H_{2} O \to Silk (- O -)_{n} Ti - ({OH}^{*})_{4 - n} \\ + (4 - n) ({CH}_{3})_{2} CHOH \end{matrix}

(2)

where * is the surface species and n = 1–3.

The film deposition rate is 0.079 nm/cycle (Fig. S1). The corresponding X-ray diffraction pattern (Fig. S2) indicated that the TiO₂ film adopted an amorphous structure. Four-hundred ALD cycles were selected for all TiO₂ deposition considering the combination properties and laundering durability. Corresponding SFs were denoted as SF-TiO₂-400.

Preparation of PVS-modified TiO₂-coated SFs

PVS-modified TiO₂-coated SFs are fabricated as follows. Firstly, 10 wt% PVS polymer solution was prepared by dissolving 5 g PVS in 45 g anhydrous ethanol. A final 50 g as-prepared PVS solution was charged into a 250 mL beaker, then was magnetically stirred at room temperature for 2 h to get a clear finishing solution. Afterwards, TiO₂-coated SFs (2 × 5 cm) were immersed in the as-prepared PVS solution under magnetic stirring for 5 h. Finally, the soaked SFs were dried at 105℃ for 3 h to obtain PVS-modified TiO₂-coated SFs. This sample was denoted as SF-TiO₂-400-PVS. Two steps, as explained in this and the previous section, are depicted in Figure 1. Note that the surface colors of the coated sample are similar to that of SFs, thus retaining the original white color.

Figure 1.

Schematic of the preparation of polyvinylsilsesquioxane-modified TiO₂-deposited silk fabrics.

Total weight gains of the SFs after the ALD process and dip-coating were calculated using the following equation:

Total weight gains % = \frac{W_{treated} - W_{original}}{W_{original}} \times 100 %

where W_treated is the mass of the as-prepared sample and W_original is the mass of the control SF. In order to ensure the accuracy of the total weight gain, all the samples were dried at 60℃ for 3 h before and after treatment. All weighing measurements were conducted six times according to the above process and the corresponding weight gains of each sample are listed in Table S1.

Characterization

Surface morphologies of the SF, SF-TiO₂-400 and SF-TiO₂-400-PVS were characterized by scanning electron microscopy (SEM) (JSM-6510LV, JEOL Co. Ltd, Japan) at an operating voltage of 20 kV. All samples were silver sputtered for 120 s before testing. The element compositions of the surfaces of samples were obtained by an energy-dispersive X-ray microanalysis system (EDX, Oxford INCA350) coupled to the SEM. Atomic force microscopy (AFM) (Multimode–Nanoscope IIIa, Digital Instruments, USA) was used to reveal the surface topology of the SF, SF-TiO₂-400 and SF-TiO₂-400-PVS. The surface roughness of the samples were compared based on the arithmetic average roughness (Ra). The X-ray spectra of the SF, SF-TiO₂-400 and SF-TiO₂-400-PVS were recorded on a X-ray photoelectron spectroscope (XPS, SPM-9700, SHIMADZU Co. Ltd), using Al-Kα (1486.6 eV) as the radiation source, under ultrahigh vacuum (UHV) (2 × 10⁻⁹ mbar). All samples were analyzed by Fourier transformation infrared spectroscopy (FTIR, Nicolet NEXUS 670, USA) in the wavenumber range of 500–4500 cm⁻¹. Static water contact angles of the SF, SF-TiO₂-400 and SF-TiO₂-400-PVS were measured by a Dataphysics OCA 30 (Germany) at room temperature (25℃). All contact angles were calculated from the images taken at 60 s after 5 µL of water drop was applied to the surface of samples. These contact angles were averaged from at least five different positions for the same fabric. UV protection properties of the SF, SF-TiO₂-400 and SF-TiO₂-400-PVS were assessed by the UV protection factor (UPF) from a Cary 5000 UV/visible light spectrophotometer (Varian, Australia), according to the European Standard EN 13758-2:2003 and GB/T 18830-2009 test method, which is defined as the ratio of the UV radiation transmittance under the wavelength range of 280–400 nm. The UPFs for all samples are averaged from at least 20 tests. UPF was calculated by the following equation:

UPF = \frac{\sum_{λ = 280}^{400} E (λ) \times ɛ (λ) \times Δ λ}{\sum_{λ = 280}^{400} E (λ) \times T (λ) \times ɛ (λ) \times Δ λ}

where E(λ) is the solar spectral irradiance (Wm^–2 nm^–1), ɛ(λ) is the relative erythema spectral effectiveness, T(λ) is the spectral transmittance at wavelength λ (%) and Δλ is the wavelength interval (nm). Optical photographs of SF, SF-TiO₂-400 and SF-TiO₂-400-PVS after exposure to UV irradiation for different times were taken by a digital camera (Nikon DSLR D5100) under ordinary white light. The light source used to differentiate the appearances of SFs after exposure to UV was a 125 W Hg lamp with a 365 nm wavelength (40 mW/cm²). The distance from the sample surfaces to the center of the light source was 10 cm.

Results and discussion

The surface morphologies and EDX spectra of the SF, SF-TiO₂-400 and SF-TiO₂-400-PVS are plotted in Figure 2. The textures can be seen for SF, SF-TiO₂-400 and SF-TiO₂-400-PVS at low magnification, as shown in Figure 2(a₁), (b₁) and (c₁). SEM images at higher magnifications (Figure 2(a₂), (b₂) and (c₂)) show some compact cracks and particle clusters for SF-TiO₂-400, which may be attributed to the aggregation between adjacent TiO₂ nanoparticles, caused by their inherent high surface energy.³ The aggregation of TiO₂ nanoparticles could increase surface roughness and contribute, in part, to the increased water contact angle (WCA). The SF-TiO₂-400 in the study shows a hydrophobic behavior, although the SF-TiO₂-400-PVS exhibits a much smoother surface, as can be seen in Figure 2(c₂). This may be associated with the chemical structures of the outermost TiO₂ deposited via ALD. Notably, the smooth surface of the SF-TiO₂-400-PVS may be ascribed to the viscoelasticity of the PVS polymer. These morphologies from the SEM images were in agreement with the subsequent characterization by AFM. Carbon, nitrogen and oxygen were discovered on the surface of the SF (Figure 2(a₃)), which is in agreement with the inherent chemical structure of the SF. After 400 cycles of ALD using TiO₂, the titanium element in the EDX spectra of the SF-TiO₂-400 implied the existence of a TiO₂ coating. The presence of the Si element in the EDX spectra of SF-TiO₂-400-PVS further confirmed the successful coating of PVS onto the surface of the SF-TiO₂-400. The Ag element in Figure 2(a₃), (b₃) and (c₃) could be introduced during the sputter coating before the SEM measurements.

Figure 2.

Morphology and energy-dispersive X-ray spectra of the silk fabric, SF-TiO₂-400 and SF-TiO₂-400-PVS samples. (a₁) and (a₂) show scanning electron microscopy images of the silk fabric at different magnifications; (b₁) and (b₂) show scanning electron microscopy images of the SF-TiO₂-400 at different magnifications; and (c₁) and (c₂) scanning electron microscopy images of the SF-TiO₂-400-PVS at different magnifications. (a₃), (b₃) and (c₃) show energy-dispersive X-ray spectra of samples corresponding to images (a₁) and (a₂), (b₁) and (b₂), and (c₁) and (c₂), respectively.

Figure 3 shows the AFM topographies and static WCAs of SF, SF-TiO₂-400 and SF-TiO₂-400-PVS. The SF revealed a relatively smooth surface with an arithmetic R_a of 16.745 nm. The SF-TiO₂-400 showed a sharply increased R_a of 76.325 nm, which was mainly attributed to the aggregation of TiO₂ particles. Further treatment by the PVS will reduce the R_a to 11.086 nm, as in Figure 3(c), which could be attributed to the viscoelasticity of PVS. SF is easy to wet by water, because of its abundant hydrophilic surface functional group, together with a capillary effect. However, after TiO₂ deposition, the WCAs of SF-TiO₂-400 increased to 116° (Figure 3(b)). This may be associated with the chemical structure of the outermost TiO₂ coating using a TIP precursor in the ALD process.¹⁸ As reported, the hydrophobicity of the surface mainly depended on both the surface energy and nanoscale surface roughness. The higher the roughness of a hydrophilic surface, the higher the water wettability of a material in the case of a surface with a fixed high surface energy. However, for a hydrophobic surface (low surface energy), high roughness generally results in a more water-repellent surface. After modification by PVS, the static WCA was further increased to 140°. This seems to contradict previous descriptions. It is reasonable to assume that the low-surface energy PVS may have affected the surface-wetting ability of the fabrics.²²

Figure 3.

Atomic force microscopy and static water droplet images on the surface of the silk fabrics. (a) silk fabric, (b) SF-TiO₂-400 and (c) SF- TiO₂-400-PVS.

Figure 4 shows the FTIR images of PVS, SF, SF-TiO₂-400 and SF-TiO₂-400-PVS. At first glance, almost no difference can be identified in the FTIR spectra of SF and SF-TiO₂-400 (before and after TiO₂ deposition). For the SF, the absorption peaks at 3298, 3076, 2934 and 1060 cm⁻¹ correspond to the stretching vibrations of N–H and O–H, –C=CH₂, –C–CH and –C–O, respectively. Four characteristic vibration peaks at 1650 (amide I), 1530 (amide II), 1260 (amide III) and 625 cm⁻¹ (amide V) indicate the coexistence of the silk I and silk II structures. However, no significant difference was observed between the SF and SF-TiO₂-400. This may be due to the limit of detection of FTIR (generally, only components higher than 1 wt% could be detected) considering the relatively small amount of deposited TiO₂. The theoretical thickness of the TiO₂ coating layer is less than 40 nm, whereas the total penetration depth of FTIR is ∼ 2 µm. That is to say, most of the contribution to the FTIR spectra of SF-TiO₂-400 is from the silk fiber. For the SF-TiO₂-400-PVS, the bands located at 1113 and 1052 cm⁻¹ are identified as asymmetric and symmetric stretching vibrations of the Si-O-Si of PVS, respectively. A sharp absorption peak at 760 cm⁻¹ is typically attributed to the stretching vibration of Si-C.³⁴

Figure 4.

Fourier transformation infrared spectroscopy spectra of the silk fabric, SF-TiO₂-400 and SF-TiO₂-400-PVS samples.

The surface chemical compositions of the SF, SF-TiO₂-400, and SF-TiO₂-400-PVS can directly determine the surface energy and, thus, affect their surface properties. Therefore, the elements and chemical bonds on the surface of the SF, SF-TiO₂-400 and SF-TiO₂-400-PVS samples were analyzed, and the corresponding survey XPS spectra are displayed in Figure 5(a). Only C 1 s, N 1 s and O 1 s were observed in the spectrum of SF. After ALD coating of TiO₂ on the surfaces of the SF, a sharp peak emerged at 460 eV, and identification of Ti 2 p signals indicated the successful deposition of TiO₂ onto the surface of SF. The corresponding atomic ratios of 2/1 for O/Ti further confirmed that this deposition was TiO₂. Two peaks at 101.74 and 152.08 eV in the spectrum of SF-TiO₂-400-PVS indicated Si 2 p and Si 2 s, respectively. Meanwhile, the disappearance of N 1 s and Ti 2 p signals after PVS modification confirmed that the silk fabric surface was fully covered by the PVS polymers.

Figure 5.

X-ray photoelectron spectroscope spectra (a) and high-resolution spectra of C 1 s (b), O 1 s (c), N 1 s (d), Ti 2 p (e) and Si 2 p (f) for silk fabric (SF), SF-TiO₂-400 and SF-TiO₂-400-PVS.

High-resolution detailed XPS spectra of C 1 s, O 1 s, N 1 s, Ti 2 p and Si 2 p are shown in Figure 5 (b)–(d). The C 1 s (Figure 5(b)) revealed three peaks at 284.5, 286.2 and 287.5 eV, which could be associated with three kinds of C atom in different chemical circumstances (–C–C–, C–OH and C=O), respectively.³⁵ The lack of C atoms with the forms of –C–C–, –C–OH, and peaks after TiO₂ deposition may be caused by some change in the chemical structure. Meanwhile, the disappearance of N 1 s and the strengthening of O 1 s peaks after TiO₂ deposition also confirmed that the SFs were coated by the TiO₂. Ti 2 p peaks of SF-TiO₂-400 at 459 and 464.7 eV were assigned to Ti 2p_3/2 and 2p_1/2, respectively.³⁶ A 5.7 eV splitting energy between the Ti 2p_3/2 and 2p_1/2 was in agreement with the characteristic signal of Ti⁴⁺.³⁷ The disappeared Ti 2 p peak, and enhanced C 1 s and O 1 s signals of SF-TiO₂-400-PVS, indicated that the surface was covered by PVS.

To investigate the anti-UV ability of the treated SFs, the UV transmittance curves of SF, SF-TiO₂-400 and SF-TiO₂-400-PVS are illustrated in Figure 6. Corresponding calculated UPF data are listed in Table 1. The results show that SF-TiO₂-400 possesses a somewhat higher UPF value (49.9 ± 0.7) than that of SF (8.7 ± 0.5). Further modification by the PVS could increase the UPF of SF-TiO₂-400 by 21.8%.

Figure 6.

Ultraviolet transmission spectra of silk fabric, SF-TiO₂-400 and SF-TiO₂-400-PVS.

Table 1.

Ultraviolet protection properties of silk fabric, SF-TiO₂-400 and SF-TiO₂-400-PVS

Sample	UPF value	UVA (%)	UVB (%)	UPF protection class
SF	8.7 ± 0.5	22.31 ± 0.9	5.76 ± 0.36	–
SF-TiO₂-400	49.9 ± 0.7	6.72 ± 0.84	1.05 ± 0.15	Excellent protection
SF-TiO₂-400-PVS	60.80 ± 0.6	4.23 ± 0.27	1.09 ± 0.12	Excellent protection

PVS: polyvinylsilsesquioxanes; SF: silk fabric; UPF: ultraviolet protection factor; UV: ultraviolet.

Yellowing resulting from age, especially under UV light, hinders the application of SFs. To demonstrate the anti-yellowing properties of the prepared samples, photographs of SF, SF-TiO₂-400 and SF-TiO₂-400-PVS, taken after they were exposed to UV for different periods, are compared in Figure 7, and the corresponding quantitative K/S values are recorded in Table S2. As shown in Figure 7, the surface of SF started to yellow after it was exposed to UV light for 30 min. As UV exposure time increased, the SF became progressively more yellow until it lost its integrity and basic wearability value. A longer time (90 min) was needed to turn the SF-TiO₂-400 yellow, revealing a much better anti-yellowing ability. This improvement may be because of the strong absorption and high refraction of TiO₂ to UV. SF-TiO₂-400-PVS exhibited the best anti-yellowing performance, requiring the longest time (150 min) to turn the fabric yellow. The improved anti-yellowing ability of SF-TiO₂-400-PVS could be attributed to the synergistic effect of TiO₂ and PVS. These results were confirmed by the K/S value (Table S2). In all, the findings indicated that UV protection was strongly improved by the ease and simplicity of this fabrication method.

Figure 7.

Optical photographs of the silk fabric, SF-TiO₂-400 and SF-TiO₂-400-PVS samples taken at different times after exposure to ultraviolet irradiation.

Conclusions

A simple two-step surface modification method, ALD of TiO₂ and subsequent PVS dip-coating, was reported. The results show that conformally nanoscale TiO₂ coating was successfully deposited onto the surface of SF. Further modification by low-surface energy PVS greatly improved the water repellency, UV-blocking and anti-yellowing properties of SFs. After surface modification, the SF could maintain its natural luster, even after exposure to UV light for 150 min. In summary, this two-step modification process provides a simple and effective strategy for the large-scale functionalization of textile materials. This process could find application in the development and utilization of new fiber materials and smart wearable devices.

Supplemental Material

Supplemental material for Facile fabrication of ultraviolet-protective silk fabrics via atomic layer deposition of TiO₂ with subsequent polyvinylsilsesquioxane modification

Supplemental Material for Facile fabrication of ultraviolet-protective silk fabrics via atomic layer deposition of TiO₂ with subsequent polyvinylsilsesquioxane modification by Huiyu Yang, Yaling Wang, Keshuai Liu, Xin Liu, Fengxiang Chen and Weilin Xu in Textile Research Journal

Footnotes

Declaration of conflicting interests

The authors declared no potential conflicts of interest with respect to the research, authorship and/or publication of this article.

Funding

The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This research was supporteded by the National Science Fund for Distinguished Young Scholars (Grant No. 51325306), the National Natural Science Foundation of China (Grant No. 51203124, 51773158) and China Postdoctoral Science Foundation (Grant No. 2018M640042). The authors are grateful to associate professor Dongzhi Chen for the synthesis and supply of PVS polymer. Huiyu Yang and Yaling Wang contributed equally to this work.

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Supplementary Material

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Facile fabrication of ultraviolet-protective silk fabrics via atomic layer deposition of TiO 2 with subsequent polyvinylsilsesquioxane modification

Abstract

Keywords

Experimental methods

Material

Synthesis of the PVS

Preparation of TiO2-deposited SFs via ALD

Preparation of PVS-modified TiO2-coated SFs

Characterization

Results and discussion

Conclusions

Supplemental Material

Supplemental material for Facile fabrication of ultraviolet-protective silk fabrics via atomic layer deposition of TiO2 with subsequent polyvinylsilsesquioxane modification

Footnotes

Declaration of conflicting interests

Funding

References

Supplementary Material

Preparation of TiO₂-deposited SFs via ALD

Preparation of PVS-modified TiO₂-coated SFs

Supplemental material for Facile fabrication of ultraviolet-protective silk fabrics via atomic layer deposition of TiO₂ with subsequent polyvinylsilsesquioxane modification