硅酸盐学报

基于硅氮陶瓷前驱体的硬韧涂层制备及性能

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王文悦 ¹ , 刘蕴钰 ¹^,² , 徐彩虹 ¹^,² , 张宗波 ¹

硅酸盐学报 | 聚合物先驱体陶瓷专题—研究论文 2024,52(9): 2806-2814

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硅酸盐学报 |聚合物先驱体陶瓷专题—研究论文 2024 , 52 (9) : 2806 -2814

基于硅氮陶瓷前驱体的硬韧涂层制备及性能

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王文悦¹, 刘蕴钰¹^,², 徐彩虹¹^,², 张宗波¹

作者信息

^1．中国科学院化学研究所，极端环境高分子材料实验室，北京 100190

^2．中国科学院大学，北京 100049

通讯作者:

张宗波（1984—），男，博士，研究员。

作者简介:

王文悦（1997—），男，硕士。

Preparation and Properties of Polysilazane Derived Hard Flexible Coatings

Wenyue WANG¹, Yunyu LIU¹^,², Caihong XU¹^,², Zongbo ZHANG¹

Affiliations

^1.Key Laboratory of Science and Technology on High-tech Polymer Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

^2.University of Chinese Academy of Sciences, Beijing 10004, China

Corresponding Author:

ZHANG Zongbo (1984-), male, Ph.D., Professor. E-mail: zongbo@iccas.ac.cn

WANG Wenyue (1997-), male, Master. E-mail: wwy2619@163.com

出版时间: 2024-09-20 doi: 10.14062/j.issn.0454-5648.20240171

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摘要

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在聚合物薄膜表面施加硬韧涂层是实现其在保持轻质、柔性性能的同时，提高表面硬度和耐磨性的最有效途径。采用硅氮陶瓷前驱体-有机聚硅氮烷OPZ181与（3-氨基丙基）三乙氧基硅烷（KH550）杂化的方式制备了一种有机-无机杂化硬韧涂层，并对涂层化学结构、力学性能、微观形貌、光学透明性、耐弯折性能以及耐磨性能进行了表征。结果表明：涂层化学结构以Si—O—Si为主，并含有—CH₃等有机基团，CH₃SiO₃为杂化涂层主要结构。涂层铅笔硬度可达6 H，纳米压痕硬度可达0.7 GPa，模量可达5.7 GPa。涂层的塑性指数（H/E）>0.1，弹性恢复值（W_e）>60%，具有良好的硬韧性能。涂层表面平整光滑，且具有优异的光学透明性。涂层在弯曲半径为1.5 mm和1 mm条件下，均可弯折10000次，表现出优异的耐弯折性能。涂层具有优异的耐磨性能，可以有效提高PET薄膜的耐磨性。本工作发展了一种杂化涂层设计新策略，为硬韧涂层的制备提供了一种新思路与方法。

关键词

陶瓷前驱体 / 聚硅氮烷 / 有机-无机杂化 / 硬韧涂层

Abstract

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Introduction

In recent years, with the rapid development of the flexible displays and wearable electronic devices, higher requirements have been placed on the performance of electronic devices, such as lightweight and flexible. Polymer films such as transparent polyimide (CPI) and polyethylene terephthalate (PET) have gained widespread attention in the field of flexible optoelectronic materials owing to their high transparency, light weight, good bendability and high mechanical strength. However, due to the characteristics of their molecular structure, polymer films generally have the problems of low surface hardness and poor abrasion resistance. Therefore, enhancing the surface hardness and abrasion resistance of polymer films without compromising their characteristics such as transparency, light weight and flexibility become an urgent problem to be solved. Among the various enhancement strategies that have been developed, applying optically transparent coatings with abrasion and bending resistance to the surface of polymer films is one of the most effective and promising approaches. Hard flexible coatings are mainly achieved by organic-inorganic hybridization to achieve both hardness and flexibility. Organic polysilazanes can retain their organic groups while forming the Si—O—Si network structure by hydrolysis condensation reaction, which can realize organic-inorganic hybridization and providing a basis for constructing hard flexible coatings. In this work, an organic-inorganic hybrid hard flexible coating was prepared at 80 ℃ 90%RH by hybridizing organic polysilazane OPZ181 with triethoxysilane (KH550). The effect of KH550 content on the conversion process of OPZ181 was investigated, and the structure and properties of the hard flexible coatings were systematically characterized.

Methods

Using n-butyl ether as solvent, OPZ181 and KH550 were mixed homogeneously at room temperature to obtain a colorless, transparent and clarified OPZ181/KH550 polymer precursor solution. OPZ181/KH550 hybrid coatingswere prepared by liquid-phase coating methods, including spin-coating, scraping and drenching. The chemical structure and compositions of the coatings were characterized by using FT-IR, ²⁹Si NMR and XPS. The micro-morphology of the surface and cross-section of the coatings was observed by SEM. The optical transmittance of the samples was tested using a UV-Vis-NIR spectrophotometer. The mechanical properties of the coatings were characterized using a pencil hardness tester and nano-indenter. The bending test was carried out using a homemade experimental setup. The abrasion resistance of the coatings was tested on the reciprocating abrasion meter using 0000^# type steel wool.

Results and discussion

The experimental results and analysis of FT-IR test show that when the ratio of OPZ181 to KH550 in the hybrid hard flexible coating is more than 2∶1, the coatings conversion efficiency to Si—O structure under hygrothermal conditions is increased, and the converted coating structure is dominated by Si—O bonds. The XPS results show that KH550 can effectively promote the conversion of OPZ181 to the Si—O structure at higher content, and —CH₃ can be retained in the coating after the conversion, which is consistent with the results of the FT-IR. Further deconvolution of Si 2p data shows that the coating is dominated by the CH₃SiO₃(T) structure with a high degree of crosslinking by the Si—O—Si structure. The ²⁹Si NMR results similarly show that OPZ181 transforms to the Si—O—Si network structure under hygrothermal conditions, and —CH₃ remains in the coating after the transformation. In addition, as the content of KH550 in OPZ181 increases, the degree of conversion and cross-linking of the Si—O—Si structure increases, and CH₃SiO₃ is the main structure of the hybrid coating. The pencil hardness as well as the nanoindentation hardness and modulus of the coatings increased with the increase of KH550 content, which is attributed to the fact that the coatings are dominated by the CH₃SiO₃ structure with a denser Si—O—Si network at the higher content of KH550. The coating has a pencil hardness up to 6 H, a nanoindentation hardness up to 0.7 GPa, and a modulus up to 5.7 GPa, indicating that the coating has good mechanical properties. Calculated from the load-displacement curves, the H/E of the coating is >0.1 and We >60%, indicating that the coating has good hard flexible properties. In the visible light range, the transmittance of the coated PET film is almost unchanged relative to that of the blank PET film, which can be kept above 90%, indicating that the coating has good optical transparency. From the SEM image, it can be observed that the surface and cross-section of the coating are flat and smooth, and there are no obvious defects such as holes and cracks produced during the transformation process. From the microscopic photographs and SEM surface morphology of the coatings after bending test 10,000 times with a bending radius (R) of 1.5 mm and 1 mm, respectively. The surface is kept flat and smooth, and there is no damage, which indicates that the coating is flexible and has excellent bending resistance. Blank PET film shows visible scratches on its surface after 20 abrasions cycles with 0000^# steel wool. In contrast, the surface of the coated PET film remained flat and smooth after 200 abrasion cycles without any scratches. This shows that the OPZ181/KH550 hybrid coatings have excellent abrasion resistance.

Conclusions

In this work, an organic-inorganic hybrid hard flexible coating was prepared at 80 ℃ 90% RH by hybridizing organic polysilazane OPZ181 with triethoxysilane (KH550). KH550 promotes the hydrolysis condensation reaction of OPZ181 under hygrothermal conditions and improves its degree of conversion. The hybrid hard flexible coatings are dominated by Si—O—Si network structure and contain organic groups such as—CH₃. The degree of cross-linking of the Si—O—Si network in the coatings increases with the increase of KH550 content, resulting in the mechanical properties of the coatings enhanced. The coating has a pencil hardness up to 6 H, nanoindentation hardness up to 0.7 GPa, and a modulus up to 5.7 GPa. The H/E of the coating is >0.1 and W_e>60%, indicating that the coating has good hard flexible properties. The surface of the coating is flat and smooth, and has excellent optical transparency. The coating has excellent bending resistance over 10 000 times under the bending radius of 1.5 mm and 1 mm. The coating can effectively improve the abrasion resistance of PET film. The above experimental results show that organic polysilazane is one of the potential materials for the preparation of organic-inorganic hybrid hard flexible coatings, which is expected to be applied to the protection of flexible devices such as flexible displays and wearable electronic devices.

Key words

ceramic precursor / polysilazane / organic-inorganic hybridization / hard flexible coating

引用本文

王文悦, 刘蕴钰, 徐彩虹, 张宗波. 基于硅氮陶瓷前驱体的硬韧涂层制备及性能. 硅酸盐学报, 2024 , 52 (9) : 2806 -2814 . DOI: 10.14062/j.issn.0454-5648.20240171

Wenyue WANG, Yunyu LIU, Caihong XU, Zongbo ZHANG. Preparation and Properties of Polysilazane Derived Hard Flexible Coatings[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (9) : 2806 -2814 . DOI: 10.14062/j.issn.0454-5648.20240171

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基础科研项目(JCKY2020203B019)

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2024年第52卷第9期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240171

接收时间：2024-03-01
首发时间：2026-10-22
出版时间：2024-09-20

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收稿日期：2024-03-01
修回日期：2024-04-04

基金

基础科研项目(JCKY2020203B019)

作者信息

^1．中国科学院化学研究所，极端环境高分子材料实验室，北京 100190

^2．中国科学院大学，北京 100049

通讯作者:

张宗波（1984—），男，博士，研究员。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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