SiO<sub>2</sub>-NH<sub>2</sub>-GA-AAS/CS席夫碱复合涂层的制备和吸湿性能

刘玲莉; 韩云龙; 钱付平; 陆彪

doi:10.13801/j.cnki.fhclxb.20220909.003

SiO₂-NH₂-GA-AAS/CS席夫碱复合涂层的制备和吸湿性能

doi: 10.13801/j.cnki.fhclxb.20220909.003

安徽工业大学　建筑工程学院，马鞍山 243032

详细信息

通讯作者:
韩云龙，博士，副教授，硕士生导师，研究方向为空调系统节能与自控技术　E-mail: hanlongy@163.com

中图分类号: TB332
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出版历程
- 收稿日期: 2022-07-01
- 修回日期: 2022-09-01
- 录用日期: 2022-09-02
- 网络出版日期: 2022-09-13
- 刊出日期: 2023-06-15

Preparation and hygroscopic properties of SiO₂-NH₂-GA-AAS/CS Schiff base composite coating

School of Architectural and Civil Engineering, Anhui University of Technology, Ma'anshan 243032, China

摘要

摘要: 为得到轻便的高吸湿材料，制备席夫碱(Schiff)复合涂层对基体材料亲水改性以提高吸湿性能。利用戊二醛(GA)作为中间体共价连接氨基化纳米二氧化硅(SiO₂)和亲水物质2-[(2-氨基乙基)氨基]乙磺酸钠(AAS)制得席夫碱复合材料(SiO₂-NH₂-GA-AAS)，将其分散在壳聚糖(CS)溶液中制得SiO₂-NH₂-GA-AAS / CS复合涂层。以高分子材料聚对苯二甲酸乙二酯醇(PET)作为基材，采用浸渍的方法将复合涂层涂覆在其表面进行改性。采用FTIR、场发射扫描电子显微镜配备能谱仪(FESEM-EDS)和接触角测量仪对涂覆复合涂层后的PET基材的微观形貌、元素分布及表面润湿性进行表征分析，并对吸附过程进行伪一级、伪二级动力学模型拟合。结果表明：当SiO₂-NH₂/AAS质量比为1∶2，SiO₂-NH₂-GA-AAS用量为10wt%时，改性后的PET基材吸湿性能最佳。FESEM-EDS显示改性后的PET基材表面较均匀地附着复合涂层且含有Schiff复合材料的特征元素，同时接触角从原始的135°变为0°，达到了超亲水效果。在25℃、97%相对湿度(RH)环境下，最优复合涂层改性后的PET基材在经过45 h吸湿后达到平衡，吸湿率高达36.94%，吸湿性能得到了极大的提高，整个吸附过程符合伪二级动力学模型。
- 席夫碱 /
- 亲水 /
- 吸湿 /
- 复合涂层 /
- 吸附动力学
Abstract: To get lightweight, highly hygroscopic materials, Schiff base composite coating was prepared to hydrophilically modify the matrix material to improve the hygroscopic performance. Glutaraldehyde (GA) as an intermediate was used to covalently link aminated nano-silica (SiO₂) and the hydrophilic substance 2-[(2-aminoethyl)amino] ethanesulfonate sodium (AAS) to prepare Schiff base composite material (SiO₂-NH₂-GA-AAS), and then the SiO₂-NH₂-GA-AAS / CS composite coating was prepared by dispersing it in chitosan (CS) solution. The polymer polyethylene terephthalate alcohol (PET) was used as the base material, and the composite coating was coated on its surface by dipping to modify it. FTIR, field emission scanning electron microscope equipped with energy dispersive spectrometer (FESEM-EDS) and contact angle measuring instrument were used to test the microscopic morphology, element distribution and surface wettability of the PET substrate coated with composite coating. The adsorption process was fitted with Pseudo-first-order and Pseudo-second-order kinetic models. The results show the modified PET substrate has the best hygroscopic performance when mass ratio of SiO₂-NH₂/AAS is 1∶2 and the amount of SiO₂-NH₂-GA-AAS is 10wt%. From the FESEM-EDS analysis, it can be seen that the surface of the modified PET substrate is coated with a uniform composite material, and the contact angle changes from the original 135° to 0°, achieving the super-hydrophilic effect. In the environment of 25℃, 97% relative humidity (RH), the PET substrate coated with the optimum composite coating reaches moisture saturation after 45 h of moisture absorption which reaches 36.94% moisture content. The moisture absorption performance has been extremely improved. The whole adsorption process conforms to the Pseudo-second-order kinetic model.
- Schiff base /
- hydrophilic /
- moisture absorption /
- composite coating /
- adsorption kinetics

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图 1 SiO₂-NH₂-GA-AAS/壳聚糖(CS)复合涂层制备过程示意图

Figure 1. Schematic diagram of preparation process of SiO₂-NH₂-GA-AAS/chitosan (CS) composite coating

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图 2 SiO₂-NH₂-GA-AAS复合材料的合成机制图

Figure 2. Synthesis mechanism diagram of SiO₂-NH₂-GA-AAS composite material

APTES—Silane coupling agent 3-aminopropyl triethoxy silane

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图 3 SiO₂-NH₂-GA-AAS的FTIR图谱

Figure 3. FTIR spertca of SiO₂-NH₂-GA-AAS

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图 4 改性后PET基材表面主要元素的EDS图谱

Figure 4. EDS spectra of the main elements on the modified PET substrate surface

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图 5 不同SiO₂-NH₂/AAS质量比对改性后PET基材吸湿性能的影响

Figure 5. Impact of different mass ratio of SiO₂-NH₂/AAS on hygroscopic properties of modified PET substrate

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图 6 不同SiO₂-NH₂-GA-AAS含量对改性后PET基材吸湿性能的影响

Figure 6. Impact of different content of SiO₂-NH₂-GA-AAS on hygroscopic properties of modified PET substrate

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图 7 SiO₂-NH₂-GA-AAS添加量为1wt% (a)、4wt% (b)、7wt% (c)、10wt% (d) 和13wt% (e) 时SiO₂-NH₂-GA-AAS/CS涂层表面状态

Figure 7. Surface state of the SiO₂-NH₂-GA-AAS/CS coating when the content of SiO₂-NH₂-GA-AAS is 1wt% (a), 4wt% (b), 7wt% (c), 10wt% (d) and 13wt% (e)

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图 8 未经处理的聚对苯二甲酸乙二酯醇(PET)、PET-CS、最优SiO₂-NH₂-GA-AAS/CS复合涂层改性后的PET基材吸湿性能随时间的变化

Figure 8. Hygroscopicity of untreated polyethylene terephthalate (PET), PET-CS and PET-SiO₂-NH₂-GA-AAS/CS changes with time

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图 9 25℃、97%相对湿度(RH)下吸附过程的伪一级动力学拟合 (a) 和伪二级动力学拟合 (b)

Figure 9. Pseudo-first-order kinetic fitting (a) and Pseudo-second-order kinetic fitting (b) of adsorption process at 25℃ and 97% relative humidity (RH)

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图 10 未经处理的PET (a)、涂覆1wt% (b)、4wt% (c)、7wt% (d)、10wt% (e) 和13wt% (f) SiO₂-NH₂-GA-AAS/CS复合涂层PET基材表面SEM图像

Figure 10. SEM images of untreated PET (a), PET substrate surface coated with 1wt% (b), 4wt% (c), 7wt% (d), 10wt% (e) and 13wt% (f) SiO₂-NH₂-GA-AAS/CS composite coating

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图 11 未经处理的PET表面水接触角图 (a)、水滴滴在SiO₂-NH₂-GA-AAS/CS涂层表面0 s时 (b) 和1 s时 (c) 的水接触角图

Figure 11. Contact angle of the untreated PET surface (a) and of the water droplet at 0 s (b) and 1 s (c) on the SiO₂-NH₂-GA-AAS/CS coating surface

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图 12 改性后PET基材在不同磨损循环下的质量变化率和接触角变化图

Figure 12. Mass change rate and contact angle change diagram of modified PET substrate under different abrasion cycles

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图 13 改性PET基材在不同pH下的质量变化率和接触角变化图

Figure 13. Mass change rate and contact angle change diagram of modified PET substrate under different pH

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表 1 不同SiO₂-NH₂/2-[(2-氨基乙基)氨基]乙磺酸钠(AAS)质量比下的SiO₂-NH₂-戊二醛(GA)-AAS复合材料配方

Table 1. SiO₂-NH₂-glutaraldehyde (GA)-2-[(2-aminoethyl)amino] ethanesulfonate sodium (AAS) composite material formulations under different mass ratio of SiO₂-NH₂/AAS

Sample number	Mass ratio of SiO₂-NH₂/AAS	SiO₂-NH₂/g	AAS/g	GA/g
SiO₂-NH₂-GA-AAS_0.125	4∶1	0.5	0.125	0.0657
SiO₂-NH₂-GA-AAS_0.25	2∶1	0.5	0.25	0.1315
SiO₂-NH₂-GA-AAS_0.5	1∶1	0.5	0.5	0.2631
SiO₂-NH₂-GA-AAS_1.0	1∶2	0.5	1	0.5263
SiO₂-NH₂-GA-AAS_2.0	1∶4	0.5	2	1.0527

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表 2 改性后PET基材表面元素含量

Table 2. Surface element content of modified PET

Element	C	O	Si	S	Na
Mass fraction/wt%	46.11	45.52	7.04	1.17	0.16

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