PDA/DTMS-纳米TiO2对蚕丝织物自修复超疏水整理

为了赋予蚕丝织物自清洁与防污性能,首先利用多巴胺(DA)在CuSO₄/H₂O₂氧化体系下快速聚合形成聚多巴胺(PDA)沉积在蚕丝织物表面,再通过十二烷基三甲氧基硅烷(DTMS)改性的纳米TiO₂对沉积PDA的织物进行超疏水功能整理。通过FTIR、SEM、XPS、接触角测量仪对改性前后蚕丝织物的化学组成、表面微观结构、疏水性能进行表征,测试了改性蚕丝织物的自清洁与防污性、疏水自修复性和抗紫外线性能。结果表明,PDA/DTMS-纳米TiO₂改性蚕丝织物表面具有分布均匀的微纳结构,且与原蚕丝织物相比,织物表面自由能下降;其水接触角为156°、滚动角为5°,防紫外线系数(UPF)为75.81,具有良好的防污自清洁能力和抗紫外线性能,与原蚕丝织物相比透气性略有下降;经O₂等离子体10次的刻蚀-修复循环或1200次机械磨损-修复循环后,蚕丝织物的疏水修复率均>96%,耐环境损伤的自修复效果明显。此外,洗涤25次后,PDA/DTMS-纳米TiO₂     

辊式涂布法构建纸基牢固超疏水表面

采用辊式涂布的方法在纸基材料上构建超疏水表面，并对超疏水表面的牢固性、自清洁性和疏水性能进行评价。用γ-氨丙基三乙氧基硅烷和1H,1H,2H,2H-全氟辛基三乙氧基硅烷（POTS）对微米级和纳米级两种尺寸的TiO₂粒子进行疏水改性处理，然后将改性后的微/纳米TiO₂涂布在纸基材料表面。采用红外光谱（FTIR）对改性后的微/纳米TiO₂的化学组成进行了分析，采用扫描电镜（SEM）对涂布纸表面结构进行了表征，通过接触角、耐磨性和自洁净测试评价了涂层表面的超疏水性、牢固性和自清洁性。改性TiO₂的FTIR分析显示在1000～1500cm^-1之间出现多个C—F键的伸缩振动峰，表明POTS通过化学键与TiO₂表面发生了结合。涂布纸表面的SEM分析可以看出，纸基材料表面上均匀分布了微米和纳米尺寸的TiO₂颗粒，具备了类似荷叶表面微-纳结构的粗糙表面。涂层表面的水接触角为153°±1.5°，滚动角为3.5°±0.5°，水滴在涂层表面呈球形，极易滑落，涂层在水中浸泡7天后，接触角没有发生明显变化，表明纸张表面具备了优异的超疏水性能，且疏水稳定性较好。涂层表面经过10次循环磨损试验后，接触角仍能达到150°，滚动角为9°，表明机械摩擦没有对涂布纸表面的化学成分和粗糙结构造成明显的破坏，超疏水表面的牢固性较好。自洁净测试表明，涂布纸表面具有良好的自清洁和防污性能。该工艺过程操作简单，易于实现工业化生产，为在纸基表面构建综合性能优异的超疏水表面提供了一种新的便利途径。     

水性环氧树脂/纳米SiO2复合疏水涂层的制备及性能研究

用氨基硅油（ APDMS）改性水性环氧树脂（ EP）得到疏水性的环氧树脂乳液（ APDMS-EP）;用 1H,1H,2H,2H-全氟辛基三乙氧基硅烷（ FAS）与纳米 SiO₂反应得到氟改性纳米 SiO₂（F-SiO₂）。采用不同比例的 F-SiO₂与 APDMS-EP进行复配,室温固化制备疏水涂层,并对 F-SiO₂的结构进行了表征,研究了 F-SiO₂用量对涂层的接触角、铅笔硬度、附着力、热稳定性及耐腐蚀性能的影响。结果表明： APDMS的引入使水性环氧树脂涂层的水接触角从 47.3°提高到 97.7°;加入 F-SiO₂后涂层疏水性进一步提高,当加入 15%的 F-SiO₂时,涂层对水和丙三醇的接触角分别为 120.3°和 104.5°,F-SiO₂的加入也增强了涂层的防腐性能。     

PFSA-PES-纳米颗粒复合纳米纤维的制备及催化性能

利用静电纺丝法制备了全氟磺酸(PFSA)-聚醚砜(PES)-纳米颗粒(SiO₂、TiO₂和Al₂O₃)复合纳米纤维,比较了SiO₂、TiO₂和Al₂O₃等不同纳米颗粒对磺酸基团在纤维表面分布的影响,并利用乙酸乙酯合成反应考察了纤维结构对表面磺酸基团活性的关系。结果表明:静电纺复合纳米纤维的比表面积可达85.6 m²·g^-1,纳米颗粒均匀分布在纤维表面,表面酸性中心占PFSA酸性基团总量最高达71.2%。酯化反应实验表明,复合纳米纤维具有很好的催化性能,纳米颗粒的存在可以提高酸中心的活性;同时,所得复合纳米纤维膜表现出很好的回收与可再生性能,有望作为一种对环境友好的固体酸催化剂。     

SiO2包覆TiO2复合纳米粒子的制备及防晒性能研究

通过溶胶-凝胶法在金红石型纳米二氧化钛（TiO₂）表面包覆二氧化硅（SiO₂）薄膜,对纳米TiO₂进行表面改性。通过优化聚乙烯吡咯烷酮（PVP）用量、硅钛比、氨水的用量确定最佳制备条件为:TiO₂用量为0.3 g,PVP用量为0.4 g,硅钛比为2∶1,氨水用量为5 m L,获得了粒径小,SiO₂包覆层薄,单分散性好的SiO₂-TiO₂复合纳米粒子。应用FT-IR,XRD,SEM,TEM和UV-vis等对改性前后的粒子进行表征。结果表明:红外光谱图中出现Si-O-Ti键的振动吸收峰,改性前后的纳米TiO₂均为金红石型,SEM及TEM显示改性后的粒子团聚现象减弱,其表面形成了约10 nm的SiO₂薄膜。经过表面改性,SiO₂成功包覆在纳米TiO₂表面,复合纳米粒子的光催化活性得到有效抑制,纳米TiO₂作为防晒剂的安全性大大提高。...     

硅烷改性环氧树脂自修复微胶囊的制备及应用

采用硅烷偶联剂γ-（2,3-环氧丙氧基）丙基三甲氧基硅烷（KH-560）对环氧树脂E-51进行改性,并以此为芯材,三聚氰胺-脲醛树脂（MUF）为壁材,原位聚合法合成微胶囊,探讨了微胶囊制备工艺,并用光学显微镜（OM）、扫描电子显微镜（SEM）、红外光谱仪（FTIR）、热重分析仪（TGA）等对其表面形貌、化学结构及热性能等进行了表征和测试;之后将改性后的微胶囊应用到自修复环氧树脂涂层中,考察了自修复涂层的力学性能和电化学性能。结果表明,当芯壁比为1.5：1、乳化剂质量分数为1.4%时,微胶囊为规则球形,表面粗糙、致密,大小均匀,平均粒径约为100μm,具有良好的热稳定性。当涂层中改性微胶囊质量分数为3%时,涂层的拉伸强度、弯曲强度、黏结强度及冲击强度均较高,且其较未改性微胶囊自修复涂层分别提高了14.9%、14.3%、16.0%和9.6%;与未改性微胶囊自修复涂层相比,改性微胶囊自修复涂层的电化学性能增强,且电化学阻抗值显著提高。     

以硅氧烷溶胶为介质制备纳米TiO2光致超亲水涂层

简单、经济、规模化制备二氧化钛（TiO₂）光致超亲水表面备受重视。本研究利用硅氧烷溶胶为介质,将TiO₂纳米颗粒浸涂到玻璃表面。考查了颗粒在表面的分散状况和TiO₂含量对涂层光致超亲水性能、透明性以及涂层牢固度和表面硬度的影响。结果发现:浸涂并经紫外辐照1h或120℃烘干3h后,TiO₂纳米颗粒能均匀、牢固地负载到玻璃表面;10min UV辐照后,表面变得超亲水;涂层附着力达0级,表面硬度达到5H。硅氧烷溶胶对玻璃表面的良好浸润性和对含羟基纳米颗粒的良好"粘结"性能是纳米颗粒在玻璃表面能均匀、牢固负载的主要原因。研究结果为大规模、低成本制备透明自清洁表面提供了理论和实验基础。     

有机改性金红石型纳米TiO2对聚乙醇酸抗光老化性能的研究

用硅烷偶联剂（A-172）对金红石型纳米TiO₂进行有机表面改性,采用红外光谱（FTIR）、透射电镜（TEM）对改性结果进行了表征。红外光谱表明,A-172以化学键的方式结合在纳米TiO₂表面;透射电镜照片表明,改性后的纳米TiO₂表现出较强疏水性。将改性后的纳米TiO₂作为紫外线屏蔽剂添加到聚乙醇酸（PGA）中,分别制备了TiO₂质量分数为0.5%、1%、1.5%和2%的复合材料,并采用氙灯气候试验机对纯PGA和PGA/纳米TiO₂复合材料进行加速老化对比试验。实验结果表明,改性后的纳米TiO₂在PGA材料中具有良好的分散性,使PGA具有更宽的紫外吸收范围和更强的紫外吸收峰,其中,当添加质量分数为1.5%时改性效果最佳,经过800h加速老化后,复合材料黄色指数只增加4.1,拉伸强度和缺口冲击强度保持率为56.34%和65.15%,分别比纯PGA提高了42.29%和37.21%,重均分子量和数均分子量保持率也分别提高了33.64%和33.99%。     

APTES-TiO2-B4C/PVDF膜的制备及其光降解有机染料的性能研究

采用3-氨丙基三乙氧基硅烷（APTES）对纳米碳化硼（B₄C）和二氧化钛（TiO₂）的混合颗粒进行改性,制备出功能化APTES-B₄C/TiO₂复合颗粒。利用相转化技术将APTES-B₄C-TiO₂复合颗粒引入聚偏氟乙烯（PVDF）膜基质中,得到具有光催化性能的APTES-B₄C-TiO₂/PVDF复合膜。通过XRD、SEM、EDS和水接触角测试对制备的复合膜进行表征。以50 mg/L的罗丹明B（RhB）水溶液模拟废水考察APTES-B₄C-TiO₂/PVDF复合膜的光催化性能。结果表明,当复合粒子的质量分数为0.5%时,复合膜具有最高的孔隙率（68.3%）、最大的膜比表面积（8.25 m²/g）和最低的水接触角（69°）。光催化实验结果表明,APTES-B₄C-TiO₂复合粒子的质量分数为0.5%时,A...     

TiO2对重整预加氢催化剂性能的影响

采用纳米TiO₂对氧化铝进行改性,并以改性氧化铝为载体制备系列催化剂,通过N₂物理吸附、XRD、H₂-TPR和NH₃-TPD等方法研究TiO₂对催化剂的孔结构、物相和酸性的影响,并考察TiO₂对重整预加氢反应性能的影响。结果表明,添加TiO₂降低催化剂的比表面积和孔容,促进氧化钼的还原,增强催化剂的中强酸,催化剂性能得到较大改善,在入口温度低10 ℃的条件下,催化剂仍具有较好的脱硫和脱氮性能。     

Multifunctional,robust, and self-healable polyurethane coatings cross-linked by Diels–Alder reaction of calix[4] arenes containing furan groups

Self-healing coatings can restore their performance after inevitable damage and are promising in the industry owing to their longer service life and lower repair cost. The use of Diels–Alder reaction bonds is well-known to generate thermally self-healing coatings. In this study, a series of cross-linked self-healing polyurethane (PU) coatings were synthesized through Diels–Alder reactions of p-tert-butyl calix[4]arene bearing furan groups (C4A-FA) as a new chain extender and a bismaleimide (BMI) polyether amine as a Diels–Alder cross-linking agent. Adding C4A-FA to PUs improves their mechanical properties, thermal stability, and self-healing ability. Additionally, these modifications can result in the formation of composite networks with PU that exhibit thermoreversibility and self-healing properties. These changes have led to PUs containing modified calix[4]arene (C4A-FA) having better properties compared with unmodified calix[4]arene PUs. The properties of prepared coatings were evaluated by Fourier transform infrared spectroscopy, scanning electron microscope, differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), and tensile tests compared with a typical PU sample. The tensile and TGA results show an improvement in the thermal and mechanical properties of the polymers by increasing the C4A-FA content. By replacing 15% of butandiol (BDO) with C4A-FA in PU pure, the tensile strength increased from 1.69 to 5.14 MPa. Furthermore, adding diels–alder (DA) bonds enhanced the tensile strength to 10.49 MPa for PU-C4A15-DA. According to DSC results, a broad endothermic peak from nearly 80–140°C confirmed the retro-DA reactions in the synthesized thermoreversible samples. The healing efficiency of the PU-C4A15-DA sample was obtained at 92.5% (measured by tensile test), which is the highest value among cross-linked self-healing PUs reported in the literature.     

Synthesis and properties of self-healing cross-linked nonisocyanate polyurethanes from biobased diglycerol bis(cyclic carbonate)

A simple and green method was established to prepare self-healing cross-linked nonisocyanate polyurethanes (SH-cNIPUs) from biobased diglycerol bis(cyclic carbonate) (DGDC). Two nonisocyanate polyurethane prepolymers with furan terminal groups (tFU-NIPUs) were synthesized through a ring-opening reaction of DGDC with furan methylamine and trimethylolpropane tris(poly[propylene glycol], amine terminated) ether, or tris(2-aminoethyl) amine under mild conditions. The SH-cNIPUs were prepared via a Diels–Alder reaction between tFU-NIPUs and a bismaleimide. SH-cNIPUs were characterized by ATI-FTIR, ¹H NMR, differential scanning calorimetry, polarized optical microscope, and tensile strength after being damaged and healed. SH-cNIPUs with glass transition temperature from 8 to 49°C, tensile strength up to 21 MPa, and self-healing efficiency from 67 to 80% were successfully synthesized.     

A Structure-Properties Relationship Study of Self-Healing Materials Based on Styrene and Furfuryl Methacrylate Cross-Linked via Diels–Alder Chemistry

A series of copolymers of styrene and furfuryl methacrylate characterized by various molecular structures (linear and star, block and random) is synthesized via atom transfer radical polymerization, and cross-linked with a bismaleimide by means of thermally reversible Diels–Alder (DA) reaction, to obtain self-healing materials. The prepared materials are studied in terms of gelation, swelling, thermal, and dynamic-mechanical analysis, with the aim of correlating relevant properties to their chemical structure. It is found that the furan/styrene ratio, as well as the molecular architecture, have a major influence on the properties. It is also found that the reversibility of the DA reaction is not complete in the solid state for materials with high cross-linking density. This study provides some important tools for the design of materials characterized by thermally reversible behavior, which find usually application as self-healing thermosets, coatings, or adhesives.     

Facile Repair of Anti-Corrosion Polymeric Composite Coatings Based on Light Triggered Self-Healing

Photothermally induced self-healing coatings are widely reported, while their application scenarios are rarely taken with concern. In addition, there is a need to achieve the balance between good properties and self-healing behaviors for closing the gap between academic research and engineering applications. Here, self-healing composite coatings are designed based on silane-modified epoxy chains with reversible crosslinking points and multifunctional fillers of cerium oxide nanoparticles grown on graphene nanosheets, and their applications are demonstrated for restricted regions. Diglycidyl ether-terminated poly(dimethylsiloxane) is co-polymerized with diglycidylether of bisphenol A with the weight ratio of 1/99–10/90 to achieve surface-tension driven crack closure, while dangling furan groups contribute to reversible crosslinking points via Diels–Alder reaction. Cerium oxide nanoparticles and graphene nanosheets enhance anti-corrosion properties, and graphene nanosheets also act as photothermal fillers. The results show that pencil hardness, polarized resistance, and coating resistance are highly improved via the introduction of multifunctional fillers at 1 and 2 phr. Good thermally and photothermally induced self-healing is demonstrated. This work provides a new application thought for light triggered self-healing coatings that can be used for restricted regions including inner walls of pipelines and reactors.     

自洁型卷材涂料的研制

对聚酯树脂进行改性,并采用特殊的自洁助剂,研制成具有良好自洁功能的卷材涂料。     

改性SiO2/聚硅氧烷无氟超疏水涂层的制备及性能

为了提高基体材料的防污能力,在基体表面制备了一种无氟超疏水复合涂层。首先,使用十六烷基三甲氧基硅烷(HDTMS)对二氧化硅(SiO_2)微纳米颗粒进行疏水改性,其次,将改性后的SiO_2颗粒与有机硅烷混合,利用硅烷的水解、聚合在基体材料的表面得到一层稳定的无氟超疏水复合涂层。采用FTIR、TGA、SEM、AFM和接触角测量仪对涂层的化学组成、表面微观结构和疏水性能进行表征。结果表明:复合涂层表面具有微纳米尺度的粗糙结构,并具有优异的自清洁性和耐磨损性;未磨损前接触角达151°,磨损100周次后接触角进一步提高至161°。     

自修复超疏水多功能协同作用涂层研究进展

自修复超疏水涂层是近年来多功能涂层研究的热点之一。文中总结了超疏水自修复涂层的修复机理,包括表面形貌的恢复和低表面能物质的补充。表面形貌的恢复可采用动态化学键和气体补偿来实现;低表面能物质的补充依靠在外界条件刺激下表面能驱动底层的低表面能物质迁移至涂层表面。目前有利用形状记忆合金实现大尺度结构损伤自修复、减少对外界刺激依赖实现自主自修复进程、利用分子结构设计自修复、多层光滑浸渍多孔表面(SLIPS)设计自修复等新的研究方向。同时介绍了自修复超疏水性能结合其他功能的多功能协同作用涂层的应用,包括超疏水自修复多功能纤维、超疏水防腐蚀自修复涂层和超疏水导电自修复涂层,各个功能间不是简单的叠加而是协同作用使涂层整体性能达到最佳,这为多功能涂层的设计提供了新思路。最后展望了自修复超疏水涂层的发展方向。     

纳米碳酸钙复合丙烯酸涂料的流变性

制备了纳米CaCO3复合丙烯酸涂料，通过对其主要性能进行检测表明，当改性纳米CaCO3的添加量为1.5%（质量）时，涂料的耐光性、耐水性、自洁性和贮存稳定性等显著改善。研究了添加轻钙、未改性纳米CaCO3、改性纳米CaCO3及其用量对丙烯酸涂料流变性的影响，结果表明，该体系的流动特性均符合Casson模型；当在丙烯酸涂料中添加1.5%改性纳米CaCO3时，其黏度对温度的敏感性下降，黏度显著降低，剪切稀化能力较强，Casson屈服应力较小，触变性增大，涂料性能改善与其流变性变化基本一致。此外，固体分改变或添加丁醇对添加改性纳米CaCO3复合丙烯酸涂料和传统丙烯酸涂料流变性的影响规律基本相同。     

Robust polymer incorporated TiO2-ZrO2 microsphere coatings by electrospraying technique with excellent and durable self cleaning,antibacterial and photocatalytic functionalities

The applications of self-cleaning coatings on large scale are limited due to their poor durability, remnants of hazardous by-products and lack of biocompatibility. We propose to solve this problem by developing TiO₂-ZrO₂ composite-based self cleaning coatings. In order to achieve this task another important aspect was to select biocompatible polymers poly (methyl methacrylate) and pluronic F-127 (PF-127) as they can enhance the self-cleaning capability of TiO₂-ZrO₂ which itself is biocompatible and endowed with anti-bacterial capability. The selection of a preparation technique that could produce coatings mimicking the nature has also been important and hence Electrospraying technique was selected as the processing method. The samples were then characterized using various techniques like field emission scanning electron microscopy, X-ray diffraction, high resolution transmission electron microscopy, Brunauer–Emmett–Teller analysis, and so forth to fathom the interlink between observed properties and morphology. High quality superhydrophobic and superhydrophilic films have been generated and the surfaces were modulated by the addition of tri-block co-polymer which was found to provide swapping of superhydrophobic nature to superhydrophilic nature. The integration of superhydrophobic, superhydrophilic, photocatalytic and antibacterial properties in the prepared microsphere coatings is a unique achievement and may interest those in the quest for self-cleaning materials for antibacterial coatings in mitigating surgical site infections, medical implants, coronary stent surfaces, and so forth.