Anatase and rutile nanoparticles in photopolymer 3D-printed nanocomposites: Band gap-controlled electron interactions in free-radical and cationic photocuring

IF 4.5 3区工程技术 Q1 CHEMISTRY, APPLIED Reactive & Functional Polymers Pub Date : 2024-05-01 DOI:10.1016/j.reactfunctpolym.2024.105923

Martina Korčušková , Juraj Svatík , Wiktoria Tomal , Aneta Šikyňová , Vishakha Vishakha , Filip Petko , Mariusz Galek , Paweł Stalmach , Joanna Ortyl , Petr Lepcio

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Abstract

The preparation of functional photopolymer nanocomposites is affected by both the physical and chemical interactions of nanoparticles (NPs) and polymer resin. Some NPs, such as semiconducting metal oxides, may contribute by their photocatalytic behavior and electron transfer, influencing the kinetics of the photopolymerization reaction. This study has investigated the complex effect of titanium dioxide (TiO₂) NPs in anatase and rutile form on the conversion, kinetics, and printability of free-radical and cationic photopolymerization resin. Two different polymorphs of TiO₂ NPs ensured identical chemical properties, but different physical effects related to their varying band gap energies and electron transfer efficiency. These parameters were found to be crucial for influencing the photopolymerization kinetics. While rutile showed a more pronounced enhancement of the free-radical photopolymerization's conversion and kinetics, cationic photopolymerization was favourably affected only by anatase NPs due to the photosensitization effect. These findings are critical in understanding and designing functional nanocomposite materials processed by vat photopolymerization 3D printing that could find use in optical, medical, or environmental applications.

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光聚合物三维打印纳米复合材料中的金红石型和金红石型纳米颗粒：自由基和阳离子光固化过程中的带隙控制电子相互作用

功能性光聚合物纳米复合材料的制备受到纳米粒子（NPs）和聚合物树脂的物理和化学相互作用的影响。一些 NPs（如半导体金属氧化物）可能通过其光催化行为和电子传递作用影响光聚合反应的动力学。本研究探讨了锐钛型和金红石型二氧化钛（TiO2）纳米粒子对自由基和阳离子光聚合树脂的转化、动力学和可印刷性的复杂影响。两种不同多晶型的二氧化钛（TiO2）氮氧化物确保了相同的化学特性，但与它们不同的带隙能和电子转移效率有关的物理效应却各不相同。研究发现，这些参数对影响光聚合动力学至关重要。金红石能更明显地提高自由基光聚合的转化率和动力学，而阳离子光聚合则由于光敏化效应只受到锐钛矿氮氧化物的有利影响。这些发现对于理解和设计通过大桶光聚合三维打印技术加工的功能性纳米复合材料至关重要，这些材料可用于光学、医疗或环境领域。

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来源期刊

Reactive & Functional Polymers 工程技术-高分子科学

CiteScore

8.90

自引率

5.90%

发文量

259

审稿时长

27 days

期刊介绍： Reactive & Functional Polymers provides a forum to disseminate original ideas, concepts and developments in the science and technology of polymers with functional groups, which impart specific chemical reactivity or physical, chemical, structural, biological, and pharmacological functionality. The scope covers organic polymers, acting for instance as reagents, catalysts, templates, ion-exchangers, selective sorbents, chelating or antimicrobial agents, drug carriers, sensors, membranes, and hydrogels. This also includes reactive cross-linkable prepolymers and high-performance thermosetting polymers, natural or degradable polymers, conducting polymers, and porous polymers. Original research articles must contain thorough molecular and material characterization data on synthesis of the above polymers in combination with their applications. Applications include but are not limited to catalysis, water or effluent treatment, separations and recovery, electronics and information storage, energy conversion, encapsulation, or adhesion.