Lupu Luchian Ana Maria, Mariş Marius, Zaharescu Traian, Marinescu Virgil Emanuel, Iovu Horia
Advanced Polymer Materials Group, University Politehnica of Bucharest, 011061 Bucharest, Romania.
Extreme Light Infrastructure-Nuclear Physics (ELI-NP), Horia Hulubei National Institute for Physics and Nuclear Engineering (IFIN-HH), 077125 Magurele, Romania.
Materials (Basel). 2022 Jul 21;15(14):5080. doi: 10.3390/ma15145080.
In this paper, the stability improvement of poly(lactic acid) (PLA)/styrene-isoprene block copolymer (SIS) loaded with silica nanoparticles is characterized. The protection efficiency in the material of thermal stability is mainly studied by means of high accurate isothermal and nonisothermal chemiluminescence procedures. The oxidation induction times obtained in the isothermal CL determinations increase from 45 min to 312 min as the polymer is free of silica or the filler loading is about 10%, respectively. The nonisothermal measurements reveal the values of onset oxidation temperatures with about 15% when the concentration of SiO particles is enhanced from none to 10%. The curing assay and Charlesby-Pinner representation as well as the modifications that occurred in the FTIR carbonyl band at 1745 cm are appropriate proofs for the delay of oxidation in hybrid samples. The improved efficiency of silica during the accelerated degradation of PLA/SIS 30/n-SiO composites is demonstrated by means of the increased values of activation energy in correlation with the augmentation of silica loading. While the pristine material is modified by the addition of 10% silica nanoparticles, the activation energy grows from 55 kJ mol to 74 kJ mol for nonirradiated samples and from 47 kJ mol to 76 kJ mol for γ-processed material at 25 kGy. The stabilizer features are associated with silica nanoparticles due to the protection of fragments generated by the scission of hydrocarbon structure of SIS, the minor component, whose degradation fragments are early converted into hydroperoxides rather than influencing depolymerization in the PLA phase. The reduction of the transmission values concerning the growing reinforcement is evidence of the capacity of SiO to minimize the changes in polymers subjected to high energy sterilization. The silica loading of 10 wt% may be considered a proper solution for attaining an extended lifespan under the accelerated degradation caused by the intense transfer of energy, such as radiation processing on the polymer hybrid.
本文对负载二氧化硅纳米粒子的聚乳酸(PLA)/苯乙烯-异戊二烯嵌段共聚物(SIS)的稳定性提高进行了表征。主要通过高精度等温及非等温化学发光程序研究了该材料热稳定性的保护效率。在等温化学发光测定中,当聚合物不含二氧化硅或填料负载量约为10%时,氧化诱导时间分别从45分钟增加到312分钟。非等温测量表明,当SiO颗粒浓度从无增加到10%时,起始氧化温度值增加约15%。固化分析、查尔斯比-平纳表征以及1745 cm处FTIR羰基带发生的变化是杂化样品中氧化延迟的适当证据。通过与二氧化硅负载量增加相关的活化能值增加,证明了二氧化硅在PLA/SIS 30/n-SiO复合材料加速降解过程中的提高效率。当原始材料添加10%的二氧化硅纳米粒子时,未辐照样品的活化能从55 kJ/mol增加到74 kJ/mol,25 kGy下γ辐照处理的材料从47 kJ/mol增加到76 kJ/mol。稳定剂特性与二氧化硅纳米粒子有关,这是由于保护了次要成分SIS烃结构断裂产生的片段,其降解片段早期转化为氢过氧化物,而不是影响PLA相的解聚。关于增强增强的透射率值降低证明了SiO有能力使经受高能灭菌的聚合物的变化最小化。10 wt%的二氧化硅负载量可被视为在由强烈能量转移(如对聚合物杂化体进行辐射处理)引起的加速降解下获得延长寿命的合适解决方案。