Ceramization mechanism of ZrB2 - boron phenolic resin modified silicone rubber thermal protection system materials and the influence of oxygen in service environment

IF 7.4 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability Pub Date : 2025-09-10 DOI:10.1016/j.polymdegradstab.2025.111664

Hang Yan , Xiao Hou , Jiming Cheng , Le Wang , Cheng Bian , Xiping Feng

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引用次数: 0

Abstract

The ceramization reaction of silicone rubber thermal protection system (TPS) materials, along with the resultant ceramic phase structure, is critical for enabling these materials to endure high-temperature environments and withstand erosion from high-velocity flows. Under service conditions, in addition to intrinsic physical and chemical transformations, the reactions between the materials and environmental constituents significantly influence the ceramization process. To investigate the influence of oxygen on ZrB₂ - boron phenolic resin modified silicone rubber TPS materials, thermal analysis experiments were conducted under varying oxygen concentrations (0 %, 5 %, 10 %, and 21 %) across a temperature range from room temperature to 1800 K. These experiments utilized a thermal analyzer, fourier-transform infrared spectrometer, X-ray diffractometer, and other instruments. The results indicate that the influence of oxygen in the service environment on the ceramization reaction can be attributed to two primary aspects. Firstly, oxygen affects the oxidation behavior of the silicone rubber matrix. In a nitrogen atmosphere, cyclic siloxanes formed during pyrolysis undergo structural reconstruction at temperatures above 1300 K. In an air atmosphere, these cyclic siloxanes are oxidized to form new C = O organic groups before undergoing pyrolysis and subsequent structural reconstruction at elevated temperatures. Secondly, in an air atmosphere, zirconium boride and boron phenolic resin fillers undergo oxidation to produce boron oxide. This boron oxide reacts with silica to form borosilicate B-O-Si structures. Additionally, the molten boron oxide acts as a pore-filling agent within the ceramic phase structure, leading to the formation denser ceramic phase structure than the network structure in a nitrogen atmosphere.

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ZrB2 -硼酚醛树脂改性硅橡胶热防护体系材料的陶化机理及使用环境中氧的影响

硅橡胶热防护系统（TPS）材料的陶化反应，以及由此产生的陶瓷相结构，对于使这些材料能够承受高温环境和高速流动的侵蚀至关重要。在使用条件下，除了固有的物理和化学转化外，材料与环境成分之间的反应也显著影响陶瓷化过程。为了研究氧对ZrB2 -硼酚醛树脂改性硅橡胶TPS材料的影响，在室温至1800 K的温度范围内，进行了不同氧浓度（0%、5%、10%和21%）下的热分析实验。实验使用了热分析仪、红外光谱仪、x射线衍射仪等仪器。结果表明，使用环境中氧气对陶化反应的影响主要有两个方面。首先，氧气影响硅橡胶基体的氧化行为。在氮气气氛中，热解形成的环硅氧烷在1300 K以上的温度下进行结构重构。在空气环境中，这些环硅氧烷被氧化形成新的C = O有机基团，然后在高温下进行热解和随后的结构重建。其次，在空气气氛中，硼化锆和硼酚醛树脂填料氧化生成氧化硼。这种硼氧化物与二氧化硅反应形成硼硅酸盐B-O-Si结构。此外，熔融的氧化硼在陶瓷相结构中充当孔隙填充剂，导致形成比氮气氛中更致密的陶瓷相结构。

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来源期刊

Polymer Degradation and Stability 化学-高分子科学

CiteScore

10.10

自引率

10.20%

发文量

325

审稿时长

23 days

期刊介绍： Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology. Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal. However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.