Jung Jae Kap, Lee Chang Hoon, Son Min Seok, Lee Ji Hun, Baek Un Bong, Chung Ki Soo, Choi Myung Chan, Bae Jong Woo
Hydrogen Energy Materials Research Center, Korea Research Institute of Standards and Science, Daejeon 34113, Korea.
Department of Biochemical and Polymer Engineering, Chosun University, Gwangju 61452, Korea.
Polymers (Basel). 2022 Feb 11;14(4):700. doi: 10.3390/polym14040700.
Filler effects on H diffusion in nitrile butadiene rubbers (NBRs) blended with carbon black and silica fillers of different concentrations are first investigated by employing a volumetric analysis. Total uptake, solubility, and diffusivity of hydrogen for ten filled-NBR, including neat NBR, are determined in an exposed pressure range of 1.3 MPa~92.6 MPa. Filler dependence on hydrogen uptake and diffusion is distinctly observed in the NBRs blended with high abrasion furnace (HAF) carbon black (CB) fillers compared to NBRs blended with medium thermal furnace (MT) CB and silica filler, which is related to the specific surface area of carbon black and interface structure. The HAF CB filled-NBR follows dual sorption behavior combined with Henry's law and the Langmuir model, responsible for two contributions of solubility from polymer and filler. However, a single gas sorption behavior coming from the polymer is observed satisfying Henry's law up to 92.6 MPa for NBR blended with MT CB filled-NBR and silica filled-NBR. Diffusion demonstrates Knudsen and bulk diffusion behavior below and above, respectively, at certain pressures. With increasing pressure, the filler effect on diffusion is reduced, and diffusivity converges to a value. The correlation observed between diffusivity and filler content (or crosslink density) is discussed.
首先通过体积分析研究了不同浓度的炭黑和二氧化硅填料填充的丁腈橡胶(NBR)中填料对氢扩散的影响。在1.3MPa至92.6MPa的暴露压力范围内,测定了十种填充NBR(包括纯NBR)的氢总吸收量、溶解度和扩散率。与中热炉(MT)炭黑(CB)和二氧化硅填料填充的NBR相比,在高耐磨炉(HAF)炭黑(CB)填料填充的NBR中,明显观察到填料对氢吸收和扩散的依赖性,这与炭黑的比表面积和界面结构有关。HAF CB填充的NBR遵循结合亨利定律和朗缪尔模型的双重吸附行为,这是聚合物和填料对溶解度的两种贡献。然而,对于MT CB填充的NBR和二氧化硅填充的NBR混合的NBR,在高达92.6MPa的压力下,观察到聚合物产生的单一气体吸附行为符合亨利定律。在一定压力下,扩散分别在低于和高于该压力时表现出克努森扩散和体扩散行为。随着压力的增加,填料对扩散的影响减小,扩散率收敛到一个值。讨论了扩散率与填料含量(或交联密度)之间的相关性。