不同化学性质的橡胶在超临界二氧化碳中的膨胀

S. T. Mikhaylova, S. V. Reznichenko, E. A. Krasnikov, P. Tsygankov, N. Menshutina, I. D. Simonov-Emel’yanov
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摘要

研究目的研究橡胶工业中使用的主要橡胶类型在超临界二氧化碳(SC-CO2)中的溶胀情况,以评估在此基础上利用流体技术获得具有多孔结构的弹性材料的可能性。橡胶在 SC-CO2 中的溶胀和随后的发泡过程是根据专门开发的技术,利用原始装置进行的。这是一个带有透明窗口的高压设备,可以使用光学技术,通过数码摄像机直接测量样品在溶胀和发泡过程中的几何尺寸。使用扫描电子显微镜对发泡橡胶的多孔结构进行了研究。研究建立了异戊二烯、丁二烯、丁二烯苯乙烯、乙烯丙烯、氯丁二烯、丙烯酸乙烯酯、硅氧烷和有机氟橡胶在 SC-CO2 中的溶胀动力学实验曲线。研究了温度和压力对溶胀速率和平衡度的影响。还测定了 SC-CO2 在不同化学性质的橡胶中的扩散系数。研究表明,橡胶在 SC-CO2 中的平衡溶胀度取决于橡胶的化学性质。它与橡胶的溶解度参数值无关,与扩散系数成正比变化,并随着温度和压力的升高而增加。研究发现,无论在 SC-CO2 中的溶胀程度如何,所研究的所有橡胶都会在压力急剧下降时密集发泡。形成的气孔大小为几十微米:明显小于使用化学气孔形成剂时形成的气孔大小。
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Swelling of rubbers of different chemical natures in supercritical carbon dioxide
Objectives. To investigate the swelling of the main types of rubbers used in the rubber industry in carbon dioxide in a supercritical state (SC-CO2), in order to assess the possibility of obtaining elastomeric materials with porous structures using fluid technology, based on them.Methods. The process of swelling of rubbers in SC-CO2 and subsequent foaming was carried out according to a specially developed technique using the original installation. This is a high-pressure apparatus with transparent windows, allowing for the use of an optical technique to directly measure the geometric dimensions of samples during swelling and foaming using a digital video camera. The study of the porous structure of foamed rubbers was carried out using scanning electron microscopy.Results. The study established experimental curves of the swelling kinetics in SC-CO2 of isoprene, butadiene, styrene butadiene, ethylene propylene, chloroprene, ethylene acrylate, siloxane, and organofluorine rubbers. The influence of temperature and pressure on the rate and equilibrium degree of swelling was studied. The diffusion coefficients of SC-CO2 in rubbers of various chemical natures were also determined.Conclusions. It was shown that the equilibrium swelling degree of rubbers in SC-CO2 depends on the chemical nature of rubbers. It does not correlate with the value of their solubility parameters, changes directly proportional to the diffusion coefficient and increases with increasing temperature and pressure. It was found that irrespective of the degree of swelling in SC-CO2, all the rubbers studied are intensively foamed at a sharp pressure drop. The size of the pores formed is tens of microns: significantly smaller than the size of pores formed when chemical pore formers are used.
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