U.S. Army Combat Capabilities Development Command Chemical Biological Center, FCDD-CBR-PF, Aberdeen Proving Ground, Maryland 21010-5424, United States.
ACS Appl Mater Interfaces. 2020 Mar 4;12(9):11094-11103. doi: 10.1021/acsami.0c00615. Epub 2020 Feb 20.
Traditional protective garments loaded with activated carbons to remove toxic gases are very bulky. Novel graphene oxide (GO) flake-based composite lamellar membrane structure is being developed as a potential component of a garment for protection against chemical warfare agents (CWAs) represented here by simulants, dimethyl methyl phosphonate (DMMP) (a sarin-simulant), and 2-chloroethyl ethyl sulfide (CEES) (a simulant for sulfur mustard), yet allowing a high-moisture transmission rate. GO flakes of dimensions 300-800 nm, 0.7-1.2 nm thickness and dispersed in an aqueous suspension were formed into a membrane by vacuum filtration on a porous poly(ether sulfone) (PES) or poly(ether ether ketone) (PEEK) support membrane for noncovalent π-π interactions with GO flakes. After physical compression of such a membrane, upright cup tests indicated that it can block toluene for 3-4 days and DMMP for 5 days while exhibiting excellent water vapor permeation. Further, they display very low permeances for small-molecule gases/vapors. The GO flakes underwent cross-linking later with ethylenediamine (EDA) introduced during the vacuum filtration followed by physical compression and heating. With a further spray coating of polyurethane (PU), these membranes could be bent without losing barrier properties vis-à-vis the CWA simulant DMMP for 5 days; a membrane not subjected to bending blocked DMMP for 15 days. For the PEEK-EDA-GO-PU-compressed membranes after bending, the separation factors of HO over other species for low gas flow rates in the dynamic moisture permeation cell (DMPC) are: α is 42.3; α is 110; and α is 1800. At higher gas flow rates in the DMPC, the moisture transmission rate goes up considerably due to reduced boundary layer resistances and exceeds the threshold water vapor flux of 2000 g/(m·day) that defines a breathable fabric. This membrane displayed considerable resistance to permeation by CEES as well. The PES-EDA-GO-PU-compressed membrane shows good mechanical property under tensile strength tests.
传统的携载活性炭的防护服用于去除有毒气体,体积庞大。新型氧化石墨烯 (GO) 片状复合层状膜结构正被开发为防护化学战剂(CWA)的防护服的潜在组成部分,这里代表的模拟物是二甲甲基膦酸酯(DMMP)(沙林模拟物)和 2-氯乙基乙基硫醚(CEES)(模拟芥子气),同时允许高湿度传输率。尺寸为 300-800nm、厚度为 0.7-1.2nm 的 GO 薄片分散在水性悬浮液中,通过在多孔聚醚砜(PES)或聚醚醚酮(PEEK)支撑膜上进行真空过滤形成膜,以与 GO 薄片发生非共价的π-π相互作用。在对这样的膜进行物理压缩之后,直立杯测试表明,它可以阻挡甲苯 3-4 天和 DMMP 5 天,同时表现出出色的水蒸气渗透率。此外,它们对小分子气体/蒸气的渗透率非常低。GO 薄片随后与真空过滤过程中引入的乙二胺(EDA)进行交联,然后进行物理压缩和加热。通过进一步喷涂聚氨酯(PU),这些膜可以弯曲而不会失去对 CWA 模拟物 DMMP 的阻隔性能,长达 5 天;未弯曲的膜可以阻挡 DMMP 长达 15 天。对于弯曲后的 PEEK-EDA-GO-PU 压缩膜,在动态湿度渗透池(DMPC)中低气流速率下对其他物种的 HO 的分离因子为:α为 42.3;α为 110;α为 1800。在 DMPC 中的较高气流速率下,由于边界层阻力降低,水蒸气传输速率大大增加,并超过了定义透气织物的 2000g/(m·天)的水蒸气通量阈值。该膜对 CEES 的渗透也表现出相当大的阻力。在拉伸强度测试中,PES-EDA-GO-PU 压缩膜显示出良好的机械性能。