Alghamdi Amjad S, Hine Peter J, Ries Michael E
Soft Matter Physics Research Group, School of Physics and Astronomy, University of Leeds, Leeds LS2 9JT, U.K.
Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia.
ACS Omega. 2025 May 21;10(21):22257-22268. doi: 10.1021/acsomega.5c03000. eCollection 2025 Jun 3.
The partial dissolution of cashmere and merino wool yarns in the ionic liquid 1-ethyl-3-methylimidazolium acetate was studied both with and without pretreatment of the yarns using sodium bisulfite. The cross sections of both yarn fibers were analyzed using optical microscopy for different dissolution times and temperatures. It was found that the dissolution of cashmere yarn (CY) and merino wool yarn (WY) has two competing processes: one rate limited by disulfide bonds and the other rate limited by hydrogen bonds. The yarn dissolution obeyed the time-temperature superposition. From this, two activation energies for each yarn were obtained, one with respect to low temperature (LT) and one for high temperature (HT), = 110 ± 12 kJ/mol, = 61 ± 6 kJ/mol, = 124 ± 14 kJ/mol, and = 35 ± 1 kJ/mol. The crossover temperature between the low- and high-temperature regimes was found to be 70 °C. The reducing agent (sodium bisulfite) was used to cleave the disulfide bonds in CY and WY. FTIR spectroscopy provided evidence that the disulfide bonds were, in fact, cleaved during this pretreatment. A single linear regime (instead of two) was found on the Arrhenius graphs of the pretreated cashmere (PCY) and the pretreated merino wool yarn (PWY), strongly confirming our hypothesis that at low temperatures, the disulfide bonds determined the rate of dissolution. The subsequent dissolution activation energies were found to be reduced from the low-temperature activation energies for the CY and WY, with their values being = 62 ± 4 kJ/mol and = 66 ± 3 kJ/mol, respectively. With further analysis, the self-diffusion coefficients of [C2mim]-[OAc] for the CY, PWY, and PCY dissolution systems were quantified and compared to the self-diffusion coefficient of pure [C2mim]-[OAc] measured using NMR.
研究了羊绒纱线和美利奴羊毛纱线在离子液体1-乙基-3-甲基咪唑醋酸盐中的部分溶解情况,包括纱线在使用亚硫酸氢钠预处理和未预处理两种情况下的溶解情况。使用光学显微镜对不同溶解时间和温度下的两种纱线纤维横截面进行了分析。结果发现,羊绒纱线(CY)和美利奴羊毛纱线(WY)的溶解存在两个相互竞争的过程:一个过程的速率受二硫键限制,另一个过程的速率受氢键限制。纱线溶解遵循时间-温度叠加原理。由此,得到了每种纱线的两个活化能,一个是低温(LT)下的活化能,另一个是高温(HT)下的活化能,CY的(E_{a1}=110±12kJ/mol),(E_{a2}=61±6kJ/mol),WY的(E_{a1}=124±14kJ/mol),(E_{a2}=35±1kJ/mol)。发现低温和高温区域之间的交叉温度为70°C。使用还原剂(亚硫酸氢钠)来裂解CY和WY中的二硫键。傅里叶变换红外光谱(FTIR)提供的证据表明,在该预处理过程中,二硫键实际上被裂解了。在预处理羊绒(PCY)和预处理美利奴羊毛纱线(PWY)的阿累尼乌斯图上发现了单一的线性区域(而不是两个),这有力地证实了我们的假设,即在低温下,二硫键决定了溶解速率。随后发现溶解活化能相对于CY和WY的低温活化能有所降低,其值分别为(E_{a}=62±4kJ/mol)和(E_{a}=66±3kJ/mol)。通过进一步分析,对CY、PWY和PCY溶解体系中([C_{2}mim]-[OAc])的自扩散系数进行了量化,并与使用核磁共振(NMR)测量的纯([C_{2}mim]-[OAc])的自扩散系数进行了比较。