GEMTEX-Laboratoire de Génie et Matériaux Textiles, ENSAIT, F-59000 Lille, France.
Department of Applied Science and Technology, Politecnico di Torino, 15121 Alessandria, Italy.
Molecules. 2020 Oct 27;25(21):4963. doi: 10.3390/molecules25214963.
Biobased lignin represents one of the possible materials for next-generation flame retardant additives due to its sustainability, environmental benefits and comparable efficiency to other flame retardant (FR) additives. In this context, this study presents the development of FR polyamide 11 (PA11) multifilament yarns and fabric structures containing different industrial lignins (i.e., lignosulfonate lignin (LL), and Kraft lignin (KL)) and zinc phosphinate (ZnP). The combination of ZnP and lignin (KL or LL) at different weight ratios were used to prepare flame retarded PA11 blends by melt mixing using a twin-screw extruder. These blends were transformed into continuous multifilament yarns by the melt-spinning process even at a high concentration of additives as 20 wt%. The mechanical test results showed that the combination of KL and ZnP achieved higher strength and filaments showed regularity in structure as compared to the LL and ZnP filaments. Thermogravimetric (TG) analysis showed the incorporation of lignin induces the initial decomposition (T) at a lower temperature; at the same time, maximum decomposition (T) shifts to a higher temperature region and a higher amount of char residue is reported at the end of the test. Further, the TGA-FTIR study revealed that the ternary blends (i.e., the combination of LL or KL, ZnP, and PA11) released mainly the phosphinate compound, hydrocarbon species, and a small amount of phosphinic acid during the initial decomposition stage (T), while hydrocarbons, carbonyls, and phenolic compounds along with CO are released during main decomposition stage (T). The analysis of decomposition products suggests the stronger bonds formation in the condensed phase and the obtainment of a stable char layer. Cone calorimetry exploited to study the fire behavior on sheet samples (polymer bulk) showed an improvement in flame retardant properties with increasing lignin content in blends and most enhanced results were found when 10 wt% of LL and ZnP were combined such as a reduction in heat release rate (HRR) up to 64% and total heat release (THR) up to 22%. Besides, tests carried out on knitted fabric structure showed less influence on HRR and THR but the noticeable effect on postponing the time to ignition (TTI) and reduction in the maximum average rate of heat emission (MARHE) value during combustion.
生物基木质素因其可持续性、环境效益和与其他阻燃剂 (FR) 添加剂相当的效率,是下一代阻燃剂添加剂的可能材料之一。在这种情况下,本研究开发了含有不同工业木质素(即木质素磺酸盐木质素 (LL) 和 Kraft 木质素 (KL)) 和磷酸锌 (ZnP) 的 FR 聚酰胺 11 (PA11) 复丝纱线和织物结构。通过双螺杆挤出机熔融共混,将 ZnP 与木质素 (KL 或 LL) 以不同的重量比组合,制备阻燃 PA11 共混物。这些共混物通过熔融纺丝工艺转化为连续的复丝纱线,即使在 20wt%的高添加剂浓度下也是如此。力学性能测试结果表明,与 LL 和 ZnP 长丝相比,KL 和 ZnP 的组合具有更高的强度和更规则的长丝结构。热重分析 (TG) 表明,木质素的加入会导致初始分解 (T) 在较低的温度下发生;同时,最大分解 (T) 移至较高的温度区域,并且在测试结束时报告了更高的残炭量。此外,TGA-FTIR 研究表明,三元共混物(即 LL 或 KL、ZnP 和 PA11 的组合)在初始分解阶段 (T) 主要释放膦酸盐化合物、烃类物质和少量亚磷酸,而在主要分解阶段 (T) 释放烃类、羰基和酚类化合物以及 CO。分解产物分析表明,在凝聚相中形成了更强的键,获得了稳定的炭层。锥形量热仪用于研究片材样品(聚合物本体)的燃烧行为,结果表明随着共混物中木质素含量的增加,阻燃性能得到改善,当 10wt%的 LL 和 ZnP 结合时,得到了最显著的结果,如放热率 (HRR) 降低了 64%,总热释放量 (THR) 降低了 22%。此外,对针织结构进行的测试表明,HRR 和 THR 的影响较小,但在点火时间 (TTI) 推迟和燃烧过程中最大平均热发射率 (MARHE) 值降低方面有明显效果。