磷/氮/硅复配协效阻燃棉织物制备及其性能

doi:10.13475/j.fzxb.20240407001

纺织学报 ›› 2025, Vol. 46 ›› Issue (03): 151-157.doi: 10.13475/j.fzxb.20240407001

磷/氮/硅复配协效阻燃棉织物制备及其性能

廖喜林¹^,²^,³, 曾媛¹, 刘淑萍¹^,²^,³, 李亮¹^,²^,³, 李淑静¹^,²^,³, 刘让同¹^,²^,³()

1.中原工学院, 河南郑州 451191
2.郑州市阻燃隔热耐火功能性服装及材料重点实验室, 河南郑州 451191
3.先进纺织装备技术省部共建协同创新中心, 河南郑州 451191

收稿日期:2024-04-28 修回日期:2024-08-15 出版日期:2025-03-15 发布日期:2025-04-16
通讯作者: 刘让同(1966—),男,教授,博士。主要研究方向为纺织服装新材料、功能性服装的研发。E-mail:ranton@126.com。
作者简介:廖喜林(1992—),男,讲师,博士。主要研究方向为多功能阻燃纤维、纺织品及纳米纤维复合材料。
基金资助:
国家重点研发计划资助项目(2017YFB0309000);河南省科技攻关项目(242102320262)

Preparation of P/N/Si composite synergistic flame retardant cotton fabric and its performance

LIAO Xilin¹^,²^,³, ZENG Yuan¹, LIU Shuping¹^,²^,³, LI Liang¹^,²^,³, LI Shujing¹^,²^,³, LIU Rangtong¹^,²^,³()

1. Zhongyuan University of Technology, Zhengzhou, Henan 451191, China
2. Zhengzhou Key Laboratory of Flame Retardant, Heat Insulating and Fire Resistant Functional Clothing and Materials, Zhengzhou, Henan 451191, China
3. Collaborative Innovation Center of Advanced Textile Equipment, Zhengzhou, Henan 451191, China;

Received:2024-04-28 Revised:2024-08-15 Published:2025-03-15 Online:2025-04-16

摘要/Abstract

摘要： 为实现棉织物的高效阻燃,以聚乙烯亚胺(PEI)、植酸(PA)、纳米二氧化硅(SiO₂)为原料,构建磷/氮/硅复配协效阻燃体系。采用喷涂法对棉织物进行阻燃整理,借助X射线能谱分析仪、垂直燃烧测试仪、扫描电子显微镜、极限氧指数测试仪、热重分析仪、微型量热仪和烟密度测试等分析了阻燃棉织物的微观形貌表面形貌、燃烧性能、阻燃性能、热释放性能、热稳定性及其阻燃机制。结果表明:PEI、PA、SiO₂三者复配整理棉织物的阻燃效果最佳,整理后棉织物的极限氧指数(LOI)为30.3%,离火自熄,损毁长度降为7.2 cm;与预处理的棉织物相比,阻燃棉织物的热释放能力和总热释放量分别下降了85.0%和83.3%;PA先于棉织物吸热降解,抑制棉织物的初始热裂解;PEI、PA、SiO₂通过协同作用形成石墨化结构的炭化层,可提高其稳定性并阻隔氧气及热量的传递,有效改善了棉织物的阻燃性能。

关键词: 棉织物, 阻燃性能, 喷涂法, 复配协效, 低温碳化, 阻燃机制

Abstract:

Objective Owing to its excellent biocompatibility, dyeing, softness, thermal and wet comfort, cotton fiber has been widely used in various fields, such as home textiles, clothing and industrial textiles. However, the limiting oxygen index of cotton fiber is about 18 and thus it is a combustible and flammable fiber. Doping flame-retardant in cotton fiber can improve its flame retardance. Treating cotton fabrics with nitrogen series, phosphorus series, boron series or silicon series alone would improve the flame resistance, but its effect is not satisfactory, and the cost is high. This research aims to achieve synergistic improvement in flame retardance by treating the cotton fabric with these flame retardants together.

Method Polyethyleneimine (PEI), phytic acid (PA) and nano-silica (SiO₂) were used as raw materials to construct a P/N/Si-modified composite for synergistic improvement in the flame retardancy. The surface morphology, thermal stability, heat release property, flame retardant property and flame-retardant mechanism of the treated cotton fabric were analyzed by scanning electron microscopy (SEM), vertical combustion test, limiting oxygen index test, thermogravimetric analysis, microcalorimetry and smoke density.

Results According to the FT-IR spectra and SEM image, N, P and Si elements exist on the fiber surface of PEI/PA/SiO₂-modified cotton fabric. The initial degradation temperature (T_5%) of PEI/PA/SiO₂-modified cotton fabric was 97 ℃, and the decomposition rate reached a maximum at 288 ℃. Compared with raw cotton fabric, the initial degradation temperature was significantly reduced, and the char residue content increased to 38.54%, indicating that the composite flame retardant can successfully slow down the thermal decomposition of cotton fabric. The subsequent burning time, smoldering time and damage length of PEI/PA/SiO₂-modified cotton fibers were significantly reduced, and the LOI values reached 30.3%. This indicates that the synergistic flame retardancy of PEI, PA and SiO₂, in which the respective attributes are integrated, can improve the flame retardancy of the fabric. The prepared fabric satisfied the related standard. Compared with pure cotton fabric, peak heat release rate (pHRR), heat release capacity (HRC) and total heat release (THR) of PEI/PA/SiO₂-modified cotton fabric decreased by 84.2%, 85.0% and 83.3%, respectively, indicating it has high carbon formation efficiency and low the volume of gas generation in the thermal decomposition process. The smoke production of PEI/PA/SiO₂-modified cotton fiber was decreased and stable, which can effectively reduce the possibility of suffocation death in the fire. The smoke release of PEI/PA/SiO₂-modified cotton fabric was the least and the most stable among all samples, which indicates that PEI/PA/SiO₂-modified cotton fabric can not only effectively improve the flame-retardant performance of cotton fabric, but also reduce the release rate and release amount of smoke during the combustion process. Compared with the raw cotton fiber, the warp breaking strength and weft breaking strength of PEI/PA/SiO₂-modified cotton fabric decreased by 14.8% and 14.1%, respectively.

Conclusion The results showed that PEI/PA/SiO₂-modified cotton fabric can promote the catalytic carbon formation of cotton fiber at low temperature, reduce the amount of smoke release, and form a highly graphitized carbon layer on the fiber surface to isolate the contact between combustible gas and fiber, and thus achieve satisfactory flame retardant effect. PEI/PA/SiO₂-modified cotton fabric shows significantly better flame retardance performance than PEI, PA or PEI/PA-modified samples and meets the standard of decorative fabric flame retardant B1 requirements. Besides, PEI/PA/SiO₂-modified cotton fabric also improves the mechanical properties of cotton fabric by decreasing the damage of strong acidity from PA.

Key words: cotton fabric, flame retardancy, spraying method, composite synergistic effect, carbonization at low temperature, flame retardant mechanism

中图分类号:

TS193.5

廖喜林, 曾媛, 刘淑萍, 李亮, 李淑静, 刘让同. 磷/氮/硅复配协效阻燃棉织物制备及其性能[J]. 纺织学报, 2025, 46(03): 151-157.

LIAO Xilin, ZENG Yuan, LIU Shuping, LI Liang, LI Shujing, LIU Rangtong. Preparation of P/N/Si composite synergistic flame retardant cotton fabric and its performance[J]. Journal of Textile Research, 2025, 46(03): 151-157.

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链接本文: http://www.fzxb.org.cn/CN/10.13475/j.fzxb.20240407001

http://www.fzxb.org.cn/CN/Y2025/V46/I03/151

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样品	增重率/%	LOI值 /%	损毁长度/cm	续燃时间/s	阴燃时间/s
预处理	—	17.5	30.0	15.0	26.0
PEI整理	6.3	18.1	30.0	13.0	8.0
PA整理	7.8	19.7	30.0	10.0	0
PEI/PA整理	14.3	25.3	9.2	3.4	0
PEI/PA/SiO₂整理	17.8	30.3	7.2	2.0	0

样品	HRC/ (J·g^-1·K^-1)	pHRR/ (W·g^-1)	THR/ (kJ·g^-1)
预处理	240	229.7	12.7
PEI整理	196	189.4	10.5
PA整理	122	120.2	6.4
PEI/PA整理	97	93.7	4.8
PEI/PA/SiO₂整理	36	36.4	2.1

样品	断裂强力/N
样品	经向	纬向
预处理	290.8	276.4
PEI整理	271.6	252.8
PA整理	197.4	191.8
PEI/PA整理	244.7	226.2
PEI/PA/SiO₂整理	247.7	237.1

磷/氮/硅复配协效阻燃棉织物制备及其性能

Preparation of P/N/Si composite synergistic flame retardant cotton fabric and its performance

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