纺织学报 ›› 2026, Vol. 47 ›› Issue (04): 17-25.doi: 10.13475/j.fzxb.20250705101

• 纤维材料 • 上一篇    下一篇

具备光热转化性再生羊毛角蛋白基复合纤维的开发

赵美宁1,2, 李博1,2(), 孙艳丽1,2, 武海良1,2, 田诗溢1,2   

  1. 1 西安工程大学 纺织科学与工程学院, 陕西 西安 710048
    2 西安工程大学 功能性纺织材料及制品教育部重点实验室, 陕西 西安 710048
  • 收稿日期:2025-07-21 修回日期:2026-01-15 出版日期:2026-04-15 发布日期:2026-06-24
  • 通讯作者: 李博(1988—),男,讲师,博士。主要研究方向为生物质材料开发和应用。E-mail:libo1988@xpu.edu.cn
  • 作者简介:赵美宁(2000—),女,硕士生。主要研究方向为角蛋白基纤维的改性和制备技术。
  • 基金资助:
    功能性纺织材料及制品教育部重点实验室开放课题项目(2024FTMP027);陕西省教育厅科学研究计划项目(25JS052)

Development of regenerated wool keratin-based composite fibers with photothermal transformation

ZHAO Meining1,2, LI Bo1,2(), SUN Yanli1,2, WU Hailiang1,2, TIAN Shiyi1,2   

  1. 1 School of Textile Science and Engineering, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China
    2 Key Laboratory of Functional Textile Materials and Products, Ministry of Education, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China
  • Received:2025-07-21 Revised:2026-01-15 Published:2026-04-15 Online:2026-06-24

摘要:

羊毛等蛋白质纤维中富含角蛋白,若能合理利用将会成为重要的天然生物质资源,但现有研究中再生角蛋白材料普遍存在利用率较低、结构及力学性能缺陷明显、功能单一等不足,严重限制其应用和推广。针对上述问题,将自制的二维过渡金属氮化物(MXene)材料引入角蛋白/聚酰胺6(PA6)共混体系制备复合纤维,在赋予角蛋白基再生纤维光热转化性能的同时,探究其对纤维结构和性能的影响,以期开发出性能优良的功能性再生角蛋白材料。首先分析了MXene材料与角蛋白/PA6共混纺丝的复合工艺条件,随后研究了复合后角蛋白基纤维的物理结构、化学特性以及光热转化性能的变化规律。得到优化的复合工艺条件:MXene质量分数为0.6%,复合温度为60 ℃,复合时间为3 h。在该条件下制得的复合纤维其光热转化性能显著提升,同时物理结构和力学性能也得到改善,复合纤维断裂强力和断裂伸长率分别达到40.44 cN和12.65%。结构分析表明,MXene与角蛋白/PA6属于物理复合,其对角蛋白基再生纤维的化学结构和结晶结构影响不显著。

关键词: 功能性再生角蛋白材料, 羊毛角蛋白, 聚酰胺6, MXene, 湿法纺丝, 复合纤维, 光热转化性能

Abstract:

Objective This study aims to develop high-performance functional regenerated keratin-based composite fibers by incorporating MXene into keratin/polyamide 6 (PA6) blends, addressing the critical drawbacks of low utilization efficiency, poor mechanical properties, and single functionality of existing regenerated keratin materials. It further seeks high-value recycling of waste wool resources, responding to global demands for green sustainability and circular economy in the textile industry, where waste textiles are mostly landfilled or incinerated, causing resource waste and environmental pollution.

Method Wool keratin was extracted via the reduction pretreatment-formic acid method using tris(2-carboxyethyl)phosphine hydrochloride as the reducing agent (80 ℃, 2 h reduction; 60 ℃, 5 h dissolution in 90% formic acid). Laboratory-synthesized MXene was compounded with keratin/PA6 (5: 5 mass ratio) spinning solution through wet spinning (30% ZnSO4 coagulation bath, 0.5% glutaraldehyde, 40 ℃ spinning temperature). Process parameters (MXene content: 0.1%-1.2%, temperature: 40-70 ℃, time: 1-4 h) were optimized, and materials were characterized by SEM, XPS, FT-IR, XRD, electronic single-fiber strength testing, and xenon lamp-induced photothermal evaluation.

Results The optimal compounding conditions were confirmed as MXene mass fraction 0.6%, temperature 60 ℃, and time 3 h, which balanced MXene dispersion and keratin structural integrity. Consistent with MXene's intrinsic photothermal property reported in literatures, the composite fiber exhibited exceptional photothermal conversion performance. Infrared thermal imaging showed a temperature rise of 42.3 ℃ after 5 min of 1 000 W xenon lamp irradiation, while the MXene-free control only increased by 20.3 ℃. This efficiency surpassed many photothermal biopolymer composites due to MXene's conductive network accelerating photon-to-heat conversion. Mechanical tests demonstrated a breakthrough compared to conventional regenerated keratin fibers. Literatures show that most have breaking strength below 20 cN, but composite fiber generated in this research reached 40.44 cN, with elongation at break of 12.65%. This well outperforms the pure keratin/PA6 fiber (15.36 cN, 21.18%) and aligns with the β-sheet reinforcement mechanism reported in keratin fiber studies. SEM observations revealed MXene eliminated surface grooves and reduced internal pores at 0.6% content, forming a compact structure. However, MXene content >0.6% caused agglomeration, as seen in similar MXene/polymer systems. XPS analysis detected 0.12% Ti element, confirming successful MXene incorporation, with the composite retaining keratin's characteristic C, N, O, S elements. FT-IR spectra showed no shifts in amide A (3 282 cm-1) and amide I (1 640 cm-1) peaks, verifying physical bonding which avoid chemical modification that impairs keratin's biocompatibility. XRD results indicated MXene induced a 37% increase in keratin's β-sheet diffraction peak (20°), enhancing crystallinity from 18.2% to 29.1%, which directly contributed to mechanical improvement. Compounding at above 70 ℃ led to keratin hydrolysis (observed via reduced amide peaks), while time longer than 3 h caused uneven MXene dispersion, both resulting in performance degradation.

Conclusion MXene effectively endows keratin/PA6 fibers with superior photothermal conversion while enhancing mechanical properties and structural uniformity through physical compounding, addressing key limitations of regenerated keratin materials highlighted in literatures. This study provides a feasible technical approach for high-value waste wool utilization, leveraging MXene's photothermal advantages and keratin/PA6 blend biocompatibility. The composite fibers hold broad applications in functional textiles (e.g., thermal management fabrics), biomass materials, and medical thermotherapy patches. The optimized process offers strong industrial potential, contributing to resource conservation and the textile industry's green transition.

Key words: functional regenerated keratin material, wool keratin, polyamide 6, MXene, wet spinning, composite fiber, photothermal conversion performance

中图分类号: 

  • TS199

图1

再生角蛋白/PA6/MXene纤维制备流程图"

图2

不同MXene质量分数再生纤维的SEM照片"

表1

不同MXene质量分数角蛋白基再生纤维的力学性能测试结果"

MXene
添加量/%
断裂强
力/cN
断裂伸长
率/%
0 15.36±6.22 21.18±9.39
0.1 40.41±20.03 10.39±6.40
0.3 20.30±9.60 13.38±8.20
0.6 21.47±10.87 7.64±5.20
0.9 27.46±14.65 8.51±5.01
1.2 43.30±22.88 7.90±5.90

图3

不同MXene质量分数纤维光热转化测试结果"

图4

不同复合温度条件下再生纤维的SEM照片"

表2

不同复合温度条件下再生纤维力学性能"

复合温度/℃ 断裂强力/cN 断裂伸长率/%
40 28.40±17.90 49.21±19.60
50 20.30±9.80 13.38±8.30
60 35.56±7.22 34.11±16.70
70 30.96±10.80 31.90±15.52

图5

不同复合温度纤维光热转化测试结果"

图6

不同复合时间复合纤维的SEM照片"

表3

不同复合时间下再生纤维力学性能"

复合时间/h 断裂强力/cN 断裂伸长率/%
1 33.95±15.71 11.78±6.25
2 38.52±18.61 10.21±6.21
3 40.44±10.14 12.65±7.65
4 31.95±11.80 10.09±6.09

图7

不同复合时间纤维光热转化测试结果"

图8

不同纤维试样的XPS谱图"

表4

各样品中元素质量分数"

样品名称 元素质量分数/%
C N O S Ti
羊毛 66.93 11.51 15.90 4.34 0
PA6 65.76 9.47 20.65 3.54 0
KE/PA6 56.47 14.46 24.76 3.70 0
KE/PA6/MXene 62.19 13.55 21.01 2.69 0.12

图9

羊毛纤维及角蛋白再生纤维红外光谱图"

图10

各试样的XRD谱图"

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