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通过电化学制备的氧化石墨烯对生物基木质素/聚酰胺长丝进行表面改性,以改善其热稳定性能,使其成为碳纤维生产的前驱体。

Biobased lignin/polyamide filaments surface-modified with electrochemically produced graphene oxide to improve their thermal stabilisation behaviour as precursors for carbon fibre production.

作者信息

Kandola Baljinder K, Hewage Trishan A M, Hajee Muhammed, Horrocks A Richard, Culebras Mario, Collins Maurice N

机构信息

Institute for Materials Research and Innovation, University of Bolton, Deane Road, Bolton BL3 5AB, UK.

Institute for Materials Research and Innovation, University of Bolton, Deane Road, Bolton BL3 5AB, UK; Colorplas Ltd., Moss Bridge Road, Rochdale, Lancashire OL16 5PQ, UK.

出版信息

Int J Biol Macromol. 2025 Sep;321(Pt 4):146553. doi: 10.1016/j.ijbiomac.2025.146553. Epub 2025 Aug 5.

DOI:10.1016/j.ijbiomac.2025.146553
PMID:40763850
Abstract

The thermal stability of melt-spun hydroxypropyl-modified lignin/polyamide (PA1010) 50:50 wt% blended precursor fibres, crucial for the thermal stabilisation stage in carbon fibre production, was enhanced by pre-treating the fibres with a graphene oxide (GO) suspension, synthesized via the modified Hummers method. This pre-treatment allowed the fibres to be subsequently thermally stabilised at a faster heating rate of 20 °C/min, compared to the typical 0.1-0.25 °C/min used for lignin-based fibres, thereby reducing overall thermal stabilisation time from 29 h to 2.5 h. The stabilised filaments were successfully carbonised at 950 °C, yielding coherent, void-free carbon fibres without inter-filament fusion. The tensile modulus of GO-treated filaments improved from 1.3 GPa to 2.3 GPa after thermal stabilisation. However, derived carbon fibres were brittle in nature. Various characterisation techniques, including DSC, TGA, FTIR, SEM-EDX, AFM, XPS, and tensile testing, were used to analyze the physico-chemical changes. DSC showed that GO improved the polycrystallinity of the precursor filaments and contributed to the formation of a three-dimensional cross-linked network during heat stabilisation, suppressing the PA melt endotherm. TGA confirmed that GO-treated filaments had higher char yields (∼40 %) than untreated fibres (∼30 %), further supporting GO-induced crosslinking reactions. FTIR, SEM-EDX, and AFM confirmed an even GO coating. A study of GO pre-treatment variables suggested that a reduction in GO concentration is required to reduce resulting carbon fibre brittleness at the expense of increased thermal stabilisation time.

摘要

通过用改进的Hummers方法合成的氧化石墨烯(GO)悬浮液对熔纺羟丙基改性木质素/聚酰胺(PA1010)50:50重量比的共混前驱体纤维进行预处理,增强了其热稳定性,这对于碳纤维生产中的热稳定阶段至关重要。与用于木质素基纤维的典型加热速率0.1-0.25℃/分钟相比,这种预处理使得纤维随后能够以20℃/分钟的更快加热速率进行热稳定化,从而将总的热稳定时间从29小时减少到2.5小时。稳定后的长丝在950℃成功碳化,得到了连贯、无空隙且无丝间融合的碳纤维。热稳定后,经GO处理的长丝的拉伸模量从1.3 GPa提高到了2.3 GPa。然而,所得碳纤维本质上是脆性的。使用了包括DSC、TGA、FTIR、SEM-EDX、AFM、XPS和拉伸测试在内的各种表征技术来分析物理化学变化。DSC表明,GO提高了前驱体长丝的多晶性,并有助于在热稳定过程中形成三维交联网络,抑制了PA的熔融吸热。TGA证实,经GO处理的长丝比未处理的纤维具有更高的炭产率(约40%),进一步支持了GO引发的交联反应。FTIR、SEM-EDX和AFM证实了GO涂层均匀。对GO预处理变量的研究表明,需要降低GO浓度以减少所得碳纤维的脆性,但代价是增加热稳定时间。

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