Cool Spinning Strategy for High-Performance Thick Aramid Fibers

Abstract

Enhancing the mechanical performance of synthetic fibers is pursued in aerospace, wearable devices, and protective textiles. However, current reinforcement methods rely on the chemical modification of polymer stock, introducing greater complexity and processing challenge. In this work, the mechanical properties of different aramid fibers and their composite fibers are improved through a cool spinning strategy. By reducing the coagulation temperature to –25 °C, the interactions between polymer chains and solvent molecules are substantially enhanced, thereby improving the drawability of the polymer solution. The draw ratio markedly increases typically from 200% to 380%, leading to optimized oriented and crystalline structures. Consequently, the tensile strength, Young’s modulus and toughness of large-diameter heterocyclic para-aramid fibers increase by 112%, 123% and 118%, respectively. The cool spinning proposal is further applied to 36-μm-thick heterocyclic para-aramid/graphene oxide composite fibers, realizing elevated tensile strength, Young’s modulus and toughness of 6.28 GPa, 119.62 GPa and 172.7 MJ⋅m⁻³, respectively. This strategy is also applicable to meta-aramid fibers, where tensile strength increases up to 1.35 GPa. The simple and universal cool spinning approach opens an avenue towards the preparation of high-performance fibers and composite fibers for structural and functional applications.

Graphical Abstract

A new cool spinning strategy for aramid fibers is proposed by reducing the coagulation temperature. This strategy dramatically enhances the interactions between polymer and solvent molecules, thereby increasing the draw ratio. It enables the preparation of different high-performance aramid fibers and their composite fibers with substantially improved tensile strength, Young’s modulus, and toughness.

Keywords

Mechanical properties / Aramid fibers / Composite fibers / Cool spinning / High-performance fibers

References

[1] Liu YJ, Xu Z, Gao WW, Gao C. Graphene and other 2D colloids: liquid crystals and macroscopic fibers. Adv Mater, 2017, 29: 1606794

[2] Li JT, Li S, Huang JY, Abdul QK, Ab BG, Zhou X, Liu ZF, Zhu MF. Spider silk-inspired artificial fibers. Adv Sci, 2022, 9: 2103965

[3] Liu FY, Pan L, Liu YF, Zhai GX, Sha Z, Zhang XG, Zhang ZH, Liu QQ, Yu SL, Zhu LP, Xiang HX, Zhou Z, Zhu MF. Biobased fibers from natural to synthetic: processing, manufacturing, and application. Matter, 2024, 7: 1977

[4] Chang D, Liu JR, Fang B, Xu Z, Liu YJ, Brassart L, Guo F, Gao WW, Gao C. Reversible fusion and fission of graphene oxide-based fibers. Science, 2021, 372: 614

[5] Yu RH, Wu L, Yang ZH, Chen HF, Pan SW, Zhu MF. Dynamic liquid metal-microfiber interlocking enables highly conductive and strain-insensitive metastructured fibers for wearable electronics. Adv Mater, 2025, 37 2415268

[6] Chen MX, Wang Z, Zhang QH, Wang ZX, Liu W, Chen M, Liu W. Self-powered multifunctional sensing based on super-elastic fibers by soluble-core thermal drawing. Nat Commun, 2021, 12 1416

[7] Gao Z, Zhu JD, Rajabpour S, Joshi K, Kowalik M, Croom B, Schwab Y, Zhang LW. Graphene reinforced carbon fibers. Sci Adv, 2020, 6 eaaz4191

[8] Liu LJ, Chang D, Gao C. A review of multifunctional nanocomposite fibers: design, preparation and applications. Adv Fiber Mater, 2024, 6: 68

[9] Li YX, Li JJ, Sun J, He HN, Li B, Ma C, Liu K, Zhang HJ. Bioinspired and mechanically strong fibers based on engineered non-spider chimeric proteins. Angew Chem Int Ed, 2020, 59: 8148

[10] Xin GQ, Yao TK, Sun HT, Scott SM, Shao DL, Wang GK, Lian J. Highly thermally conductive and mechanically strong graphene fibers. Science, 2015, 349: 1083

[11] Zhang XS, Lei XD, Jia XZ, Sun TZ, Xu XH, Li LJ, Yan D, Shao YL, Zhang J. Carbon nanotube fibers with dynamic strength up to 14 Gpa. Science, 2024, 384: 1318

[12] Ding L, Xu TQ, Zhang JW, Ji JP, Song ZT, Zhang YN, Xu YJ, Liu T, Liu Y, Zhang ZH, Gong WB, Wang YN, Shi ZZ, Ma RZ, Geng JX, Ngo HT, Geng FX, Liu ZF. Covalently bridging graphene edges for improving mechanical and electrical properties of fibers. Nat Commun, 2024, 15: 4880

[13] Liao XJ, Dulle M, de Souza e Silva JM, Wehrspohn RB, Agarwal S, Forster S, Hou HQ, Smith P, Greiner A. High strength in combination with high toughness in robust and sustainable polymeric materials. Science, 2019, 366: 1376

[14] Sun JK, Guo WJ, Mei GK, Wang SL, Wen K, Wang ML, Feng DY, Qian D, Zhu MF, Zhou X, Liu ZF. Artificial spider silk with buckled sheath by nano-pulley combing. Adv Mater, 2023, 35 2212112

[15] He WQ, Wang ML, Mei GK, Liu SY, Khan AQ, Li C, Feng DY, Su ZH, Bao LL, Wang G, Liu EZ, Zhu YT, Bai J, Zhu MF, Zhou X, Liu ZF. Establishing superfine nanofibrils for robust polyelectrolyte artificial spider silk and powerful artificial muscles. Nat Commun, 2024, 15: 3485

[16] He AN, Xing TH, Liang ZH, Luo YX, Zhang Y, Wang MQ, Huang ZY, Bai J, Wu LY, Shi ZC, Zuo HM, Zhang WS, Chen FX, Xu WL. Advanced aramid fibrous materials: fundamentals, advances, and beyond. Adv Fiber Mater, 2024, 6: 3

[17] Chen FX, Zhai LS, Yang HY, Zhao SC, Wang ZL, Gao C, Zhou JY, Liu X, Yu ZW, Qin Y, Xu WL. Unparalleled armour for aramid fiber with excellent UV resistance in extreme environment. Adv Sci, 2021, 8 2004171

[18] Chi MC, Cai CC, Liu YH, Zhang S, Liu T, Du GL, Meng XJ, Luo B, Wang JL, Shao YZ, Wang SF, Nie SX. Aramid triboelectric materials: opportunities for self-powered wearable personal protective electronics. Adv Funct Mater, 2024, 34 2411020

[19] Guo Q, Tian HH, Cheng Y, Wang SJ, Li ZL, Hao H, Liu JY, Jiao K, Gao X, Zhang J. Structural-functional integrated graphene-skinned aramid fibers for electromagnetic interference shielding. ACS Nano, 2024, 18: 33566

[20] Sun H, Yang B, Zhang MY. Functional-structural integrated aramid nanofiber-based honeycomb materials with ultrahigh strength and multi-functionalities. Adv Fiber Mater, 2024, 6: 1122

[21] Li MM, Chen X, Li XT, Dong J, Zhao X, Zhang QH. Controllable strong and ultralight aramid nanofber-based aerogel fibers for thermal insulation applications. Adv Fiber Mater, 2022, 4: 1267

[22] Fu XT, Si LM, Zhang ZX, Yang TT, Feng QH, Song JW, Zhu SZ, Ye DD. Gradient all-nanostructured aerogel fibers for enhanced thermal insulation and mechanical properties. Nat Commun, 2025, 16: 2357

[23] Luo JJ, Wen YY, Jia XZ, Lei XD, Jian MQ, Xiao ZH, Li LY, Zhang JW, Li T, Dong HL, Wu XQ, Gao EL, Jiao K, Zhang J. Fabricating strong and tough aramid fibers by small addition of carbon nanotubes. Nat Commun, 2023, 14 3019

[24] Luo JJ, Wen YY, Li T, Jia XZ, Lei XD, Zhang ZY, Xiao ZH, Wu XQ, Gao ZF, Gao EL, Jiao K, Zhang J. High interfacial shear strength and high tensile strength in heterocyclic aramid fibers with improved interchain interaction. Adv Funct Mater, 2024, 34: 2310008

[25] Li JQ, Wen YY, Xiao ZH, Wang SJ, Zhong LX, Li T, Jiao K, Li LY, Luo JJ, Gao ZF, Li SZ, Zhang Z, Zhang J. Holey reduced graphene oxide scaffolded heterocyclic aramid fibers with enhanced mechanical performance. Adv Funct Mater, 2022, 32 2200937

[26] Gao ZF, Song QQ, Xiao ZH, Li ZL, Li T, Luo JJ, Wang SS, Zhou WL, Li LY, Yu JR, Zhang J. Submicron-sized, high crystalline graphene-reinforced meta-aramid fibers with enhanced tensile strength. Acta Phys-Chim Sin, 2023, 39: 2307046

[27] Kong HJ, Teng CQ, Liu XD, Zhou JJ, Zhong HP, Zhang Y, Han KQ, Yu MH. Simultaneously improving the tensile strength and modulus of aramid fiber by enhancing amorphous phase in supercritical carbon dioxide. RSC Adv, 2014, 4: 20599

[28] Dai Y, Han YT, Yuan YH, Meng CB, Cheng Z, Luo LB, Qin JQ, Liu XY. Synthesis of heterocyclic aramid fiber based on solid-phase cross-linking of oligomers with reactive end group. Macromol Mater Eng, 2018, 303: 1800076

[29] Dai Y, Meng CB, Cheng Z, Luo LB, Liu XY. Nondestructive modification of aramid fiber based on selective reaction of external cross-linker to improve interfacial shear strength and compressive strength. Compos Part A Appl Sci Manuf, 2019, 119: 217

[30] Lyu JW, Chen YY, Liu MX, Liu BY, Yang JL, Liu Y, Liu XY. Latent active unit triggered crosslinking inside aramid fiber with improved transverse connection and composite properties. Compos Sci Technol, 2023, 241 110104

[31] Wang YL, He J, Zou LW, Zou LM, Wang HJ, Wang C, Li YV. Effect of the solid content of spinning solutions on the structure properties of large-diameter polyvinyl alcohol fiber. J Polym Res, 2024, 31 55

[32] Lu S, Blanco C, Rand B. Large diameter carbon fibres from mesophase pitch. Carbon, 2002, 40: 2109

[33] Otto WILLIAMH. Relationship of tensile strength of glass fibers to diameter. J Am Ceram Soc, 1954, 38: 122

[34] Chen CF, Wang XY, Wang FD, Peng T. Preparation and characterization of para-aramid fibers with the main chain containing heterocyclic units. J Macromol Sci B, 2020, 59: 90

[35] Dong ZH, Qu Y, Jiao YJ, Jiao YY, Xue K, Zhu WG, Liu H, Qi JG, Wang YL. Temperature response behavior of poly(1-vinyl-3-methylimidazole dimethyl phosphate-co-N-isopropylacrylamide) in aqueous and ester solutions driven by hydrogen bonding. J Mol Liq, 2024, 395 123848

[36] Joseph J, Jemmis ED. Red-, blue-, or no-shift in hydrogen bonds: a unified explanation. J Am Chem Soc, 2007, 129: 4620

[37] Pimentel GC, McClellan AL. Hydrogen bonding. Annu Rev Phys Chem, 1971, 22: 347

[38] Meng T, Sun YW, Tong C, Zhang P, Xu DY, Yang JL, Gu P, Yang JK, Zhao Y. Solid-state thermal memory of temperature-responsive polymer induced by hydrogen bonds. Nano Lett, 2021, 21: 3843

[39] Guo R, Wang LD, Chen FF, Li KW, Gao Y, Shen CW, Ye X, Liu SP, Wang Y, Li ZS, Li P, Xu Z, Liu YJ, Gao C. Hydrogen bonding-regulated miscibility of graphene oxide and nonionic water-soluble polymers. Nanoscale, 2024, 16: 19510

[40] Liu K, Han PB, Yu SF, Wu XJ, Tian YY, Liu QH, Wang JH, Zhang MM, Zhao CZ. Hydrogen-bonding-induced clusteroluminescence and UCST-type thermoresponsiveness of nonconjugated copolymers. Macromolecules, 2022, 55(198599

[41] Wang F, Fang WZ, Ming X, Liu YJ, Xu Z, Gao C. A review on graphene oxide: 2d colloidal molecule, fluid physics, and macroscopic materials. Appl Phys Rev, 2023

[42] Ling S, Kaplan DL, Buehler MJ. Nanofibrils in nature and materials engineering. Nat Rev Mater, 2018, 3: 18016

[43] Fang B, Yan JM, Chang D, Piao JL, Ma MK, Gu Q, Gao P, Chai Y, Tao XM. Scalable production of ultrafine polyaniline fibres for tactile organic electrochemical transistors. Nat Commun, 2022, 13: 2101

[44] Li P, Liu YJ, Shi SY, Xu Z, Ma WG, Wang ZQ, Liu SP, Gao C. Highly crystalline graphene fibers with superior strength and conductivities by plasticization spinning. Adv Funct Mater, 2020, 30 2006584

[45] Wang ZF, Sangroniz L, Xu J, Zhu CZ, Müller A. Polymer physics behind the gel-spinning of UHMWPE fibers. Macromol Rapid Comm, 2024, 45: 2400124

[46] Teramoto Y, Kubota F. High-performance and specialty fibers: concepts, technology and modern applications of man-made fibers for the future, 2016, Japan, Springer

[47] Schaller R, Feldman K, Smith P, Tervoort TA. High-performance polyethylene fibers “Al Dente”: improved gel-spinning of ultrahigh molecular weight polyethylene using vegetable oils. Macromolecules, 2015, 48: 8877

[48] Morgan R, Allred R. Reference book for composites technology, 1989, Boca Raton, CRC Press1431

[49] Xu Y, Zhang H, Huang G. Review on the mechanical deterioration mechanism of aramid fabric under harsh environmental conditions. Polym Test, 2023, 128 108227

[50] Kühne TD, Iannuzzi M, Del Ben M, Rybkin VV, Seewald P, Stein F, Laino T. CP2K: an electronic structure and molecular dynamics software package - Quickstep: efficient and accurate electronic structure calculations. J Chem Phys, 2020

[51] VandeVondele J, Hutter J. Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J Chem Phys, 2007

[52] Zhang X, De Volder M, Zhou WB, Issman LR, Wei XJ, Kaniyoor A, Portas JT, Smail F, Wang ZB, Boies A. Simultaneously enhanced tenacity, rupture work, and thermal conductivity of carbon nanotube fibers by raising effective tube portion. Sci Adv, 2022, 8 eabq3515

[53] Hegde M, Yang L, Vita F, Ryan JF, van de Renee W, Norder B, Lafont U, Oriano F, Louis AM, Stephen JP, Edward TS, Dingeman TJ. Strong graphene oxide nanocomposites from aqueous hybrid liquid crystals. Nat Commun, 2020, 11: 830

[54] Kinloch IA, Suhr J, Lou J, Robert JY, Pulickel MA. Composites with carbon nanotubes and graphene: an outlook. Science, 2018, 362: 547

[55] Sun XM, Sun H, Li HP, Peng HS. Developing polymer composite materials: carbon nanotubes or graphene?. Adv Mater, 2013, 25: 5153

[56] Zhang ZY, Wang YH, Zhou H, Dai HB, Luo JJ, Chen YZ, Li ZL, Li MD, Li C, Gao EL, Jiao K, Zhang J. Fabricating aramid fibers with ultrahigh tensile and compressive strength. Adv Fiber Mater, 2025, 7: 774

[57] Li KM, Ni XP, Wu QQ, Yuan CS, Li CL, Li D, Chen HF, Lv YG, Ju AQ. Carbon-based fibers: fabrication, characterization and application. Adv Fiber Mater, 2022, 4: 631

[58] Liu Y, Kumar S. Recent progress in fabrication, structure, and properties of carbon fibers. Polym Rev, 2012, 52: 234

[59] Cao KK, Liu YF, Yang Y, Yuan F, Wang J, Liu HM, Jiang MJ, Yang J. The preparation and characterization of a heterocyclic meta-aramid fiber with outstanding thermal stability. High Perform Polym, 2020, 33: 554

Funding

the National Natural Science Foundation of China(52090030)

National Key Research and Development Program of China(2022YFA1205300)

Pioneer and Leading Goose R&D Program of Zhejiang(2023C01190)

the Natural Science Foundation of Zhejiang Province(LR23E020003)

Hundred Talents Program of Zhejiang University(188020*194231701/113)

the Fundamental Research Funds for the Central Universities(226-2024-00074)

Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2022SZ-TD014)

the fellowship of China National Postdoctoral Program for Innovative Talents(BX20230309)

RIGHTS & PERMISSIONS

Donghua University, Shanghai, China