Research progress of shape memory polymer fibers and reinforced composites
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摘要: 形状记忆聚合物纤维及增强复合材料是从形状记忆聚合物中发展起来的一种新型智能材料。它除了具有质量轻便、价格低廉、变形能力优异、模量变化可逆、驱动方式多样、设计结构简单等优点，还具备弹性模量较高、回复应力较大等特点，有效地弥补了传统形状记忆聚合物的不足。首先概述了形状记忆聚合物纤维及纤维增强形状记忆聚合物复合材料的驱动方法，并总结了制备形状记忆聚合物纤维的纺丝方法，其次分析了形状记忆聚合物纤维及纤维增强形状记忆聚合物复合材料在多个领域的潜在应用，最后讨论了目前存在的问题并对未来的研究进行了展望。
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关键词:
- 形状记忆聚合物纤维 /
- 纤维增强形状记忆聚合物复合材料 /
- 驱动方法 /
- 纺丝方法 /
- 潜在应用
Abstract: Shape memory polymer fibers and reinforced composites are novel smart materials developed from shape memory polymers. They have advantages of light weight, low price, excellent deformation capability, reversible modulus, various driving methods and simple structures. Furthermore, they have some characteristics, like high elastic modulus, large recovery stress, etc., that can effectively amend the shortcomings of traditional shape memory polymers. This article first outlines the driving methods of shape memory polymer fibers and fiber reinforced shape memory polymers, and summarizes the spinning methods of shape memory polymer fibers. Then the potential applications of shape memory polymer fibers and fiber reinforced shape memory polymers in various fields are analyzed. Finally, the current problems are discussed and the future research is prospected. -
图 1 水驱动：(a) 水驱动调温羊毛针织衫[28]；(b) 大壶腹状蛛丝蛋白2(eMaSp2)的基因设计[33]；(c) eMaSp2纤维的超牵引能力[33]；(d) 蜘蛛丝定向收集水滴的能力[34]
Figure 1. Actuation by water: (a) Water-driven temperature-adjustable wool knitwear[28]; (b) Genetic design of engineered major ampullate spidroin 2 (eMaSp2)[33]; (c) Supercontraction of eMaSp2 fiber[33]; (d) Ability of spider fiber to collect water droplets directionally[34]
Hd—Dry state; Hw—Wet state
图 2 热驱动：(a) 屏蔽效能与回复角的关系[38]；(b) 复杂结构的形状记忆效应[39]；(c) 冷编程复合材料的形状记忆效应[40]；(d) 体温触发纤维的形状记忆效应[41]
Figure 2. Actuation by heat: (a) Relationship between shielding effect and recovery angle[38]; (b) Shape memory effect of complex structures[39]; (c) Shape memory effect of cold-programming composite[40]; (d) Shape memory effect of fiber by body temperature[41]
图 3 电驱动: ((a)~(d)) 50 V、35 V、15.87 V、60 V电压下复合材料的形状回复过程[51-54]；(e) 电触发纤维的可逆驱动[58]
Figure 3. Actuation by electricity: ((a)-(d)) Shape recovery process of composites under 50 V, 30 V, 15.87 V and 60 V[51-54]; (e) Reversible change of fibers by electricity[58]
Uoff—Voltage source off; Uon—Voltage source on
图 4 光驱动：(a) 光触发界面损伤自修复[62]；(b) 不同功率密度的近红外光诱导形状记忆行为[63]；(c) 光驱动纤维超大收缩的示意图[64]；((d)~(e)) 光驱动精确折纸、回复断裂蜘蛛网、闭合绳袋、筛选不同尺寸的玻璃球[64]
Figure 4. Actuation by light: (a) Self-healing of interface damage by light[62]; (b) Shape memory behavior induced by near infrared light at different power densities[63]; (c) Schematic diagram of ultra large shrinkage of fiber by light[64]; ((d)-(e)) Origami, recover broken spider webs, close rope bags and screen glass balls of different sizes by light[64]
RT—Room temperature
图 5 静电纺丝方法；(a) 纤维网孔径的可逆变化[66]；(b) 纤维支架的形状回复过程[67]；(c) 双重静电纺丝装置示意图[71]；(d) 三重形状记忆效应示意图[72]
Figure 5. Electrospinning method: (a) Reversible change of the pore sizes[66]; (b) Shape recovery process of the fiber scaffolds[67]; (c) Schematic diagram of the double electrospinning device[71]; (d) Schematic diagram of the triple shape memory effect[72]
εA—Permanent shape; εB,load—First temporary shape; εB—First temporary fixed shape; εC,load—Second temporary shape; εC—Second temporary fixed shape; εB,rec—Recovered shape of εB; εA,rec—Recovered shape of εA
图 6 熔融纺丝方法及湿法纺丝方法：(a) 熔融纺丝装置示意图[75]；(b) 恒定应力下纤维的双向形状记忆效应[78]；(c) 蒸汽处理后纤维的形状记忆效应[80]；(d) 湿法纺丝装置示意图[33]
Figure 6. Melt spinning method and wet spinning method: (a) Schematic diagram of melt spinning device[75]; (b) Two-way shape memory effect of fiber under constant stress[78]; (c)Shape memory effect of fiber after steam treatment[80]; (d) Schematic diagram of wet spinning device[33]
图 7 生物医学应用：(a) 微弯曲回复过程的有限元模拟示意图[87]；(b) 外科手术缝合线的应用过程[88]；(c) 药物输送系统示意图[89]；(d) 伤口敷料示意图[91]
Figure 7. Biomedical applications: (a) Schematic diagram of finite element simulation of microbending recovery process[87]; (b) Process of applying the surgical suture[88]; (c) Schematic diagram of drug delivery system[89]; (d) Schematic diagram of wound dressing[91]
图 8 软机器人应用：(a) 卷绕式复合纱线的收缩机制示意图[94]；(b) 捕鱼用形状记忆空心笼[95]；(c) 抓取5 g螺栓的电活性抓手[96]；((d)~(e)) 热驱动花朵、机械手[97]；((f)-(g)) 电致动机械抓手、步行机器人[98]
Figure 8. Applications in soft robotics: (a) Schematic diagram of the shrinkage of coiled yarn[94]; (b) Shape memory cage for fishing[95]; (c) Electricity-driven gripper for grabbing 5 g bolt[96]; ((d)-(e)) Thermally-driven flower and gripper[97]; ((f)-(g)) Electricity-driven gripper and walking robot[98]
图 9 航空航天应用：(a) 变刚度机翼模型[99]；(b) 平板式可展开结构的形状回复过程[100]；(c) 箱型结构的形状回复过程[102]；(d) 立方体结构的形状回复过程[103]
Figure 9. Aerospace applications: (a) Variable stiffness wing model[99]; (b) Shape recovery process of flat expandable structure[100]; (c) Shape recovery process of box structure[102]; (d) Shape recovery process of cube structure[103]
图 10 纺织服装应用及自愈合应用：(a) 针织结构对羊毛针织物形状记忆性能的影响[105]；(b) 一体式压力长袜结构示意图[107]；(c) 自愈合的空心金字塔[109]；(d) 自愈合涂层[110]；(e) 水泥裂纹闭合的概念模型[111]
Figure 10. Applications in textile and self-healing: (a) Influence of knitting structure on the shape memory effect of wool fabrics[105]; (b) Structure diagram of one-piece pressured stockings[107]; (c) Self-healing hollow pyramid[109]; (d) Self-healing coating[110]; (e) Conceptual model of closing cement crack[111]
表 1 形状记忆聚合物纤维(SMPFs)和纤维增强形状记忆聚合物复合材料(FRSMPs)的种类、驱动方式和应用前景的总结
Table 1. Summary of the types, driving methods and applications of shape memory polymer fibers (SMPFs) and fiber reinforced shape memory polymers (FRSMPs)
SMPF Types Driving methods Applications Artificial spider silk fiber Water Textile/aerospace[30,33-34] Ga@TPU fiber Heat Textile[41] TPU-Ag-Cu2S-PBO fiber Light Self-healing[62] Linear liquid crystal polymer fiber Light Soft robotics[64] PCL fiber Heat Biomedical [66] poly(D,L-lactide-co-trimethylene carbonate) fiber Heat Biomedical [67] PLA-OLA fiber Heat Biomedical [69] SMPU fiber Heat Textile[73,75,80-82,106-107] EVA fiber Heat Soft robotics/biomedical [78] BCH-SMPU fiber Heat Biomedical [88-89] HA-DEX-SMPU fiber Heat Biomedical [90] PLLA-a-PHB fiber Heat Biomedical [92] UHMWPE fiber Heat Soft robotics[93] CNT/TPU yarn Electricity Soft robotics[94] PCL-SEBS fiber Heat Self-healing[109] FRSMP CF/EP Heat, electricity, light Aerospace[35-36,52,59,101,102-103] CF/PVA Heat, electricity Soft robotics[37,51] CF/SMPU Heat Microwave shielding/biomedical [38,87] GF/EP Heat Aerospace[39] CF-MWCNT/EP Heat Aerospace[40] Ag@CF/EP Electricity Aerospace[54] CNT/SMPU Electricity, light Soft robotics/strain sensors[56-57] PAn/PVA Light Soft robotics[63] Skin collagen fiber/waterborne polyurethane Water Biomedical [91] Ag@CF/PVA Electricity Soft robotics[96] Steel fiber/EP Heat Soft robotics[97] CNT/POE Electricity, light Soft robotics[98] PU fiber-nylon fiber/EP Heat Aerospace[99] CF-CB/EP Electricity Aerospace[100] PCL fiber/EP Heat Self-healing[110] Notes: TPU—Thermoplastic polyurethane; PBO—Poly(p-phenylene benzobisoxazole); PCL—Polycaprolactone; PLA—Polylactic acid; OLA—Oligomer polylactic acid; SMPU—Shape memory polyurethane; EVA—Poly[ethylene-co-(vinyl acetate)]; BCH—Berberine hydrochloride; HA—Hydroxyapatite; DEX—Dexamethasone; PLLA—Poly(L-lactide); a-PHB—Atactic polyhydroxybutyrate; UHMWPE—Ultrahigh molecular weight polyethylene; CNT—Carbon nanotube; SEBS—Styrene ethylene butylene styrene; EP—Epoxy; PVA—Polyvinyl alcohol; MWCNT—Multi-walled carbon nanotubes; PAn—Polyaniline; PU—Polyurethane; CF—Carbon fiber; POE—Poly(ethylene-co-octene). 
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