Preparation technologies and advanced applications of transparent plant fiber-based composites
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摘要: 植物纤维作为一种天然可再生和生物降解的绿色环保材料，来源广泛、储量丰富，如林业木竹和作物秸秆资源，广泛应用于制造纤维增强树脂/硅酸盐等复合材料，市场巨大、前景广阔。植物纤维基透明功能材料的研发，对于突破传统工程材料(如纤维板、木塑复合材料)光学不透明的技术瓶颈，拓宽农林木质制品应用范围具有科学意义与研究价值。文章详细梳理了纤维基透明材料的最新研究进展，系统归纳了纤维材料绿色漂白以及透明化的制备机理，以及制备技术的优缺点和关键技术难点。论证了初步脱色透明化处理的透明材料可以优化工艺，在保留植物纤维特性的同时实现多功能化。重点从植物纤维基透明材料的力学、透明度、雾度、阻燃、隔热等方面进行阐述，探讨了纤维透明材料在节能建筑、光电子器件、储能材料领域的应用前景。植物纤维透明材料的开发，未来仍需大量系统化的基础理论研究。随着制备技术及改性方法的不断完善，其性能将得到进一步提升，推动在建筑、光电、储能等领域的应用。Abstract: The plant fiber, as a natural renewable, biodegradable green and eco-friendly material, has a wide range of sources and abundant reserves, such as forestry wood, bamboo, and crop straw resources. It is widely used in the manufacturing of composite materials, such as fiber-reinforced resins/silicates, with a huge market and broad prospects. The development of transparent functional materials based on plant fibers has scientific significance and research value in breaking through the technical bottleneck of optical opacity for the traditional engineering materials (such as fiberboard and wood plastic composites) and expanding the application range of agricultural and forestry biomass products. The article provides a detailed overview of the latest research progress on fiber-based transparent materials. It systematically summarizes the mechanisms of green bleaching and transparency of plant fiber materials, as well as the characteristics and key difficulties of for the preparation techniques. It has been demonstrated that transparent materials treated with preliminary decolorization and transparency can optimize the process, and achieve the multifunctionality while retaining the characteristics of plant fibers. This article focuses on the mechanics, transparency, haze, flame retardancy, and thermal insulation of plant fiber based transparent materials, and explores the application prospects of fiber transparent materials in energy-saving buildings, optoelectronic devices, and energy storage materials. There is still a lot of systematic research to be promoted in the utilization of plant fiber transparent materials. With the continuous improvement of preparation technology and modification methods, its performance will be further improved, promoting its application in fields such as architecture, optoelectronics, and energy storage.
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图 1 透明植物纤维基复合材料的(a)微观结构；(b)制备原理
Figure 1. (a) microstructure and (b) preparation principle for transparent plant fiber-based composites
图 2 透明纤维材料的分类及制备过程：(a)透明木材照片[20]；(b)透明木SEM图[20]；(c)透明纤维板照片[24]；(d)透明纤维板SEM图[24]；(e)纯生物质透明板照片[25]；(f)纯生物质透明板SEM图[25]
Figure 2. Classification and preparation process of transparent fiber materials: (a) photograph and (b) SEM image of transparent wood[20]; (c) photograph and (d) SEM image of transparent fiberboard[24]; (e) photograph and (f) SEM image of pure biomass transparent board[25]
图 3 不同界面改性的透明纤维材料：(a)多层透明木[40]；(b)蒸汽爆破处理的竹纤维材料[41]；(c)热处理亚麻纤维增强材料三维模型[44]；(d)HA-PVA水凝胶的冷冻辅助盐析处理[43]；(e)碱溶胀处理水凝胶[45]；(f)透明杨木贴面乙酰化改性[48]；(g)琥珀酰化处理的透明木[49]；(h)基于硫醇-烯体系聚合的透明木 [50]
Figure 3. Transparent fiber materials in different interface modifications: (a) multi-layer transparent wood[40]; (b) bamboo fiber materials treated by steam explosion[41]; (c) three dimensional model of flax fiber reinforced material by heat treatment [44]; (d) freeze-assisted salting out treatment of HA-PVA hydrogel[43]; (e) alkali swelling treated hydrogel[45]; (f) acetylation modification of transparent poplar veneer[48]; (g) succinylation treatment of transparent wood[49]; (h) transparent wood by thiol ene system polymerization[50]
图 4 纤维基透明材料的不同复合方法：(a)溶液浸渍法制备透明木[55]；(b)熔融浸渍法制备储能透明材料[53]；(c)纤维混杂法制备秸秆纤维透明材料[24]；(d)纤维混杂法制备木粉增强透明材料[54]
Figure 4. Different composite methods of fiber based transparent materials: (a) preparation of transparent wood by solution impregnation[55]; (b) preparation of energy storage transparent materials by melt immersion method[53]; (c) preparation of straw fiber transparent materials by fiber mixing method[24]; (d) preparation of wood powder reinforced transparent materials by fiber mixing method[54]
图 5 纤维透明材料的光学性能比较：(a)木基透明材料的光线传输图；(b)不同纤维透明材料的透光率[34]；(c)透明木材的透射图及其散射图[20]；(d)天然木与透明木的透射率[20]；(e)不同厚度纤维材料的透光率 [68]；(f)锑掺杂透明木和玻璃的隔热实验温度-时间曲线[70]；(g)玻璃及不同纤维透明材料的导热系数[71]；(h)椴木、环氧树脂及其透明木材的热释放率[72]；(i)不同透明木和PVA薄膜的储能模量[74]；(j)原始竹材、脱木质素竹材和透明竹材的抗拉强度比较[75]；(k)纤维板及其层压板的拉伸应力-应变曲线[77]；(l)层压板、透明玻璃和树脂的弯曲应力-应变曲线[77]
Figure 5. Optical properties comparison of fiber transparent materials: (a) light transmission of wood-based transparent materials; (b) transmittance of different transparent materials[34]; (c) transmission and scattering images of transparent wood[20]; (d) transmittance of natural and transparent woods[20]; (e) transmittance of fiber materials with different thicknesses[68]; (f) temperature-time curves of insulation experiments for glass and antimony doped transparent wood [70]; (g) thermal conductivities of glass and fiber transparent materials [71]; (h) heat release rate of basswood, epoxy resin, and transparent wood[72]; (i) storage modulus of transparent woods and PVA thin films[74]; (j) tensile strength comparison of treated bamboos[75]; (k) tensile stress-strain curves of fiberboard and laminates [77]; (l) bending stress-strain curves of laminated panels, transparent glass, and resin[77]
图 6 纤维透明材料的节能建筑应用：(a)木材填充通道结构中碳点、聚乙烯醇和纤维素之间的氢键相互作用[9]；(b)发光透明材料对甲醛气体进行实时视觉检测[9]；(c)冷态无色与热态彩色可逆变色透明竹材[78]；(d)含二氧化钛纳米粒子的双功能透明木[79]；(e)基于两层透明木材的玻璃系统的U因子和太阳热增益系数变化曲线[12]；(f, g)插入纤维素气凝胶薄膜的中空玻璃[80]
Figure 6. Energy saving building applications of fiber transparent materials: (a) hydrogen bonding interactions between carbon dots, polyvinyl alcohol, and cellulose in wood filled channel structures[9]; (b) real time visual detection of formaldehyde gas using luminescent transparent materials[9]; (c) cold colorless and hot colored reversible color changing transparent bamboo[78]; (d) double functional transparent wood containing titanium dioxide nanoparticles[79]; (e) the U-factor and solar thermal gain coefficient variation curve of a glass system based on two-layer transparent wood[12];(f, g) hollow glass inserted with cellulose aerogel film[80]
图 7 纤维透明材料在光电子器件的应用：(a)透明纸铺覆砷化镓电池的电流密度与电压特性关系曲线[13]；(b)砷化镓电池反射率与入射角和波长的函数等值线图[13]；(c)入射到太阳能电池上的光分布示意图[16]；柔性导电透明木材 (d)点亮LED灯泡照片，(e)电导率与温度的关系和(f)不同温度变化循环的电导率变化[10]；FeCl3/聚丙烯酸透明木材(g)电导率随FeCl3浓度的变化关系和(h, i)人体动作电学响应[81]；涂覆铟锡氧化物的透明木材(j)模型图，(k，l)透射/反射功率的比较[82]
Figure 7. Optoelectronic devices applications of fiber transparent materials: (a) relationship curve between current density and voltage characteristics of transparent paper coated gallium arsenide batteries[13]; (b) contour plot of reflectivity as a function of incident angle and wavelength for gallium arsenide batteries[13]; (c) schematic diagram of light distribution incident on solar cells[16]; (d) photos of LED bulbs, (e) relationship between conductivity and temperature, and (f) conductivity changes under different temperature cycles for flexible conductive transparent wood[10]; (g) relationship between conductivity and FeCl3 concentration, (h, i) electrical response of human actions for FeCl3/polyacrylic acid transparent wood[81]; (j) model diagram, (k, l)comparison of transmission/reflection power for transparent wood coated with indium tin oxide[82]
图 8 纤维透明材料的热能储存性能：(a)热能储存透明木材[49]；(b, c)不同热能储存的透明木材加热与冷却的DSC谱图[49]；透光储能木材(d)界面结合机制，(e)光传输和热传导和(f)DSC曲线[11]；共聚柔性透明木材(g)共聚物网络，(h)不同温度下的透明度和(i)热导率和热扩散率[8]
Figure 8. Thermal energy storage performance of fiber transparent materials: (a) thermal energy storage of transparent wood[49]; (b, c) DSC spectra of transparent wood with different heat energy storage for heating and cooling[49]; (d) interface binding mechanism, (e) light transmission and thermal conductivity, and (f) DSC curve for translucent energy storage wood [11]; (g) copolymer network, (h) transparency at different temperatures, and (i) thermal conductivity and thermal diffusivity for flexible transparent wood[8]
表 1 植物纤维材料脱色方法比较
Table 1. Comparison of decolorization methods for plant fiber materials
Method Mechanism Character Document Acid delignification Sodium chlorite solution decomposed into chlorine gas and chlorine dioxide by reacting with lignin as a widely used method Good selectivity, moderate process conditions, intact fiber structure, release of harmful gases [35] Alkali delignification The ether bond broken by sodium hydroxide and sodium sulfite reacting with lignin Most lignin and hemicelluloses removed, little cellulose dissolved [36] Biological enzyme delignification The lignin degraded by enzyme to achieve decolorization Eco-friendly , slow reaction speed, no obvious effects [33] Delignification of ionic liquids Low vapor pressure, high solubility and high stability, selectively dissolved lignin Expensive, high purity requirement, toxic [37, 38] Lignin modification Instead of extracting lignin, change the structure and remove the chromophores Structural stability, simple process, low requirement [34, 39] 
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表 2 木材的纤维素、木质素和常见树脂的折射率
Table 2. Refractive index of cellulose, lignin and common resins of wood
Matter Refractive index Basic property Document Air 1.00 Cellulose 1.53 The main component of plant fiber [56,57] Lignin 1.61 Contains special chromophores. [56,57] Polymethyl methacrylate 1.49 Low density, high mechanical strength, unstable nature, explosive [58] Epoxy resin 1.50 Good compatible fiber, difficult to degrade [60] Polyvinylpyrrolidone 1.53 Environmentally friendly, biodegradable, hydrophilic, good
compatible fiber[51] Polylimonene acrylate 1.50 Soluble in alcohol, ether and other organic solvents ,insoluble in water [49] Mercaptan and ene monomer polymer 1.59 High yield, easy photoinduced polymerization, complex shrinkage
strain is low[50] Chitosan and cellulose nanofibers 1.52 Biodegradable, antioxidant, antibacterial, UV protection [59] polyvinyl alcohol 1.51 Low cost, biodegradable, low viscosity, excellent film formation,
toughness, and transparency[18]
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