High-performance ZnS∶Cu Based Mechanoluminescent Elastomers and Their Applications in Visually Interactive Fabrics

WANG Yue; YANG Wei-feng; CHEN Hao-ting; ZHONG Xin; ZENG Guo-ping; LI Yao-gang; HOU Cheng-yi

doi:10.37188/CJL.20220233

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High-performance ZnS∶Cu Based Mechanoluminescent Elastomers and Their Applications in Visually Interactive Fabrics

Luminescence Industry and Technology Frontier | Updated：2022-11-04

- High-performance ZnS∶Cu Based Mechanoluminescent Elastomers and Their Applications in Visually Interactive Fabrics Enhanced Publication
- Chinese Journal of Luminescence Vol.43, Issue 10, (2022)
- Affiliations：
  
  State Key Laboratory for Modification of Chemical Fibers and Polymer Material， College of Materials Science and Engineering， Donghua University,Shanghai,China,201620;Anta（China） Co.， Ltd.,Xiamen,China,361000;Engineering Research Center of Advanced Glass Manufacturing Technology， Ministry of Education，College of Materials Science and Engineering， Donghua University,Shanghai,China,201620
- Author bio：
- Funds：
  
  Shanghai Rising-Star Program(20QA1400300);DHU Distinguished Young Professor Program(LZB2019002)
- DOI：10.37188/CJL.20220233 CLC： O482.31
- Published：05 October 2022，
  
  Received：16 June 2022，
  
  Revised：01 July 2022，
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王玥,杨伟峰,陈浩廷等.高性能ZnS∶Cu基力致发光弹性体及其在视觉交互织物中的应用[J].发光学报,2022,43(10):1609-161910.37188/CJL.20220233.

WANG Yue,YANG Wei-feng,CHEN Hao-ting,et al.High-performance ZnS∶Cu Based Mechanoluminescent Elastomers and Their Applications in Visually Interactive Fabrics[J].Chinese Journal of Luminescence,2022,43(10):1609-161910.37188/CJL.20220233.
王玥,杨伟峰,陈浩廷等.高性能ZnS∶Cu基力致发光弹性体及其在视觉交互织物中的应用[J].发光学报,2022,43(10):1609-161910.37188/CJL.20220233. DOI：

WANG Yue,YANG Wei-feng,CHEN Hao-ting,et al.High-performance ZnS∶Cu Based Mechanoluminescent Elastomers and Their Applications in Visually Interactive Fabrics[J].Chinese Journal of Luminescence,2022,43(10):1609-161910.37188/CJL.20220233. DOI：

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"data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "纳米粒子掺杂的方法来增加应力传递位点，从而提高ZnS∶Cu复合弹性体的发光强度。通过挤出包覆、3D打印、丝网印刷等工艺实现了力致发光智能织物的连续化和图案化制备，改善了力致发光纺织品的力⁃光转换的灵敏度和穿戴舒适性问题，其在可穿戴传感、运动健康监测、智慧交通警示等方面具有潜在的应用价值。" } ] } ] }, { "lang": "en", "data": [ { "name": "p", "data": [ { "name": "text", "data": "With the rapid development of flexible wearable electronics， the demand for intelligent wearable devices has remarkably increased. Smart luminescent clothing with the ability of visual interaction has attracted wide attention due to its versatile functions. Elastico-mechanoluminescent materials such as ZnS∶Cu mechanoluminescent elastomers have potential applications in smart luminescent cloths/garments because of their repeatable force-to-light visualized sensing capabilities. In this work， we increased the stress transfer sites in ZnS∶Cu mechanoluminescent elastomers through tunning the network structure of the elastic polymer matrix and the doping of Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " nanoparticles， thus improved the luminescence intensity of the mechanoluminescent elastomer. The continuous and patterned preparation of mechanoluminescent textile has also been achieved through extrusion coating， 3D printing， and screen printing mechanoluminescent elastomers on traditional textiles. The sensitivity and wearing comfort of the luminescent woven textiles have therefore been improved， which provides potential value for this mechanoluminescent elastomers in applications including wearable sensing， health monitoring， traffic warning， " }, { "name": "italic", "data": [ { "name": "text", "data": "etc" } ] }, { "name": "text", "data": "." } ] } ] } ], "keyword": [ { "lang": "zh", "data": [ [ { "name": "text", "data": "力致发光" } ], [ { "name": "text", "data": "弹性体" } ], [ { "name": "text", "data": "纳米粒子" } ], [ { "name": "text", "data": "可视化响应" } ], [ { "name": "text", "data": "发光织物" } ] ] }, { "lang": "en", "data": [ [ { "name": "text", "data": "mechanoluminescence" } ], [ { "name": "text", "data": "elastomers" } ], [ { "name": "text", "data": "nanoparticles" } ], [ { "name": "text", "data": "visualized mechanical sensing" } ], [ { "name": "text", "data": "luminescent textiles" } ] ] } ], "highlights": [], "body": [ { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "1　引　　言" } ], "level": "1", "id": "s1" } }, { "name": "p", "data": [ { "name": "text", "data": "在过去的十年中，可穿戴设备的出现促进了显示技术、传感、电子和能量收集与存储等各领域的发展。便携式或可穿戴电子设备通常需要可视化显示作为信息交互和传播的关键工具" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "1", "type": "bibr", "rid": "R1", "data": [ { "name": "text", "data": "1" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。然而，传统的发光器件严重依赖于外部能源供应，刚性的电池组件导致这种系统牺牲了穿戴舒适性和轻量化特性，难以满足下一代可穿戴设备的要求。因此，亟需开发一种无需依赖外部电源的新型发光器件，如仅需要在简单的环境刺激下就能够产生光的发光材料" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "2", "type": "bibr", "rid": "R2", "data": [ { "name": "text", "data": "2" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "4", "type": "bibr", "rid": "R4", "data": [ { "name": "text", "data": "4" } ] } } ], "rid": [ "R2", "R3", "R4" ], "text": "2-4", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。力致发光（Mechanoluminescence，ML）是指材料在受到机械应力的作用，如摩擦、挤压、碰撞、破碎以及超声等产生的发光现象。其中，力致发光材料中力学信号和光学信号之间具有对应关系，且光学信号可以随着力学信息的改变而呈现出明显的变化" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "5", "type": "bibr", "rid": "R5", "data": [ { "name": "text", "data": "5" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "6", "type": "bibr", "rid": "R6", "data": [ { "name": "text", "data": "6" } ] } } ], "rid": [ "R5", "R6" ], "text": "5-6", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "，这为可视化力学传感提供了可能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "7", "type": "bibr", "rid": "R7", "data": [ { "name": "text", "data": "7" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "1999年，Xu等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "8", "type": "bibr", "rid": "R8", "data": [ { "name": "text", "data": "8" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "首次从ZnS∶Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "和SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "∶Eu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "中发现了弹性材料力致发光现象，并介绍了将无机力致发光材料与有机弹性体复合用于目标结构应力或应变可视化观测的基本原理，这标志着现代力致发光现象研究领域的一个转折点。ZnS∶Mn/Cu半导体体系与SrAl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "∶Eu电介质体系不同的是，前者不需要额外的紫外光激发就可以实现重复的发光，而且弹性力致发光强度高、可重复性好，是典型的自恢复型弹性力致发光材料。ZnS半导体材料的能量带隙较大，其本征发射峰主要位于紫外区域，金属阳离子掺杂不仅可以提高量子点的荧光产率及稳定性，而且还能调节ZnS材料的发射光谱范围，其掺杂的激活剂离子主要来源于过渡金属离子（Mn" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "、Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "）" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "9", "type": "bibr", "rid": "R9", "data": [ { "name": "text", "data": "9" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "11", "type": "bibr", "rid": "R11", "data": [ { "name": "text", "data": "11" } ] } } ], "rid": [ "R9", "R10", "R11" ], "text": "9-11", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。大多数研究人员认为弹性ML本质上与压电性和陷阱水平有关" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "12", "type": "bibr", "rid": "R12", "data": [ { "name": "text", "data": "12" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "14", "type": "bibr", "rid": "R14", "data": [ { "name": "text", "data": "14" } ] } } ], "rid": [ "R12", "R13", "R14" ], "text": "12-14", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "：非对称的ZnS∶Mn/Cu压电材料在力致作用下会产生压电性，使能带倾斜，陷阱能级深度减小，从而释放陷阱中的载流子；然后载流子复合的能量转移到弹性ML的发光中心，进而产生发光。弹性力致发光器件的组成和结构通常比较简单，不仅易于制造，而且具有高度稳定的机械和光学性能" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "15", "type": "bibr", "rid": "R15", "data": [ { "name": "text", "data": "15" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "能够感知并响应环境变化的信息交互纺织品，即智能纺织品，近年来随着柔性电子产业的发展而备受关注。特别是，发光纺织品因其具有视觉交互的特性，成为智能纺织品的重要门类，在安全警示、运动健康检测、舞台装饰等具有重要应用。目前研究较多的发光服装多集中在电致发光领域，但这类发光服装须配有便携式的随身能源，这很大程度上限制了其在智能服装领域的发展。而ML弹性复合材料可与传统的纺织品相结合制备出可穿戴发光织物，实现对人体特定部位的皮肤、关节、肌肉和骨骼发生的各种变形的可视化运动监测，满足当前轻质化、柔性化的可穿戴需求。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "近年来，科学家在ML可穿戴器件上取得了一系列成果，Zhang等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "16", "type": "bibr", "rid": "R16", "data": [ { "name": "text", "data": "16" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "通过简单地将力致发光过渡金属掺杂硫化锌（ZnS）/聚二甲基硅氧烷（PDMS）材料沉积在PDMS制备而成的弹性纤维上，设计了一种可伸缩的柔性机械发光纤维。这种ML纤维经拉伸、扭转、弯曲等变形后，力学性能和光学性能稳定。这些纤维可以被编织成可伸展和可弯曲的显示器及夜间照明设备的织物。Park等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "17", "type": "bibr", "rid": "R17", "data": [ { "name": "text", "data": "17" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "开发了一种基于复合纤维（ZnS∶Cu/PDMS）和聚四氟乙烯纤维的纺织品运动驱动电致发光系统，这种纺织品系统与之前一些研究者的研究工作相比，制备工艺相对能规模化，比较容易制造并应用于智能服装。这些ML发光器件由于弹性基体的应力耗散作用，大量机械能在沿高分子链传递时发生损耗，导致其发光强度较弱。Song等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "18", "type": "bibr", "rid": "R18", "data": [ { "name": "text", "data": "18" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "以导电纺织纤维为电极，将其嵌入到平行取向的PDMS/ZnS复合材料中，实现了ML与EL（电致发光）的综合发光效果，从而增强了发光亮度。此外，ML发光器件多为手工制造的二维薄膜形态，受到制备工艺较复杂、与织物基底的适配性差、批量化制造技术不成熟的限制，难以适应人体关节的三维大尺度机械形变，无法实现人体运动的准确监测。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文利用调控弹性聚合物基体和添加纳米粒子等方法，克服了现有力致发光织物发光性能较差的问题；开发了基于织物基底的ML材料柔性印刷工艺和ML纤维器件的连续化制备工艺，改善了力致发光纺织品的力-光转换的灵敏度和穿戴舒适性的问题。当Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "粒径为10 nm、添加量为力致发光粉的15%、聚合物基体为混合胶（等质量比混合）时，该体系具备最佳的力致发光效果，同时也具有一定的发光稳定性。基于上述复合体系，我们还开发了多种力致发光纺织品制备体系：采用挤出包覆工艺实现力致发光纤维的批量化制备，克服了现有力致发光材料不能连续化制备的缺陷，并通过编织工艺进一步得到智能发光织物；通过3D打印技术和丝网印刷技术实现弹性力致发光材料在织物基底上的图案化制备，为开发具有实用价值的智能发光服饰提供了方案。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2　实　　验" } ], "level": "1", "id": "s2" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1　智能发光织物的制备" } ], "level": "2", "id": "s2a" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1.1　ZnS∶Cu力致发光弹性体的制备" } ], "level": "3", "id": "s2a1" } }, { "name": "p", "data": [ { "name": "text", "data": "称取适量自制的ZnS∶Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "@Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "力致发光粉（粉体制备如下：称取适量ZnS、助熔剂NaCl和MgCl" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "分别占ZnS基质的6%和10%以及0.15%的激活剂CuSO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "，混合均匀并烘干后，在1 150 ℃的马弗炉内煅烧3 h，反应结束后立即取出置于室温下冷却，粉体冷却后去除杂质并对粉体进行清洗干燥；将处理后的粉体置入pH=5的缓冲溶液中常温搅拌30 min，取适量浓度为0.1 mol/L的Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（SO" }, { "name": "sub", "data": [ { "name": "text", "data": "4" } ] }, { "name": "text", "data": "）" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "溶液并用注射泵（滴速为7 mL/min）缓慢滴入悬浮液中并保持搅拌状态。滴加完毕后，继续在70 ℃下反应1 h。反应结束后，向体系中滴加NaOH溶液调节至中性；洗涤干燥后再经300 ℃下煅烧2 h，得到包覆量为15%的ZnS∶Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "@Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "粉体）以及不同的聚合物胶体：聚二甲基硅氧烷PDMS（道康宁公司（美国））（其中PDMS弹性基质和固化剂按照质量比10∶1混合）、硅胶Silicone（安踏（中国）有限公司提供）（硅胶基质和固化剂按照质量比10∶1混合）、混合胶Mixed-silicone（PDMS与硅胶按照不同质量比混合），其中，力致发光粉与聚合物胶体的质量比均为1∶2。称取适量的不同尺寸（10，20，50，100，150 nm）的SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "（苏州远特新材料有限公司）和Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "（苏州远特新材料有限公司）纳米粒子，将上述五种尺寸的两类纳米粒子分别按照不同质量比掺进混有发光粉的三种聚合物胶体中组成相应的复合弹性体。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "上述所有复合弹性体均采取以下实验步骤：将混合物搅拌均匀，并用真空干燥箱进行真空脱泡，随即倒入聚四氟乙烯磨具（长50 mm、宽8 mm、厚2 mm）中，将装有混合浆料的磨具放进烘箱内干燥固化，固化温度为90 ℃，固化时间为30 min。最后，取出磨具冷却至室温，得到相应的力致发光弹性体，并测试力致发光强度，得到力致发光强度最高的复合体系。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.1.2　力致发光弹性体与织物的结合" } ], "level": "3", "id": "s2a2" } }, { "name": "p", "data": [ { "name": "text", "data": "将上述制备的复合体系材料进行脱泡及预固化处理后倒入自搭的纤维连续化制备装置包覆模具中。将透明的弹性硅胶纤维（直径为1 mm）通过辊轮传送设备，依次通过包覆模具（包覆模具孔径为1.2 mm）来涂覆浆料，随即经过加热装置进行高温固化（固化温度设置为200 ℃），固化后的ML弹性纤维经过一段距离的传送后会降温冷却并经过辊轮进行收集，最终得到ML纤维。将ML纤维与弹性包芯纱线进行编织，可以得到ML织物。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "另将上述制备的复合体系材料进行脱泡及预固化处理后，使用计算机辅助设计软件（AutoCAD）进行数字编程以形成定制图案效果。将所需织物固定在80 ℃的热台上，ML复合材料在织物表面经过3D打印后直接固化，多次通过原始路径打印以增加ML复合体的厚度。打印结束后，得到相应定制化的ML织物。同样地，把弹性织物固定在丝网印刷台上，将混合浆料印刷于织物表面并用热风枪进行烘干，待浆料固化后，重复进行多次印刷步骤以增加ML复合体的厚度，得到ML织物。" } ] } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "2.2　样品性能与表征" } ], "level": "2", "id": "s2b" } }, { "name": "p", "data": [ { "name": "text", "data": "制备的力致发光弹性体样品通过场发射扫描电子显微镜（日立 S-3000N）表征弹性体样品的微观形态；利用光纤光谱仪（ER4000）以及线性机械马达（P01-37X120-C_C1）测试复合弹性体的力致发光强度以及循环发光稳定性；使用电子万能试验机（Instron 5567）对弹性体进行力学性能测试；使用梅特勒动态热机械分析仪（DMA1）对复合弹性体进行损耗分析；力致发光性能测试实验均是由实验室内自主搭建（如" }, { "name": "xref", "data": { "text": "图1", "type": "fig", "rid": "F1", "data": [ { "name": "text", "data": "图1" } ] } }, { "name": "text", "data": "）。该试验平台分为力学测试系统（线性机械马达）和光学检测系统（光纤光谱仪）两个部分。设定线性机械马达实验参数条件为：拉伸速率1 m/s，拉伸加速度0.1 m/s" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，拉伸减速度0.1 m/s" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，拉伸伸长率为100%；所有发光都通过光纤光谱仪的检测（ML光谱积分时间为4 000 ms）。" } ] }, { "name": "fig", "data": { "id": "F1", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图1" } ], "title": [ { "name": "text", "data": "力致发光测试表征示意图" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.1" } ], "title": [ { "name": "text", "data": "Schematic diagram of ML characterization method" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472242&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472249&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472246&type=", "width": "77.13085938", "height": "56.56213379", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3　结果与讨论" } ], "level": "1", "id": "s3" } }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.1　基体网络结构对复合弹性体力致发光的影响" } ], "level": "2", "id": "s3a" } }, { "name": "p", "data": [ { "name": "text", "data": "PDMS是ML体系中应用最为广泛的基体之一。另外，硅胶是用作织物印花中常用的材料，也具备弹性体的特征。二者均是柔性的交联聚合物，PDMS的分子主链是由Si—O键相连，侧基连接甲基基团以及少量其他侧基基团，而硅胶是由含甲基和少量乙烯基的硅氧链节组成，官能基团不同导致它们具有不同的机械性能。我们尝试将两种胶体按照不同比例配置成混合胶体系（Mixed-silicone），最后发现当二者质量比为1∶1的条件下具有最佳的发光效果（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（a）），比单一组分的PDMS复合体以及印花硅胶复合体力致发光强度都高（" }, { "name": "xref", "data": { "text": "图2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图2" } ] } }, { "name": "text", "data": "（b））。这是由于两种组分在1∶1条件下，二者的分子链段相互缠结交联的作用最强。从混合胶的ML弹性体断面图可以看出（" }, { "name": "xref", "data": { "text": "图 2", "type": "fig", "rid": "F2", "data": [ { "name": "text", "data": "图 2" } ] } }, { "name": "text", "data": "（c）），ZnS颗粒可以均匀分散在混合胶基体中，界面间的结合紧密，有利于应力传递。为了进一步探究混合胶ML强度较高的原因，我们还对不同聚合物基体做了耗散比对。应力传递和耗散可用拉伸-回缩循环来表征（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（a）~（c））。在没有能量损耗的前提下，样品的拉伸曲线应和回缩曲线重合。如果曲线没有重合则表明外力所做的拉伸功与样品作用于外力的收缩功不吻合，就会产生机械滞后曲线，曲线包围的面积代表了非辐射能量的耗散。滞后曲线包围的面积越大，代表了能量耗散得越多。从图中可以看出，混合胶体系整体的能量损耗均小于其他体系。另外，从动态力学分析（DMA）中也可以得出这一结论（" }, { "name": "xref", "data": { "text": "图3", "type": "fig", "rid": "F3", "data": [ { "name": "text", "data": "图3" } ] } }, { "name": "text", "data": "（d）~（f））。分别测试了三种ML弹性体的储能模量" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "text", "data": "′以及损耗模量" }, { "name": "italic", "data": [ { "name": "text", "data": "E" } ] }, { "name": "text", "data": "″，从而得知损耗tan" }, { "name": "italic", "data": [ { "name": "text", "data": "δ" } ] }, { "name": "text", "data": "的大小。可以看出，混合胶基体在不同频率下的损耗因子都是最小的，这表明其内耗最小，在获取相同机械能时可传输到发光粉颗粒上最多的机械能。这也表明了作用在ML上的有效功最多，发光效果最好。" } ] }, { "name": "fig", "data": { "id": "F2", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图2" } ], "title": [ { "name": "text", "data": "（a）不同比例的混合胶弹性体的ML；（b）三种弹性体力致发光光谱；（c）混合胶弹性体断面扫描电子显微镜图。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.2" } ], "title": [ { "name": "text", "data": "（a）The relative ML intensities of various as-synthesized elastomers of mixed-silicone with different proportion. （b）The ML spectra of three kinds of elastomers. （c）SEM images of ZnS∶Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "/Mixed-silicone composite elastomer." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472253&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472257&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472255&type=", "width": "153.60076904", "height": "45.52944946", "fontsize": "" } ] } }, { "name": "fig", "data": { "id": "F3", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图3" } ], "title": [ { "name": "text", "data": "三种ML弹性体拉伸回缩应力-应变曲线：（a）ZnS/PDMS，（b）ZnS/Silicone，（c）ZnS/Mixed-silicone；三种ML弹性体动态力学分析：（d）ZnS/PDMS，（e）ZnS/Silicone，（f）ZnS/Mixed-silicone。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.3" } ], "title": [ { "name": "text", "data": "Mechanical hysteresis curves of various as-synthesized elastomers：（a）ZnS/PDMS，（b）ZnS/Silicone，（c）ZnS/Mixed-silicone. Dynamic mechanical analysis of ML elastomers：（d）ZnS/PDMS，（e）ZnS/Silicone，（f）ZnS/Mixed-silicone." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472262&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472268&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472265&type=", "width": "164.47082520", "height": "78.32568359", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "在热固性化学交联材料体系中，ML发光粉颗粒处于分子链的三维交联网络中。当受到外部机械力的刺激时，这些复合材料内部的高分子链段会得以伸展并表现为材料的形变，应力同时会通过高分子链段上的化学交联点传递到ML粉体颗粒上" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "19", "type": "bibr", "rid": "R19", "data": [ { "name": "text", "data": "19" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。之所以混合胶基体表现出更强的ML，是因为混合胶的基体是PDMS和硅胶混合后经过化学交联以及加热固化后，最终形成热固性的弹性体。这两种大分子链段的分子间以及分子内部的相互作用形成了非单一分子链的“双网络”结构，这种结构交联网点要比单一分子链段的“单网络”结构（如PDMS、硅胶）更多。当有应力传输时，交联网点也能将应力更多地作用在ZnS粒子上。而当应力消除后，ML弹性体因其自身具有自恢复的属性，其分子链段可恢复到受力前的状态。" } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.2　纳米粒子对复合弹性体力致发光的影响" } ], "level": "2", "id": "s3b" } }, { "name": "p", "data": [ { "name": "text", "data": "ML弹性体受到应力刺激后，其弹性变形缓冲了作用于刚性ZnS微粒的应力或拉伸，使压电场变形减弱从而不能引发大量的电子脱陷和明显的ML。在复合材料中，通常会在聚合物中额外添加一些纳米粒子起到增韧的目的，以此来改善该材料的性能。物理掺杂是构筑高分子聚合物刚性环境的常用方法之一，即直接将颗粒物质以混合的方式渗入高分子基质中，这种方法操作简便且掺杂的比例可调控" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "20", "type": "bibr", "rid": "R20", "data": [ { "name": "text", "data": "20" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。纳米粒子具有与微粒子和块体材料不同的机械性能，纳米粒子的机械效应可以影响摩擦效应或者增强复合基质的韧性" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "21", "type": "bibr", "rid": "R21", "data": [ { "name": "text", "data": "21" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。在ZnS基复合ML材料体系中，可以通过添加一些掺杂粒子将应力更有效地传递给嵌入的ZnS微粒并触发弹性ML。Qian等" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "22", "type": "bibr", "rid": "R22", "data": [ { "name": "text", "data": "22" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "将二氧化硅纳米粒子掺杂进PDMS里面，增强了ML效果。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "在三种聚合物基体（PDMS、Silicone、Mixed-silicone）中分别添加了不同尺寸、不同含量的SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，相应地组成了ZnS/PDMS/SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "、ZnS/Silicone/SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "以及ZnS/Mixed-silicone/SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的复合弹性体。以ZnS/Mixed-silicone/SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "弹性体为例（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（a）~（f）），可以看出，它们的ML会随着纳米粒子含量的增加而增大，当纳米粒子的含量为15%时出现最大值，而继续增加含量，ML会下降，但仍比未掺杂时要高。这可以归因于光散射，当掺杂浓度大于15%时，颗粒密度的增加会阻碍光的散射。与此同时，可以发现纳米粒子的尺寸越小，其ML的强度越高，即掺杂10 nm的粒子效果最好。这是因为在相同的掺杂量条件下，纳米颗粒尺寸的增大导致纳米颗粒数量减少，从而导致掺杂纳米颗粒与ML复合弹性体之间的活性点数减少。经测试发现，SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "尺寸以及含量的影响在PDMS以及硅胶体系中的影响相同，即当SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "含量为15%、尺寸为10 nm时具有最佳的力致发光效果。因此，我们对添加了15%的10 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "的三种弹性体做了ML对比（" }, { "name": "xref", "data": { "text": "图4", "type": "fig", "rid": "F4", "data": [ { "name": "text", "data": "图4" } ] } }, { "name": "text", "data": "（g）），可以看出混合胶体系的ML强于其他两种体系。" } ] }, { "name": "fig", "data": { "id": "F4", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图4" } ], "title": [ { "name": "text", "data": "ZnS/Mixed-silicone/SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "弹性体的力致发光强度：（a）10 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（b）20 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（c）50 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（d）100 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（e）150 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（f）15% SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "；（g）添加15% 10 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "不同弹性体的ML光谱。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.4" } ], "title": [ { "name": "text", "data": "The ML characterization of ZnS/Mixed-silicone/SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " composite elastomers：（a）10 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（b）20 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（c）50 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（d）100 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（e）150 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，（f）15% SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": ". （g）ML spectra of various composite elastomers doped 10 nm SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": " with 15% concentration." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472271&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472276&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472274&type=", "width": "155.19830322", "height": "62.05969238", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "除了SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "以外，我们还发现Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "同样有增强ML的效果。按照同样的测试方法，我们探究了Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "尺寸以及含量对发光强度的影响。以ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "弹性体为例（" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（a）~（f）），可以看出，当Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "含量为15%、尺寸为10 nm时具有最佳的力致发光效果。在PDMS以及硅胶体系中Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "的影响亦相同。将三种聚合物基底以及两种纳米粒子的弹性体做了ML测试（" }, { "name": "xref", "data": { "text": "图5", "type": "fig", "rid": "F5", "data": [ { "name": "text", "data": "图5" } ] } }, { "name": "text", "data": "（g）），可以看出，掺杂Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "的ML相对强度要比SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "更大，这是因为当Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "作为散射粒子与硅-氧链段的聚合物结合时，在可见光范围内具有较高的透光性，透明度更高，且与SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "相比具有较大的介电常数" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "23", "type": "bibr", "rid": "R23", "data": [ { "name": "text", "data": "23" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。同样条件下，Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "相比于SiO" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "对光的阻碍更少。将所有体系的复合弹性体进行力致发光强度的表征，最终ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "体系具有最佳的发光效果。" } ] }, { "name": "fig", "data": { "id": "F5", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图5" } ], "title": [ { "name": "text", "data": "ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "弹性体的力致发光强度：（a）10 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（b）20 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（c）50 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（d）100 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（e）150 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（f）15% Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "；（g）所有复合弹性体的ML光谱。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.5" } ], "title": [ { "name": "text", "data": "The ML characterization of ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " composite elastomers：（a）10 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（b）20 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（c）50 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（d）100 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（e）150 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "，（f）15% Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": ". （g）ML spectra of all of composite elastomers." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472279&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472286&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472282&type=", "width": "155.64894104", "height": "62.19616699", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "我们对ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " 弹性体做了拉伸循环测试（调整积分时间100 ms）。具有双网络结构的复合弹性体在经历4 h的拉伸循环后，我们测试了其近3 500个拉伸循环的力致发光强度，ML没有出现衰减的趋势，始终保持稳定的发光效果（" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（a））。并且从断面图可以看出，经历拉伸循环后的弹性体的基体与颗粒间没有明显的孔隙产生，保持紧密的状态（" }, { "name": "xref", "data": { "text": "图6", "type": "fig", "rid": "F6", "data": [ { "name": "text", "data": "图6" } ] } }, { "name": "text", "data": "（b））。" } ] }, { "name": "fig", "data": { "id": "F6", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图6" } ], "title": [ { "name": "text", "data": "（a）ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "弹性体拉伸4 h后的ML循环测试；（b）拉伸后的ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "弹性体断面SEM照片。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.6" } ], "title": [ { "name": "text", "data": "（a）The relative ML intensities at last tensile 3 500 cycles of ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " elastomer. （b）Cross-sectional SEM images of the tensile ML elastomer." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472289&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472295&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472292&type=", "width": "147.67230225", "height": "52.38778687", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "纳米粒子的加入带来了更多的应力传输活性位点，使得复合弹性体的ML得到提升。综合聚合物基体网络体系对应力传输的影响，我们对掺杂了纳米粒子的混合胶体系的应力发光效果增强绘制了机制图（" }, { "name": "xref", "data": { "text": "图7", "type": "fig", "rid": "F7", "data": [ { "name": "text", "data": "图7" } ] } }, { "name": "text", "data": "），从图中可以看出，这种新的应力发光复合体系（如ZnS/Mixed-silicone/Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "）要比传统的单一组分复合体系（如ZnS/PDMS）能够表现出良好的ML，归因于前者具备更多的应力传位点。" } ] }, { "name": "fig", "data": { "id": "F7", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图7" } ], "title": [ { "name": "text", "data": "（a）单一网络体系的力致发光强度机制示意图；（b）纳米粒子增强双网络体系的力致发光强度机制示意图。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.7" } ], "title": [ { "name": "text", "data": "（a）Schematic diagram of the ML mechanism in single network system. （b）Schematic diagram of the ML enhancing mechanism with dopant nanoparticles in dual network system." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472298&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472303&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472301&type=", "width": "122.60833740", "height": "58.66455078", "fontsize": "" } ] } } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "3.3　基于ZnS∶Cu基力致发光弹性体的可视化传感应用" } ], "level": "2", "id": "s3c" } }, { "name": "p", "data": [ { "name": "text", "data": "在保持一定浓度的ML颗粒（50% ZnS）条件下，已经验证了双网络的混合基底以及添加15% 10 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "粒子能够提升弹性体的ML强度。而复合体系内随着ZnS发光粉的含量增多，其ML也必然会增大，但发光粉浓度不是越大越好。保持一定量的混合胶基体，向其中分别加入四种不同浓度ZnS发光粉：50%、75%、100%、125%，并同时加入相应含量的Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "纳米粒子，当发光粉的含量为125%时，复合浆料无法固化，这是由于ML颗粒（ZnS∶Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "@Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "发光粉）的浓度超出了聚合物基底“溶解度”。类似现象在其他的研究中重现过" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "24", "type": "bibr", "rid": "R24", "data": [ { "name": "text", "data": "24" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。从" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "（a）～（c）可以看出，当发光粉含量为100%时，其断裂伸长率在130%左右，这就不适用于具有形变较大的场景应用。而含量为75%时的应变率可维持在200%左右。在应变为100%条件下测试了其他三种弹性体（50%、75%、100%）的ML光谱（" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "（d））并同时用亮度计采集了实际发光亮度（" }, { "name": "xref", "data": { "text": "图8", "type": "fig", "rid": "F8", "data": [ { "name": "text", "data": "图8" } ] } }, { "name": "text", "data": "（e）），实验结果表明发光粉颗粒数目增多导致其亮度增加。发光粉含量为100%时，它的实际发光强度约为5.5 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "，比75%时（4.9 cd/m" }, { "name": "sup", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "）略微增大，但实际视觉增加的效果并不明显。综合其力学性能的影响，因此，当发光粉含量为75%时更加适合实际应用。" } ] }, { "name": "fig", "data": { "id": "F8", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图8" } ], "title": [ { "name": "text", "data": "含有不同浓度发光粉的弹性体的应力-应变曲线：（a）50%，（b）75%，（c）100%；（d）复合弹性体的力致发光光谱；（e）复合弹性体的亮度值。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.8" } ], "title": [ { "name": "text", "data": "Stress-strain curve of as-synthesized elastomers with different proportions of ZnS phosphors：（a）50%，（b）75%，（c）100%. （d）ML spectra of as-synthesized elastomers. （e）Actual luminance of as-synthesized elastomers." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472307&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472312&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472310&type=", "width": "148.23559570", "height": "75.58810425", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "上述比例制备的ML弹性体对不同模式的机械力刺激具有灵敏的可视化响应，在无外部供电的情况下实现了应力的可视化传感，同时可以保持优异的机械性能。随着可穿戴设备的快速发展，传统的刚性和不可拉伸结构的发光器件已经很难满足柔性、可伸缩性以及舒适性的要求。满足大形变的可拉伸性是模拟人体各种不规则运动的基本且关键的性质，保持柔性的同时还要满足较大形变的可拉伸性对于ML可穿戴器件具有重要意义" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "blockXref", "data": { "data": [ { "name": "xref", "data": { "text": "25", "type": "bibr", "rid": "R25", "data": [ { "name": "text", "data": "25" } ] } }, { "name": "text", "data": "-" }, { "name": "xref", "data": { "text": "26", "type": "bibr", "rid": "R26", "data": [ { "name": "text", "data": "26" } ] } } ], "rid": [ "R25", "R26" ], "text": "25-26", "type": "bibr" } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。为了实现对人体特定部位的皮肤、关节、肌肉和骨骼发生的各种变形的可视化监测，ML智能服装作为良好的穿戴载体，能完美地兼容人体大尺度的三维形变，满足日常运动需求（" }, { "name": "xref", "data": { "text": "图9", "type": "fig", "rid": "F9", "data": [ { "name": "text", "data": "图9" } ] } }, { "name": "text", "data": "）。" } ] }, { "name": "fig", "data": { "id": "F9", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图9" } ], "title": [ { "name": "text", "data": "身体不同部位活动时的运动受力" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.9" } ], "title": [ { "name": "text", "data": "Schematic of mechanical conditions during activities in different parts of body" } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472315&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472320&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472318&type=", "width": "74.76742554", "height": "34.17205811", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "通过自搭建的设备，设计出一种可通过连续化制备方法来实现力致发光纤维的长程构筑（如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "（a））。在设备的设计中，纤维的传输速率要与固化的速度相匹配。整个锟轮的传输速率过快无法保证浆料的完全固化，传输速率过慢则会导致部分浆料由于重力作用聚集成液滴状，这样固化后的纤维包覆不均匀。经过反复调试，最终整个过程中纤维传输速度保持为3 m/min，这样得到的纤维包覆均匀且完全固化，可实现力致发光纤维的批量制备。所制备的ML纤维在外力作用下能重复发光，响应速度快，是具有高度伸长性和柔韧性的机械发光纤维（如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "（b））；将制备得到的ML纤维进一步通过编织工艺，可以与不同材质的纱线进行混合编织，从而可以构建出不同的柔性ML织物（" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "（c））。" } ] }, { "name": "fig", "data": { "id": "F10", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图10" } ], "title": [ { "name": "text", "data": "（a）纤维连续化制备装置示意图；（b）ML纤维结构示意图；（c）ML织物实物及演示发光；（d）3D打印示意图；（e）丝网印刷示意图；（f）印刷图案优化。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.10" } ], "title": [ { "name": "text", "data": "（a）Schematic illustration of continuous preparation process of the ML fibers. （b）Schematic diagram of ML fibers structure. （c）Physical image of ML fabric. （d）Illustration of 3D printing. （e）Illustration of silk-screen printing. （f）Optimization of printing patterns." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472322&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472327&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472325&type=", "width": "122.42797852", "height": "54.42265320", "fontsize": "" } ] } }, { "name": "p", "data": [ { "name": "text", "data": "柔性印刷技术是制备柔性传感器的重要基础，3D打印和丝网印刷是常用的柔性印刷技术" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "27", "type": "bibr", "rid": "R27", "data": [ { "name": "text", "data": "27" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。相比于ML纤维编织的织物，柔性印刷技术在制备工艺方面更加实用。对于一些定制化设计的发光服装，3D打印可以实现小批量的制备。ML浆料可以通过3D打印机打印在弹性织物上，织物下方放入热台，在打印的同时直接加热固化浆料（如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "（d））。3D打印技术可直接将ML浆料与织物相结合得到ML智能服饰，在夜晚光线下拉伸ML服饰可以观察到比较好的发光效果。弹性织物可以选用棉、锦纶、氨纶、聚酯纤维、棉仿等常用的面料，此外，打印针孔的直径可以根据图案的精细化程度来进行调整，以获得更高的分辨率和更精细的定制化发光服饰。丝网印刷是采用刮刀挤压油墨且透过具有图案化模板的网孔转移到承印物表面而实现大量印刷的方法（如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "（e）），它成本低廉、设备应用灵活且印刷精度高，在服装制备、柔性传感、图案设计和电子显示等方面具有广泛的应用。基于前期3D打印的经验，打印的一些“实心”式的连续化图案会因受力不均匀导致图案只能局部发光。为了实现更高效的力致发光效果，ML图案可以根据运动时不同的受力模式来调整。如运动时背部多受到拉伸力，为此，在图案设计上可以采用“横向条纹模式”，这可以更好地与拉伸力匹配，从而优化受力后的发光效果（如" }, { "name": "xref", "data": { "text": "图10", "type": "fig", "rid": "F10", "data": [ { "name": "text", "data": "图10" } ] } }, { "name": "text", "data": "（f））。同时，印花的厚度也会影响实际发光效果。厚度层越厚代表ML颗粒浓度越大，发光效果会提升；而当印刷达到7层（约0.56 mm）时，发光效果比5层（约0.4 mm）较弱，这是由于ML层过厚会阻碍光的散射。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "经过前面的印花工艺的调整，最终设计出适合运动时的最佳发光效果的ML服饰（如" }, { "name": "xref", "data": { "text": "图11", "type": "fig", "rid": "F11", "data": [ { "name": "text", "data": "图11" } ] } }, { "name": "text", "data": "）。模特穿着ML服饰并模拟拉伸运动以及跑步运动姿势，可以基本满足夜晚运动时的发光需求，发光效果可以起到安全警示作用。后续也可进一步与特制的服装面料相结合，可用于监测专业运动员的肢体动态压力分布，避免运动损伤以及强化运动训练" }, { "name": "sup", "data": [ { "name": "text", "data": "[" }, { "name": "xref", "data": { "text": "28", "type": "bibr", "rid": "R28", "data": [ { "name": "text", "data": "28" } ] } }, { "name": "text", "data": "]" } ] }, { "name": "text", "data": "。通过丝网印刷工艺可实现ML服饰大批量生产，提升其实际应用价值，使其在智能发光服装领域具有良好的应用前景。" } ] }, { "name": "fig", "data": { "id": "F11", "caption": [ { "lang": "zh", "label": [ { "name": "text", "data": "图11" } ], "title": [ { "name": "text", "data": "力致发光服装展示。（a）ML服装实物照片；（b）背部做拉伸运动的演示发光；（c）手肘弯曲运动的演示发光；（c）下肢弯曲运动的演示发光。" } ] }, { "lang": "en", "label": [ { "name": "text", "data": "Fig.11" } ], "title": [ { "name": "text", "data": "The show of ML clothes. （a）Physical image of ML clothes. Optical photos of the ML of the clothes under various mechanical stimuli. （b）The back stretching exercises. （c）The elbow bending exercises. （d）The knee bending exercises." } ] } ], "subcaption": [], "note": [], "graphics": [ { "print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472330&type=", "small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472336&type=", "big": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=36472333&type=", "width": "140.47448730", "height": "73.45663452", "fontsize": "" } ] } } ] } ] }, { "name": "sec", "data": [ { "name": "sectitle", "data": { "title": [ { "name": "text", "data": "4　结　　论" } ], "level": "1", "id": "s4" } }, { "name": "p", "data": [ { "name": "text", "data": "本文通过改善弹性聚合物基体、添加Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "纳米粒子等途径来增强力致发光效果，通过纤维制备、3D打印、丝网印刷等手段实现了制备智能发光织物及应用。主要结论如下：" } ] }, { "name": "p", "data": [ { "name": "text", "data": "（1）将PDMS、硅胶、混合胶（PDMS与硅胶等质量比混合）三种不同的聚合物基体分别与ZnS∶Cu" }, { "name": "sup", "data": [ { "name": "text", "data": "2+" } ] }, { "name": "text", "data": "@Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "力致发光粉复合，通过测试力致发光弹性体的ML强度，发现混合胶基底（PDMS与印花硅胶等比例混合）因其具有更多的交联网点（应力传递位点）能够实现较好的ML效果。为进一步提升发光效果，向体系中添加纳米粒子以增多应力传递位点，从而提升ML强度。纳米粒子尺寸、掺杂量以及种类等因素会对ML发光效果产生影响，最终获得掺杂15%的10 nm Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": "粒子的混合胶体系具备最佳ML效果并能保持发光的稳定性。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "（2）在弹性力致发光复合体系基础上，进一步优化了ML粉体浓度比例，即发光粉含量为混合胶的75%，Al" }, { "name": "sub", "data": [ { "name": "text", "data": "2" } ] }, { "name": "text", "data": "O" }, { "name": "sub", "data": [ { "name": "text", "data": "3" } ] }, { "name": "text", "data": " 纳米粒子掺杂含量为发光粉的15%，这种配方的复合浆料能适应多种工业生产方案：通过自搭建的连续化纺丝设备制备出ML纤维，进一步编织ML纤维得到智能发光织物；为提高ML服装的实际应用价值，还利用3D打印、丝网印刷技术实现ML复合材料在织物基底上的图案化制备，解决了ML织物器件的力-光转换的灵敏度和穿戴舒适性问题，为制备智能发光服饰带来实际应用价值。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "随着科技的不断发展，可拉伸的力致发光柔性器件在可视化交互、传感、显示技术等领域有着巨大的潜能。与传统的电致发光器件相比，力致发光器件不需要外部电源即可实现发光。然而，力致发光器件存在着应力带动发光所需阈值较高以及稳定性差等缺点，在实现产业化的道路上还需要不断地探索。" } ] }, { "name": "p", "data": [ { "name": "text", "data": "本文专家审稿意见及作者回复内容的下载地址：" }, { "name": "extlink", "data": { "text": [ { "name": "text", "data": "http://cjl.lightpublishing.cn/thesisDetails# 10.37188/CJL.20220233." } ], "href": "http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20220233." } } ] } ] } ], "footnote": [], "reflist": { "title": [ { "name": "text", "data": "参考文献" } ], "data": [ { "id": "R1", "label": "1", "citation": [ { "lang": "en", "text": [ { "name": "text", "data": "SHI X" }, { "name": "text", "data": "， " }, { "name": "text", "data": "ZUO Y" }, { "name": "text", "data": "， " }, { "name": "text", "data": "ZHAI P" }, { "name": "text", "data": "， " }, { "name": "text", "data": "et al" }, { "name": "text", "data": ". 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