CN115556454A - 柔性红外低辐射型智能变色伪装薄膜 - Google Patents
柔性红外低辐射型智能变色伪装薄膜 Download PDFInfo
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Abstract
本发明公开了一种柔性红外低辐射型智能变色伪装薄膜,由高透明宽域红外低辐射膜系结构ZMD、电致变色膜系结构ED、柔性透明基底三部分堆叠构成;所述高透明宽域红外低辐射膜系结构ZMD的膜层的结构为ZMD;所述电致变色膜系结构ED是由导电薄膜层1、电致变色层、固态电解质层、导电薄膜层2组合构成的;所述透明柔性基底的材料选自聚对苯二甲酸乙二醇酯等。所述柔性红外低辐射型智能变色伪装薄膜在制备隐身装备、变色伪装装备中的应用。本发明综合发挥了可见光透射诱导、红外禁带、电致变色等多效应协同作用,实现了红外低辐射、可见光智能变色双重伪装功能于一体的兼容隐身效果,具备的高柔性可实现装备表面共形贴附,具备军民两用前景。
Description
技术领域
本发明涉及一种柔性红外低辐射型智能变色伪装薄膜,属于多频谱兼容隐身材料技术领域。
背景技术
当前探测与制导技术趋向于多源多模联合形式发展,尤其可见光与热红外在光电探测技术中起到了至关重要的地位。然而现有技术中广泛使用的可见光伪装迷彩涂料与低发射率红外伪装涂料已经在规避多源联合探测、识别与打击领域显得举步维艰,因此发展可见光与红外兼容的多波段隐身材料技术已经成为伪装领域势在必行的发展方向。此外,当前地面装备都需要开展沙漠、山地、草原、公路等多地域背景环境的运用场景,即使同地域背景环境特性也会随季节、时间等变换。因此,发展能随背景环境变换而实时自适应改变自身色彩的智能变色隐身材料亦已成为伪装领域迫待发展的必然趋势。
目前在变色材料研究领域取得了一定的突出进展,可通过光致、力致、热致、电致等不同刺激源诱导产生一系列色彩变化的材料。然而,光、热、力等方式刺激并不能很好地精确操控变色响应过程,唯独电热致变色与电致变色两类电场控制方式能对色彩变换与切换速度实现精确控制,因而被广泛发展。其中,电致变色材料是在电场下产生电子、离子的注入与抽取,或者诱发氧化还原反应,进而可控、可逆的实现光学性质变化。电致变色材料组装的电致变色设备(ECD),具有色彩丰富、耗能更低、智能可控等优点, 在智能窗户、智能信息显示、汽车防炫目后视镜、可穿戴电子设备、军事伪装等有巨大的市场应用空间。然而,现有技术中的电致变色器件仍然以开发单一变色功能、刚性结构的电致变色器件为主。随着先进材料技术、电子信息技术等的快速发展,具有柔性、可穿戴、智能化、多功能等优势特征的新型电子器件将在未来展现出更重要的价值。因此,开发具备一定的柔性、多功能化的电致变色器件是该领域的重要发展趋势。
发明内容
针对上述现有技术,本发明提供了一种柔性红外低辐射型智能变色伪装薄膜。本发明利用多层异质薄膜结构设计方法,集成了透射诱导、红外禁带、电致变色等多种综合效应,实现了中远红外低辐射与可见光智能变色,最终实现了红外伪装与可见光智能变色伪装双重功能一体化设计。
本发明是通过以下技术方案实现的:
一种柔性红外低辐射型智能变色伪装薄膜,其结构是由高透明宽域红外低辐射膜系结构ZMD、电致变色膜系结构ED、柔性透明基底三部分堆叠构成的,其自上而下堆叠的结构形式包括以下两种:①ZMD/透明柔性基底/ED,②ZMD/透明柔性基底/ED/ZMD。
所述高透明宽域红外低辐射膜系结构ZMD是实现红外低辐射与可见光高透明双重功能的复合薄膜层,其膜层的结构为ZMD;外部介质薄膜层Z的材料选自ZnTe、ZnSe,厚度为20~50 nm;中间金属薄膜层M的材料选自Ag、Au、Cu等金属材料,厚度为10~20 nm;内部介质薄膜层D的材料选自Al2O3或AZO(掺杂铝的氧化锌),厚度为20~50 nm。
所述电致变色膜系结构ED是在电场控制下实现智能变色功能的,是由导电薄膜层1、电致变色层、固态电解质层、导电薄膜层2组合构成的;各层薄膜厚度均为100~500 nm。
进一步地,所述透明柔性基底的材料选自聚对苯二甲酸乙二醇酯(PET)、聚二甲基硅氧烷(PDMS)、聚酰亚胺(PI)、聚乙烯(PE)、聚丙烯(PP)、聚碳酸酯(PC)等柔性基底材料;所述透明柔性基底的厚度为0.1~0.5 mm。
进一步地,所述导电薄膜层1、导电薄膜层2的导电薄膜材料选自ITO(氧化铟锡)、AZO、ATO(掺锑的SnO2)、FTO(掺氟的SnO2)等。
进一步地,所述电致变色层的材料选自WO3、MoO3、TiO2、NiO、V2O5等金属氧化物电致变色薄膜材料。
进一步地,所述固体电解质层的材料选自钽酸锂(LiTaO3)、铌酸锂(LiNbO3)、氧化锆(ZrO2)、氧化钽(Ta2O5)等固态电解质材料。
进一步地,制备柔性红外低辐射型智能变色伪装薄膜时,在透明柔性基底外侧表面采用磁控溅射、真空蒸发镀等工艺制备ZMD膜系结构,然后在透明柔性基底内侧表面采用磁控溅射、真空蒸发镀等镀膜工艺制备镀制ITO、AZO、ATO、FTO等导电薄膜,形成导电薄膜层1;然后,再在导电薄膜层1镀膜制备电致变色层;继而再镀膜制备固态电解质层;继而再镀膜制备导电薄膜层2;当电致变色膜系结构ED下侧还有一层ZMD结构时,再在导电薄膜层2上依次镀膜制备ZMD膜系结构。
所述柔性红外低辐射型智能变色伪装薄膜在制备隐身装备、变色伪装装备中的应用。
本发明的柔性红外低辐射型智能变色伪装薄膜,通过微纳膜层结构设计技术综合发挥了可见光透射诱导、红外禁带、电致变色等多效应协同作用,实现了红外低辐射、可见光智能变色双重伪装功能于一体的兼容隐身效果。同时,具备的高柔性可实现装备表面共形贴附。因此,本发明的新型超构薄膜材料既能适用于机动地面装备的红外与可见光兼容隐身的军事领域,还可用于智能窗等绿色节能建筑民用行业领域,具备军民两用前景。
本发明使用的各种术语和短语具有本领域技术人员公知的一般含义。
附图说明
图1:柔性红外低辐射型智能变色伪装薄膜结构ZMD/ED示意图。
图2:膜系结构ZnTe\Ag\Al2O3可见光透射光谱特性示意图。
图3:膜系结构ZnTe\Ag\Al2O3的红外反射光谱特性示意图。
图4:柔性红外低辐射型智能变色伪装薄膜结构ZMD/ED/ZMD示意图。
图5:膜系结构ZnSe\Cu\AZO可见光透射光谱特性示意图。
图6:膜系结构ZnSe\Cu\AZO红外反射光谱特性示意图。
具体实施方式
下面结合实施例对本发明作进一步的说明。然而,本发明的范围并不限于下述实施例。本领域技术人员能够理解,在不背离本发明的精神和范围的前提下,可以对本发明进行各种变化和修饰。
下述实施例中所涉及的仪器、试剂、材料,若无特别说明,均为现有技术中已有的常规仪器、试剂、材料,可通过正规商业途径获得。下述实施例中所涉及的实验方法、检测方法等,若无特别说明,均为现有技术中已有的常规实验方法、检测方法。
实施例1 柔性红外低辐射型智能变色伪装薄膜
由高透明宽域红外低辐射膜系结构ZMD、电致变色膜系结构ED、柔性透明基底堆叠构成,如图1所示,其堆叠结构形式为ZMD/透明柔性基底/ED。
所述高透明宽域红外低辐射膜系结构ZMD是实现红外低辐射与可见光高透明双重功能的复合薄膜层,其膜层的结构为ZMD;外部介质薄膜层Z的材料为ZnTe,厚度为20 nm;中间金属薄膜层M的材料为Ag,厚度为15 nm;内部介质薄膜层D的材料为Al2O3,厚度为30 nm。
所述透明柔性基底为0.15 mm厚度的PET。
所述电致变色膜系结构ED是在电场控制下实现智能变色功能的,是由导电薄膜层1、电致变色层、固态电解质层、导电薄膜层2组合构成的;所述导电薄膜层1的导电薄膜材料为FTO,厚度为100 nm;所述电致变色层的材料为TiO2,厚度为250 nm;所述固体电解质层的材料为ZrO2,厚度为250 nm;所述导电薄膜层2的导电薄膜材料为AZO,厚度为500 nm。
制备时,在透明柔性基底外侧表面采用真空蒸发镀膜工艺制备“外部介质薄膜层Z-中间金属薄膜层M-内部介质薄膜层D”膜系结构。然后,在透明柔性基底(0.15 mm厚度的PET)内侧表面采用真空蒸发镀膜工艺制备镀制FTO薄膜,形成导电薄膜层1;然后,再在导电薄膜层1镀膜制备电致变色层;继而再镀膜制备固态电解质层,再镀膜制备AZO薄膜,形成导电薄膜层2。
模拟计算分析该隐身膜系结构中上部的ZnTe\Ag\Al2O3部分在0.38~0.8μm可见光波段的透过率,如图2所示。由图2可见,该新型膜系结构在0.4~0.78μm可见光的透射率均大于70%,且平均透过率为86.1%。这说明该ZMD膜系结构因受益于透射诱导效应而具有很高的透明特性,可使电致变色膜系结构的可见光色泽顺利能得以极高透射率方式显示。由于电致变色膜系结构ED采用TiO2电致变色薄膜,能在-2~2 V电压范围内实现颜色在无色、蓝色与褐色间相互可逆性变化,因此整个薄膜结构ZMD/ED在电场精确控制下呈现色彩响应性变化。
模拟计算薄膜结构ZnTe\Ag\Al2O3在3~15μm中远红外波段的反射率,如图3所示,该新型膜系结构在3~1μm中远红外波段的反射率都能大于67.8 %,且在整个中远红外波段的平均反射率为87.3%,因此具备覆盖中远红外窗口区域的宽域红外隐身能力。因此,可在不影响电致变色膜系结构ED的可见光智能变色视觉隐身的基础上抑制中远红外辐射,达到智能变色与红外兼容隐身效果。
综上,本实施例通过利用多层异质薄膜结构设计方法来集成透射诱导、红外禁带、电致变色等多种综合效应,实现了中远红外低辐射与可见光智能变色,最终实现了红外伪装与可见光智能变色伪装双重功能一体化设计。同时,由于整个膜系结构是依托于PET柔性基底,且所有的材质(包括两片PET基底)厚度少于0.33 mm,因此整个膜系结构具备高柔性,可很好实现装备表面的共形贴附效果。
实施例2 柔性红外低辐射型智能变色伪装薄膜
由高透明宽域红外低辐射膜系结构ZMD、电致变色膜系结构ED、柔性透明基底堆叠构成,如图4所示,其堆叠结构形式为ZMD/透明柔性基底/ED/ZMD。
所述高透明宽域红外低辐射膜系结构ZMD是实现红外低辐射与可见光高透明双重功能的复合薄膜层。两侧的高透明宽域红外低辐射膜系结构ZMD的膜层的结构均为ZMD;外部介质薄膜层Z的材料为ZnSe,厚度为40 nm;中间金属薄膜层M的材料为Cu,厚度为10 nm;内部介质薄膜层D的材料为AZO,厚度为50 nm。
所述透明柔性基底为0.2 mm厚度的PI。
所述电致变色膜系结构ED是在电场控制下实现智能变色功能的,是由导电薄膜层1、电致变色层、固态电解质层、导电薄膜层2组合构成的;所述导电薄膜层1的导电薄膜材料为ITO,厚度为200 nm;所述电致变色层的材料为V2O5,厚度为250 nm;所述固体电解质层的材料为LiTaO3,厚度为300 nm;所述导电薄膜层2的导电薄膜材料为ATO,厚度为400 nm。
制备时,在透明柔性基底外侧表面采用磁控溅射工艺制备“外部介质薄膜层Z-中间金属薄膜层M-内部介质薄膜层D”膜系结构。然后,在透明柔性基底(0.2 mm厚度的PI)内侧表面采用磁控溅射工艺制备镀制ITO薄膜,形成导电薄膜层1;然后,再在导电薄膜层1镀膜制备电致变色层;继而再镀膜制备固态电解质层,再镀膜制备ATO薄膜,形成导电薄膜层2;然后,再在导电薄膜层2上依次镀膜制备ZMD膜系结构。
模拟计算分析该隐身膜系结构中两端的ZnSe\Cu\AZO部分在0.38~0.8μm可见光波段的透过率,如图5所示。由图5可见,该新型膜系结构在整个可见光波段的透射率均大于40%,且平均透过率为58.6%。这说明该ZMD膜系结构因受益于透射诱导效应而具有较高的透明特性,可使电致变色膜系结构的可见光色泽顺利能得以较高透射率方式显示。由于电致变色膜系结构ED采用V2O5电致变色薄膜,能在-3~3 V电压范围内实现颜色在蓝灰色与浅绿色间相互可逆性变化,因此整个薄膜结构ZMD/ED/ZMD可在电场精确控制下呈现色彩响应性变化。
模拟计算两侧薄膜结构ZnSe\Cu\AZO在3~15μm中远红外波段的反射率,如图6所示,该新型膜系结构在3~15μm中远红外波段的反射率都能大于65.5%,且在整个中远红外波段的平均反射率为85.9 %,因此具备覆盖中远红外窗口区域的宽域红外隐身能力。因此,两侧薄膜结构ZnSe\Cu\AZO可在不影响电致变色膜系结构ED的可见光智能变色视觉隐身的基础上抑制中远红外辐射,达到智能变色与红外兼容隐身效果。
综上,本实施例的薄膜结构ZMD/ED/ZMD结构在电场控制作用下可实现可逆性变色过程的高透光显示,同时还兼具宽域红外低辐射特性,从而达到红外伪装与可见光智能变色伪装双重功能一体化设计效果。同样,由于整个膜系结构是依托于PI柔性基底,且所有的材质(包括两片PI基底)厚度少于0.45 mm,因此整个膜系结构具备高柔性,可很好实现装备表面的共形贴附效果。
给本领域技术人员提供上述实施例,以完全公开和描述如何实施和使用所主张的实施方案,而不是用于限制本文公开的范围。对于本领域技术人员而言显而易见的修饰将在所附权利要求的范围内。
Claims (10)
1.一种柔性红外低辐射型智能变色伪装薄膜,其特征在于:其结构是由高透明宽域红外低辐射膜系结构ZMD、电致变色膜系结构ED、柔性透明基底三部分堆叠构成的,其自上而下堆叠的结构形式为以下两种之一:①ZMD/透明柔性基底/ED,②ZMD/透明柔性基底/ED/ZMD;
所述高透明宽域红外低辐射膜系结构ZMD,其膜层的结构为ZMD;外部介质薄膜层Z的材料选自ZnTe、ZnSe,厚度为20~50 nm;中间金属薄膜层M的材料选自Ag、Au、Cu,厚度为10~20 nm;内部介质薄膜层D的材料选自Al2O3或AZO,厚度为20~50 nm;
所述电致变色膜系结构ED,是由导电薄膜层1、电致变色层、固态电解质层、导电薄膜层2组合构成的;各层薄膜的厚度均为100~500 nm。
2.根据权利要求1所述的柔性红外低辐射型智能变色伪装薄膜,其特征在于:所述透明柔性基底的材料选自聚对苯二甲酸乙二醇酯、聚二甲基硅氧烷、聚酰亚胺、聚乙烯、聚丙烯、聚碳酸酯中的任意一种。
3.根据权利要求1所述的柔性红外低辐射型智能变色伪装薄膜,其特征在于:所述透明柔性基底的厚度为0.1~0.5 mm。
4.根据权利要求1所述的柔性红外低辐射型智能变色伪装薄膜,其特征在于:所述导电薄膜层1、导电薄膜层2的导电薄膜材料选自ITO、AZO、ATO、FTO。
5.根据权利要求1所述的柔性红外低辐射型智能变色伪装薄膜,其特征在于:所述电致变色层的材料选自WO3、MoO3、TiO2、NiO、V2O5。
6.根据权利要求1所述的柔性红外低辐射型智能变色伪装薄膜,其特征在于:所述固体电解质层的材料选自钽酸锂、铌酸锂、氧化锆、氧化钽。
7.根据权利要求1所述的柔性红外低辐射型智能变色伪装薄膜,其特征在于:制备柔性红外低辐射型智能变色伪装薄膜时,在透明柔性基底外侧表面采用磁控溅射或真空蒸发镀工艺制备ZMD膜系结构;然后在透明柔性基底内侧表面采用磁控溅射或真空蒸发镀工艺制备镀制导电薄膜层1;然后再镀膜制备电致变色层;继而再镀膜制备固态电解质层;继而再镀制导电薄膜层2;当电致变色膜系结构ED下侧还有一层ZMD结构时,再在导电薄膜层2上依次镀膜制备ZMD膜系结构。
8.根据权利要求1~7中任一项所述的柔性红外低辐射型智能变色伪装薄膜,其特征在于:由高透明宽域红外低辐射膜系结构ZMD、电致变色膜系结构ED堆叠构成,其堆叠结构形式为ZMD/ED;
所述高透明宽域红外低辐射膜系结构ZMD,其膜层的结构为ZMD;外部介质薄膜层Z的材料为ZnTe,厚度为20 nm;中间金属薄膜层M的材料为Ag,厚度为15 nm;内部介质薄膜层D的材料为Al2O3,厚度为30 nm;
所述透明柔性基底为0.15 mm厚度的PET;
所述电致变色膜系结构ED是由导电薄膜层1、电致变色层、固态电解质层、导电薄膜层2组合构成的;所述导电薄膜层的导电薄膜材料为FTO,厚度为100 nm;所述电致变色层的材料为TiO2,厚度为250 nm;所述固体电解质层的材料为ZrO2,厚度为250 nm;所述导电薄膜层2的导电薄膜材料为AZO,厚度为500 nm。
9.根据权利要求1~7中任一项所述的柔性红外低辐射型智能变色伪装薄膜,其特征在于:由高透明宽域红外低辐射膜系结构ZMD、电致变色膜系结构ED堆叠构成,其堆叠结构形式为ZMD/ED/ZMD;
所述高透明宽域红外低辐射膜系结构ZMD,其膜层的结构为ZMD;外部介质薄膜层Z的材料为ZnSe,厚度为40 nm;中间金属薄膜层M的材料为Cu,厚度为10 nm;内部介质薄膜层D的材料为AZO,厚度为50 nm;
所述透明柔性基底为0.2 mm厚度的PI;
所述电致变色膜系结构ED是由导电薄膜层1、电致变色层、固态电解质层、导电薄膜层2组合构成的;所述导电薄膜层1的导电薄膜材料为ITO,厚度为200 nm;所述电致变色层的材料为V2O5,厚度为250 nm;所述固体电解质层的材料为LiTaO3,厚度为300 nm;所述导电薄膜层2的导电薄膜材料为ATO,厚度为400 nm。
10.权利要求1~9中任一项所述的柔性红外低辐射型智能变色伪装薄膜在制备隐身装备、变色伪装装备中的应用。
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