CN112095351B - 一种频带可调的一体化多层吸波平面织物及其制备方法 - Google Patents

一种频带可调的一体化多层吸波平面织物及其制备方法 Download PDF

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CN112095351B
CN112095351B CN202010862505.4A CN202010862505A CN112095351B CN 112095351 B CN112095351 B CN 112095351B CN 202010862505 A CN202010862505 A CN 202010862505A CN 112095351 B CN112095351 B CN 112095351B
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张恒宇
肖红
陈剑英
王焰
冯硕
季惠
施楣梧
王妮
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Donghua University
Institute of Quartermaster Engineering Technology Institute of Systems Engineering Academy of Military Sciences
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Abstract

本发明公开了一种频带可调的一体化多层吸波平面织物及其制备方法。所述平面织物依次包括吸波层、频率选择层、织物层、导电层或频率选择层、吸波层、织物层、导电层；所述频率选择层由周期阵列分布的导电单元构成，所述吸波层由吸波剂和粘合剂构成。制备方法为：在织物的一面制备导电层；在织物的另一面制备导电单元，烘干后，在导电单元上刮涂吸波层，室温晾干；或者在织物的另一面刮涂吸波层，在吸波层未完全干燥时，将导电单元加压嵌入吸波层使导电单元与吸波层的表面处于同一平面，室温晾干。通过不同层对电磁波的选择透过、吸收、反射的一体化结合，具有面密度低、厚度薄、机械性能优良、吸波频带宽、吸波强度高、工作频带可调的优点。

Description

一种频带可调的一体化多层吸波平面织物及其制备方法
技术领域
本发明涉及一种频带可调的一体化多层吸波平面织物及其制备方法，特别涉及带有频率选择层、吸波层、导电层的一体化吸波织物及其制备方法。属于微波吸收材料技术领域。
背景技术
电磁吸波材料通过将电磁波能量转化为热能或其他形式能达到耗散电磁波的目的，以解决电磁干扰导致的人体免疫力下降、设备精度降低、信息泄露等问题，轻质、柔性、高效的吸波材料是解决电磁干扰和电磁辐射的理想途径。现如今电子设备精密化、高速化的发展，对电磁吸波材料提出新的要求，不仅要满足高吸收性，还需要具备轻薄、柔软、高尺寸适应性等性能。
吸波材料需满足两个条件，一是材料与自由空间的阻抗尽可能相当，二是具有高的电磁波损耗能力，以最大程度将电磁波能量转换为热能或其他形式能，而不会像电磁屏蔽材料产生二次污染。常用的吸波剂有羰基铁、铁氧体等。比如，羰基铁是一种高磁导率的依靠磁滞损耗、涡流损耗衰减电磁波的吸波材料，但是为了达到吸收效果，常伴随厚重、机械性能差等问题。不同吸波剂存在不同的优缺点。
不同设备的工作频段不同，为了保证设备的正常运行和设备周边环境的安全，需要一种工作频带可调的吸波材料及其制备方法。频率选择表面(FSS)是一种周期结构，对电磁波具有选择透过作用。借鉴频率选择表面FSS的制备方法，将导电单元周期性的阵列在非导电织物表面，或者在导电织物上周期性的阵列开孔，可以形成频率选择织物(FSF)，实现对特定频段电磁波的透过，而截止其他频段电磁波。这样的织物既可以满足透气性的要求，又可以解决防护需求。
单一吸波材料往往存在阻抗匹配差、吸收性能有限、吸波频带窄的缺点。通过不同层的叠加组合降低复合材料面密度并改善吸波性能较为常见。专利CN106469858A，一种吸波体结构中以金属板、蜂窝层、电阻片多层叠加，获得了宽频带、强吸收的吸波材料，但是金属板重量大，且复合材料总厚度超过20cm，CN 106961827A，多层结构吸波橡胶材料及其制备方法，虽然经硫化加压解决层间脱落问题，但是所述反射层为金属板，重量较大，且不能够对特定频率的电磁波选择性透过，CN 207038717U频率选择表面天线罩、CN 106329040A一种复合十字形缝隙频率选择表面、CN103682672A基于频率选择表面的超轻薄宽带吸波材料，均利用频率选择表面与介质层多层叠加以拓宽吸波频带，但导电单元均为金属贴片，不具备FSF特有的透气性，且介质层厚度较大。这些专利中多层复合吸波材料各层均有一定的厚度和质量，在实现宽频吸收的同时很难满足轻薄，且层与层之间存在孔隙、层间阻抗匹配、结合度较差等问题。
发明内容
本发明所要解决的技术问题是：传统的多层复合吸波材料各层均有一定的厚度和质量，在实现宽频吸收的同时很难满足轻薄，且层与层之间存在空隙、层间阻抗匹配、结合度较差等问题。
为了解决上述技术问题，本发明提供了一种频带可调的一体化多层吸波平面织物，其特征在于，所述平面织物为复合结构，依次包括吸波层、频率选择层、织物层、导电层或频率选择层、吸波层、织物层、导电层；所述频率选择层由周期阵列分布的导电单元构成，所述吸波层由吸波剂和粘合剂构成。不同于多层复合吸波材料，该织物为通过特定技术实现的完整的、难以分割的整体，具有柔软、轻质和高效的吸波特性。
优选地，所述织物为棉、粘胶、涤纶、锦纶、维纶、丙纶、芳纶和超高分子量聚乙烯中的任意一种或几种纤维的混纺或交织类织物。
优选地，所述导电层的电导率大于222S/m；所述导电层内含有的金属为银、铜、镍或铝。
优选地，所述频率选择层中导电单元的形状为十字形、耶路撒冷形、圆环形、U形和偶极子中的至少一种；所述导电单元的材质为银、铝、铜、镍、氧化银、氧化铝、氧化铜和氧化镍中的任意一种或几种的混合物。
优选地，所述吸波层中吸波剂为羰基铁、羟基镍、羟基钴、铁氧体、碳化硅、钛酸钡、石墨、氮化硅、氮化铁、碳纤维或氧化锌；所述粘合剂为水性聚氨酯、油性聚氨酯、聚乙烯醇和聚氯乙烯中的任意一种或几种。
优选地，所述吸波剂与粘合剂的质量比为(1:4)～(9:1)。
优选地，所述吸波层的厚度为0.1～5mm。
本发明还提供了上述频带可调的一体化多层吸波平面织物的制备方法，其特征在于，包括以下步骤：
步骤1)：在织物的一面制备导电层；
步骤2)：依据目标谐振点，利用仿真模拟软件设计出导电单元的形状、尺寸及排列方式；
步骤3)：将吸波剂与粘合剂混合制备吸波层；
步骤4)：在织物的另一面制备导电单元，烘干后，在导电单元上刮涂吸波层，室温晾干；或者在织物的另一面刮涂吸波层，在吸波层未完全干燥时，将导电单元加压嵌入吸波层使导电单元与吸波层的表面处于同一平面，室温晾干。
优选地，所述步骤1)中的导电层通过化学镀、电镀或磁控溅射方法将金属或金属氧化物镀覆于织物上，或者通过涂层方式将金属或金属氧化物导电浆料涂布于织物上。
优选地，所述步骤4)中的导电单元通过丝网印刷、金属/金属氧化物的选择性电镀、化学镀或溅射方法形成。
本发明提供的一体化多层吸波织物，具有轻薄柔软、机械性能优良，吸波频带宽，吸波频带可调等优点。
与现有技术相比，本发明的有益效果在于：
导电单元直接涂敷于织物层非导电层的一侧或嵌入到吸波层内，可减小复合材料整体厚度，吸波层-频率选择层-织物层-导电层复合中优选织物可同时作为导电层与频率选择层的基底，频率选择层-吸波层-织物层-导电层复合中吸波层同时作为导电单元的介质基底，与导电单元构成频率选择表面，优选织物可同时作为导电层与吸波层的基底。该一体化多层复合平面织物可依据目标频段调整复合材料的有效工作频段，各功能层为一个整体，通过对电磁波的选择透过、吸收、反射的一体化结合，拓宽吸波频带、提高吸波强度，减小了厚度，改善以往多层复合材料层与层之间结合度差、厚重、层间存在空隙、工作频带单一的缺陷，具有柔软、轻薄和吸波频带可调高效的吸波特性。
附图说明
图1为不同形状、类型频率选择层的对比图；其中，黑色为导电单元部分，其余为织物基底；
图2为实施例1-3得到的一体化多层吸波平面织物(吸波层-频率选择层-织物层-导电层)的结构示意图；
图3为实施例4-6得到的一体化多层吸波平面织物(频率选择层-吸波层-织物层-导电层)的结构示意图；
图4吸波层-频率选择层-织物层-高导电层一体化多层吸波平面织物反射率测试结果；
图5频率选择层-吸波层-织物层-高导电层一体化多层吸波平面织物反射率测试结果。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，并配合附图作详细说明如下。
实施例1-3的结构如图2所示，所述平面织物为复合结构，依次包括吸波层1、频率选择层、织物层3、导电浆料涂层4；所述频率选择层由周期阵列分布的导电单元2构成，所述吸波层1由吸波剂和粘合剂构成。
实施例4-6的结构如图3所示，所述平面织物为复合结构，依次包括频率选择层、吸波层1、织物层3、导电浆料涂层4；所述频率选择层由周期阵列分布的导电单元2构成，所述吸波层1由吸波剂和粘合剂构成。
实施例1
以棉机织物为基底，采用化学镀层的方式，将银浆涂敷于棉机织物的一面，待其烘干后获得导电层，电导率为230S/m，然后利用丝网印刷将铜镍浆料以十字形导电单元涂敷于棉机织物的另一面，每18×18cm2内导电单元排列为8×8个，获得频率选择层。最后在频率选择层上面用刮刀再刮涂一层吸波层，羰基铁粉(北京新荣源科技有限公司)与聚乙烯醇(1788,上海臣启化工科技有限公司)质量比为1:4，吸波层厚度为0.15mm，室温晾干，从而形成一体化多层吸波平面织物。
在2-18GHz测试范围内，反射率最小值为14.1dB，反射率小于-10dB的带宽为0.8GHz(17.2-18GHz)，小于-5dB带宽为0.96GHz(6-6.96GHz)和2.96GHz(15.04-18GHz)。
实施例2
以涤纶针织物为基底，采用电镀层的方式，将银浆涂敷于涤纶针织物的一面，待其烘干后获得导电层，电导率为222S/m，利用丝网印刷将铜镍浆料以U形导电单元涂敷于棉机织物的另一面，每18×18cm2内导电单元排列为16×16个，获得频率选择层。最后在频率选择层上面刮涂吸波层，碳化硅(巩义市优星矿产品有限公司)与油性聚氨酯(PU110,苏州三纳新材料有限公司)的质量比为4:3，吸波层厚度为0.22mm，室温晾干，从而形成一体化多层吸波平面织物。
在2-18GHz测试范围内，反射率峰值为-14.8dB，小于-10dB带宽为3.04GHz(7.92-10.96GHz)和0.32GHz(13.12-13.44GHz)，小于-5dB带宽为5.84GHz(6.08-11.92GHz)和1.6GHz(12.64-14.24GHz)。
实施例3
以锦纶机织物为基底，采用化学镀层的方式，将铜镍浆料涂敷于锦纶机织物的一面，待其烘干后获得导电层，电导率为300S/m，然后利用选择性电镀将氧化镍浆料以耶路撒冷形导电单元涂敷于棉机织物的另一面，每18×18cm2内导电单元排列为10×10个，获得频率选择层。最后在频率选择层上面刮涂一层吸波层，羰基铁粉(北京新荣源科技有限公司)与聚乙烯醇(2488,上海臣启化工科技有限公司)质量比为7:3，吸波层厚度为0.35mm，室温晾干，从而形成一体化多层吸波平面织物。
在2-18GHz测试范围内，出现双反射率峰，峰值分别为-21.6dB，-16.9dB，小于-10dB的带宽为4.9GHz(9.2-14.1GHz)，小于-5dB带宽为9.1GHz(7.7-16.8GHz)。
实施例4
以涤纶机织物为基底，采用化学镀层的方式，将铜镍浆料涂敷于涤纶机织物的一面，待其烘干后获得导电层，电导率为320S/m，然后在涤纶机织物另一面用刮刀刮涂一层吸波层，羟基镍粉(上海杳田新材料科技有限公司)与水性聚氨酯(PU-3731广州亨缌克新材料有限公司)的质量比为2:3，待吸波层快要干燥完全时，将圆环形导电单元依据仿真模拟的周期排列方式，即每18×18cm2内导电单元排列为10×10个，置于吸波层上，加压使其嵌入吸波层，吸波层/导电单元厚度为0.3mm，室温下固化成型，从而形成一体化嵌入式多层吸波平面织物。
在2-18GHz测试范围内，反射率峰值为19.1dB，小于-5dB带宽为9.4GHz(6.96-17.36GHz)，小于-10dB带宽为3.6GHz(8.32-11.92GHz)和1.48GHz(12.48-14.96GHz)。
实施例5
以棉针织物为基底，采用电镀层的方式，将氧化银浆料涂敷于棉的针织物一面，待其烘干后获得导电层，电导率为350S/m，然后在棉针织物的另一面刮涂一层吸波层，羰基铁粉(北京新荣源科技有限公司)与水性聚氨酯(PU-3731广州亨缌克新材料有限公司)的质量比为3:2，待吸波层快要干燥完全时，将十字形导电单元依据仿真模拟的周期排列方式，即每18×18cm2内导电单元排列为8×8个，置于吸波层上，加压使其嵌入吸波层，吸波层/导电单元厚度为0.21mm，室温下固化成型，从而形成一体化嵌入式多层吸波平面织物。
在2-18GHz测试范围内，反射率最小值为-17.1dB，小于-5dB带宽为9.12GHz(8.16-17.28GHz)，小于-10dB带宽为5.4GHz(9.92-14.32GHz)。
实施例6
以维纶针织物为基底，采用磁控溅射的方式，将氧化镍涂敷于维纶针织物的一面，待其烘干后获得导电层，电导率为260S/m，然后在维纶针织物另一面刮涂吸波层，碳化硅(巩义市优星矿产品有限公司)与油性聚氨酯(PU110,苏州三纳新材料有限公司)的质量比为4:1，待吸波层快要干燥完全时，将圆环形导电单元依据仿真模拟的周期排列方式，即每18×18cm2内导电单元排列为6×6个，置于吸波层上，加压使其嵌入吸波层，吸波层/导电单元厚度为0.42mm，室温下固化成型，从而形成一体化嵌入式多层吸波平面织物。
在2-18GHz测试范围内，反射率峰值为—-12.5dB，小于-10dB带宽为2.88GHz。小于-5dB带宽为7.64GHz(10.24-17.88GHz)。

Claims (8)

1.一种频带可调的一体化多层吸波平面织物，其特征在于，所述平面织物为复合结构，依次包括吸波层（1）、频率选择层、织物层（3）、导电层（4）或频率选择层、吸波层（1）、织物层（3）、导电层（4）；所述频率选择层由周期阵列分布的导电单元（2）构成，所述吸波层（1）由吸波剂和粘合剂构成；所述频率选择层中导电单元（2）的形状为十字形、耶路撒冷形、圆环形和U形中的至少一种；
所述的频带可调的一体化多层吸波平面织物的制备方法，包括以下步骤：
步骤1）：在织物的一面制备导电层；
步骤2）：依据目标谐振点，利用仿真模拟软件设计出导电单元的形状、尺寸及排列方式；
步骤3）：将吸波剂与粘合剂混合制备吸波层；
步骤4）：在织物的另一面制备导电单元，烘干后，在导电单元上刮涂吸波层，室温晾干；或者在织物的另一面刮涂吸波层，在吸波层未完全干燥时，将导电单元加压嵌入吸波层使导电单元与吸波层的表面处于同一平面，室温晾干；所述导电单元通过丝网印刷、金属/金属氧化物的选择性电镀、化学镀或溅射方法形成。
2.如权利要求1所述的频带可调的一体化多层吸波平面织物，其特征在于，所述织物（3）为棉、粘胶、涤纶、锦纶、维纶、丙纶、芳纶和超高分子量聚乙烯中的任意一种纤维制成的织物，或上述几种纤维的混纺或交织类织物。
3.如权利要求1所述的频带可调的一体化多层吸波平面织物，其特征在于，所述导电层（4）的电导率大于222s/m；所述导电层（4）内含有的金属为银、铜、镍或铝。
4.如权利要求1所述的频带可调的一体化多层吸波平面织物，其特征在于，所述导电单元（2）的材质为银、铝、铜、镍、氧化银、氧化铝、氧化铜和氧化镍中的任意一种或几种的混合物。
5.如权利要求1所述的频带可调的一体化多层吸波平面织物，其特征在于，所述吸波层（1）中吸波剂为羰基铁、羟基镍、羟基钴、铁氧体、碳化硅、钛酸钡、石墨、氮化硅、氮化铁、碳纤维或氧化锌；所述粘合剂为水性聚氨酯、油性聚氨酯、聚乙烯醇和聚氯乙烯中的任意一种或几种。
6.如权利要求1所述的频带可调的一体化多层吸波平面织物，其特征在于，所述吸波剂与粘合剂的质量比为（1:4）~（9:1）。
7.如权利要求1所述的频带可调的一体化多层吸波平面织物，其特征在于，所述吸波层（1）的厚度为0.1~1mm。
8.如权利要求1所述的频带可调的一体化多层吸波平面织物，其特征在于，所述步骤1）中的导电层通过化学镀、电镀或磁控溅射方法将金属或金属氧化物镀覆于织物上，或者通过涂层方式将金属或金属氧化物导电浆料涂布于织物上。
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