CN106588124A - 一种对8~18GHz频段内的吸波陶瓷涂层的低温制备方法 - Google Patents

一种对8~18GHz频段内的吸波陶瓷涂层的低温制备方法 Download PDF

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CN106588124A
CN106588124A CN201610989902.1A CN201610989902A CN106588124A CN 106588124 A CN106588124 A CN 106588124A CN 201610989902 A CN201610989902 A CN 201610989902A CN 106588124 A CN106588124 A CN 106588124A
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wave
wave absorbing
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殷小玮
叶昉
刘晓菲
莫然
成来飞
张立同
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Northwestern Polytechnical University
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Abstract

本发明涉及一种对8～18GHz频段内的吸波涂层的低温制备方法，即采用涂刷技术先将含有吸波剂的浆料均匀涂刷在基底材料表面，静置阴干后再通过化学气相沉积技术，在吸波剂表面制备透波层。本发明中吸波涂层与基底材料结合良好，并可显著改善材料的吸波性能。该方法具有很强的可设计性，例如通过调整吸波剂种类、透波层种类和沉积时间等参数，可优化涂层结构和组分，从而使基底材料获得更佳的吸波性能。

Description

一种对8～18GHz频段内的吸波陶瓷涂层的低温制备方法
技术领域
本发明涉及一种吸波陶瓷涂层的低温制备方法，具体指经涂刷-化学气相沉积(Chemical vapor deposition，CVD)两个核心步骤在基底材料表面制备对8～18GHz频段内的吸波涂层的方法。
背景技术
现代雷达技术、电子技术和军事技术的迅猛发展使各国对高温吸波材料的研究与需求日益迫切。高温吸波材料主要包括高温吸波陶瓷和高温结构型吸波材料。由于兼具承载/吸波性能，高温结构型吸波材料被视为最有潜力的高温吸波材料。
连续纤维增韧陶瓷基复合材料(CFCC)具有很高的强度与韧性，同时对裂纹不敏感，不发生灾难性损毁，是一种优异的高温结构材料。目前，将CFCC发展为兼具承载和减小雷达反射截面双重功能的高温结构型吸波材料，已逐渐成为各国研究的热点。然而，根据文献报道可知，常见的CFCC(如C/SiC、SiC/SiC、SiC/Nasicon)虽具备优异的力学性能，但其吸波效果并不理想。因此，对此类材料进行改性优化以提高材料的电磁吸波能力是解决这一问题的关键。
改善CFCC吸波性能的方法可以从纤维和基体两方面入手。对纤维的改性主要目的在于降低其电导率，从而减少其对电磁波的反射。降低纤维电导率的方法包括降低纤维的晶化程度和制备非晶包覆层。然而，降低纤维的晶化程度会显著影响纤维的强度，致使复合材料的力学性能降低；在纤维表面制备非晶包覆层会减小纤维的体积分数，也不利于材料强度的提高。从基体相入手改善CFCC吸波性能的主要方法为选择具有一定吸波性能或透波性能的陶瓷材料作为基体相，这可一定程度改善复合材料对电磁波的强反射特性。然而，通常情况下为了保证复合材料的力学性能，CFCC中纤维预制体的体积分数均较高，因此调整基体的电磁性能对复合材料吸波性能的改善效果并不显著。
综上所述，从复合材料的基本组成单元(纤维、基体)出发提高材料的吸波性能具有一定局限性。近年来，研究人员通过在材料表面制备吸波涂层，已经实现复合材料吸波性能的显著提高。制备吸波涂层的主要工艺有涂刷、化学镀、热喷涂和溶胶-凝胶技术。涂刷法工艺简单，涂层厚度可控，但通常需要进一步的烧结以保证涂层强度和涂层与基底的结合性，因此需在浆料中添加足够的粘结剂或烧结助剂(烧结温度高)。化学镀方法要求基底材料具有化学稳定性，不与镀液反应，且通常局限于制备金属或合金涂层，如镍涂层或铁钴合金涂层。热喷涂法需将涂层材料加热到熔融或半熔融状态，因此不适用于难熔材料且温度较高。同时，有一定比例CFCC的耐温性能低于陶瓷的烧结问题。由此可见，以上方法应用于CFCC吸波涂层的制备时均存在一定局限性。因此，亟待需要发展一种新方法，使采用该法低温制备获得的吸波涂层不仅满足复合材料的高温使用需求，而且能够有效改善CFCC的吸波效果。
发明内容
要解决的技术问题
为了避免现有技术的不足之处，本发明提出一种对8～18GHz频段内的吸波陶瓷涂层的低温制备方法，是一种“涂刷技术”结合“化学气相沉积技术”的涂层低温制备方法，其流程图如附图1所示。
技术方案
一种对8～18GHz频段内的吸波陶瓷涂层的低温制备方法，其特征在于步骤如下：
步骤1、制备含有吸波剂的浆料：按照浆料的体积分数配比物质为：60～75％的溶剂、3％的分散剂磷酸三乙酯、3％的粘结剂聚乙烯醇缩丁醛、2％的增塑剂、2％的除泡剂、15～30％的吸波剂；将上述物质混合后，通过超声处理使浆料混合充分，成为均匀的悬浮液；
所述溶剂是体积比0.1～10的甲苯与异丙醇的混合溶剂；
所述增塑剂是体积比0.1～1150的丙三醇与邻苯二甲酸二乙酯的混合物；
上述除泡剂是体积比0.1～10的正丁醇与乙二醇的混合物；
步骤2：将步骤1的浆料按照设计厚度涂刷在基底材料表面，然后静置阴干；
步骤3：通过化学气相沉积技术CVD在涂刷浆料的基底材料上低温制备透波层。
所述吸波剂为碳纳米管、石墨烯、纳米碳化硅晶粒或碳化硅晶须。
所述基底材料为陶瓷和陶瓷基复合材料、金属及金属基复合材料、树脂及树脂基复合材料。
有益效果
本发明提出的一种对8～18GHz频段内的吸波陶瓷涂层的低温制备方法，在交变电场下，陶瓷、陶瓷基复合材料、金属和树脂基复合材料等，通常对电磁波表现为反射或透过特性，因此材料的吸波性能较差。为进一步改善材料的吸波性能，本发明涉及一种针对8～18GHz频段内的吸波涂层的低温制备方法，即采用涂刷技术先将含有吸波剂的浆料均匀涂刷在基底材料表面，静置阴干后再通过化学气相沉积技术，在吸波剂表面制备透波层。本发明中吸波涂层与基底材料结合良好，并可显著改善材料的吸波性能。该方法具有很强的可设计性，例如通过调整吸波剂种类、透波层种类和沉积时间等参数，可优化涂层结构和组分，从而使基底材料获得更佳的吸波性能。
附图2显示了本发明中吸波涂层的结构示意图。采用本发明方法制备获得的吸波涂层，具有以下主要优点：
(1)与基底材料粘结性优良，制备过程中能够保持复合材料力学性能不下降；
(2)具有良好的耐高温、抗氧化性，能够满足复合材料的高温使用要求；
(3)可设计性强，涂层结构组分可调可控，能够制备具有不同性能的吸波涂层；
(4)适用范围广，不仅可以用于改善CFCC的吸波性能，还可用于使用温度在涂层制备温度以上的陶瓷材料、金属及树脂基复合材料的吸波性能的优化。
附图说明
图1：吸波涂层制备工艺流程图
图2：本发明中吸波涂层的结构示意图
图3：(a)吸波涂层的表面形貌SEM照片和(b)表面化学成分EDS分析
图4：含有吸波涂层的二维SiC/SiBCN复合材料的电磁反射系数随涂层厚度的变化规律
图5：(a)MWCNTs剖面形貌TEM照片和(b)吸波涂层表面形貌SEM照片
具体实施方式
现结合实施例、附图对本发明作进一步描述：
针对吸波涂层的制备过程，本发明提出一种“涂刷技术”结合“化学气相沉积技术”的涂层低温制备方法，其流程图如附图1所示。该制备工艺主要包括以下三个核心环节：
(1)配料，将吸波剂与粘结剂、增塑剂和溶剂等材料混合均匀；
(2)涂刷，将(1)中混合浆料均匀涂刷在基底材料表面；
(3)沉积，在(2)中材料表面化学气相沉积透波涂层。
具体地说，首先，配料是本发明的基础环节。为了将吸波剂均匀涂刷在复合材料表面，需向其中添加多种有机物，配成满足一定黏度的浆料。添加的有机组分包括：溶剂(甲苯与异丙醇，体积比0.1～10)作为分散介质，占浆料的体积分数为60～75％；分散剂(磷酸三乙酯)，占浆料的体积分数为3％，使粉末态的吸波剂分散更加均匀；粘结剂(聚乙烯醇缩丁醛，PVB)，占浆料的体积分数为3％，使浆料具有一定的粘性，便于涂刷，并使干燥后的涂层具有一定的强度；增塑剂(丙三醇与邻苯二甲酸二乙酯，体积比0.1～1150)，占浆料的体积分数为2％，使涂刷层具有一定的塑性，便于后续流程；除泡剂(正丁醇与乙二醇，体积比0.1～10)，占浆料的体积分数为2％，减少浆料中的气泡，使涂刷更均匀。吸波剂(占浆料的体积分数为15～30％)与这些有机组分混合后，通过超声处理使浆料混合充分，成为均匀的悬浮液。
其次，涂刷是本发明的关键环节。由于每一遍涂刷后基底材料的厚度增加很小，因此需要不断重复这一步骤。为了保证浆料均匀涂刷在基底材料表面，相邻两遍的涂刷方向相反且间隔时间相等。达到预定厚度后，材料在室温空气中静置，使部分有机组分挥发。
最后，沉积是本发明的重要环节。单纯的吸波剂由于具有较高的介电常数和介电损耗，因此与自由空间之间存在阻抗失配现象，不能有效吸收电磁波。而且经涂刷、阴干后，附着在复合材料表面的吸波剂微粒与基底材料结合力很弱，容易脱落。化学气相沉积技术(CVD)具有优异的沉积渗透性，通过改变前驱体气源和沉积工艺参数(温度、反应气比例、沉积时间)，可制备出变厚度、变组分的各种耐高温透波阻抗匹配层，包括CVD Si3N4、CVD BN、CVD B4C、CVD BCN、CVD SiCN和CVD SiBCN等。将此技术应用于涂刷浆料后的材料表面，可使CVD过程的沉积产物很好的渗透进入吸波剂微粒层，固定包裹吸波剂使其与基底材料紧密结合。同时，沉积产物必须具备透波特性，使其作为吸波涂层的外部材料能够满足电磁波的阻抗匹配要求。而且其与吸波剂的包覆组合可以进一步调整吸波剂微粒层的介电常数，从而有效提高材料的吸波性能。
实施方案：
下面对本发明的实施作进一步描述。
实施例1：
选取二维SiC纤维增韧SiBCN基复合材料作为基底材料，材料尺寸为180mm×180mm×3.2mm。选用40wt.％A粉与60wt.％B粉形成的混合粉体作为吸波剂(其中，A粉为经过高温热处理的含纳米SiC的SiBCN粉体，B粉为未经高温热处理的不含纳米SiC的SiBCN粉体)。浆料中混合粉体的体积分数为30％，溶剂的体积分数为60％，分散剂和粘结剂的体积分数均为3％，增塑剂和除泡剂的体积分数均为2％。浆料超声处理2小时后，立即开始涂刷。涂刷完成后，复合材料在室温空气下静置12小时。浆料阴干后，将复合材料置于真空反应炉中化学气相沉积Si3N4。反应温度为800℃，先驱体系为SiCl4-NH3-H2-Ar，[Si]:[N]＝1:3，H2与SiCl4稀释比为10:1。吸波涂层制备完成后，采用弓形法对复合材料在8～18GHz内的电磁性能进行测试。附图3显示了此处制备的吸波涂层的表面形貌和表面化学组成。附图4显示了含有吸波涂层的复合材料在8～18GHz内的电磁反射系数随涂层厚度的变化情况。
实施例2：
选取Al2O3纤维毡增强SiCN基复合材料作为基底材料，材料尺寸为180mm×180mm×2mm。选用多壁碳纳米管(MWCNTs)作为吸波剂。浆料中吸波剂的体积分数为15％，溶剂的体积分数为75％，分散剂和粘结剂的体积分数均为3％，增塑剂和除泡剂的体积分数均为2％。浆料超声处理1小时后，立即开始涂刷。涂刷完成后，复合材料在室温空气下静置12小时。浆料阴干后，将复合材料置于真空反应炉中化学气相沉积B4C。反应温度为950℃，先驱体系为BCl3-CH4-H2-Ar，[B]:[C]＝3:1。吸波涂层制备完成后，采用弓形法对复合材料在8～18GHz内的电磁性能进行测试。附图5显示了本实施例中使用的MWCNTs的剖面形貌及吸波涂层的表面形貌。
实施例3：
选取C纤维增强的Si3N4基复合材料作为基底，材料尺寸为180mm×180mm×2mm。选用SiC晶须作为吸波剂。浆料中吸波剂的体积分数为20％，溶剂的体积分数为70％，分散剂和粘结剂的体积分数均为3％，增塑剂和除泡剂的体积分数均为2％。浆料超声处理1.5小时后，立即开始涂刷。涂刷完成后，复合材料在室温空气下静置12小时。浆料阴干后，将复合材料置于真空反应炉中化学气相沉积SiCN。反应温度为1000℃，先驱体系为SiCl4–C3H6–NH3–H2–Ar，[Si]:[N]＝4.25:1，[C]:[N]＝9:1。
实施例4：
选取致密的Si3N4陶瓷片作为基底材料，材料尺寸为22.86mm×10.16mm×3mm。选用ZnO-ZnAl2O4复合陶瓷粉末作为吸波剂。浆料中吸波剂的体积分数为25％，溶剂的体积分数为65％，分散剂和粘结剂的体积分数均为3％，增塑剂和除泡剂的体积分数均为2％。浆料超声处理1.5小时后，立即开始涂刷。涂刷完成后，在室温空气下静置12小时。浆料阴干后，将材料置于真空反应炉中化学气相沉积BN。反应温度为650℃，先驱体系为BCl3-NH3-H2-Ar，[B]:[N]＝1:3。

Claims (3)

1.一种对8～18GHz频段内的吸波陶瓷涂层的低温制备方法，其特征在于步骤如下：
步骤1、制备含有吸波剂的浆料：按照浆料的体积分数配比物质为：60～75％的溶剂、3％的分散剂磷酸三乙酯、3％的粘结剂聚乙烯醇缩丁醛、2％的增塑剂、2％的除泡剂、15～30％的吸波剂；将上述物质混合后，通过超声处理使浆料混合充分，成为均匀的悬浮液；
所述溶剂是体积比0.1～10的甲苯与异丙醇的混合溶剂；
所述增塑剂是体积比0.1～1150的丙三醇与邻苯二甲酸二乙酯的混合物；
上述除泡剂是体积比0.1～10的正丁醇与乙二醇的混合物；
步骤2：将步骤1的浆料按照设计厚度涂刷在基底材料表面，然后静置阴干；
步骤3：通过化学气相沉积技术CVD在涂刷浆料的基底材料上低温制备透波层。
2.根据权利要求1所述对8～18GHz频段内的吸波陶瓷涂层的低温制备方法，其特征在于：所述吸波剂为碳纳米管、石墨烯、纳米碳化硅晶粒或碳化硅晶须。
3.根据权利要求1所述对8～18GHz频段内的吸波陶瓷涂层的低温制备方法，其特征在于：所述基底材料为陶瓷和陶瓷基复合材料、金属及金属基复合材料、树脂及树脂基复合材料。
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