CN115093208A - 一种可变形仿生陶瓷/聚合物复合防护材料及其制备方法 - Google Patents

一种可变形仿生陶瓷/聚合物复合防护材料及其制备方法 Download PDF

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CN115093208A
CN115093208A CN202210869904.2A CN202210869904A CN115093208A CN 115093208 A CN115093208 A CN 115093208A CN 202210869904 A CN202210869904 A CN 202210869904A CN 115093208 A CN115093208 A CN 115093208A
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ceramic
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protective material
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何汝杰
张学勤
李营
方岱宁
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Beijing Institute of Technology BIT
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Abstract

本发明公开一种可变形仿生陶瓷/聚合物复合防护材料及其制备方法，属于仿生材料技术领域，具体包括以下步骤：(1)片状陶瓷/聚合物复合材料的制备；(2)仿生柔性聚合物基板的制备；(3)仿生陶瓷/聚合物复合防护材料的制备。本发明得到的可变形仿生陶瓷/聚合物复合防护材料具有优良的力学性能，能够适应不同的工作空间，可实现对全身的高效防护。另外，本发明中陶瓷浆料制备方法简单、易操作，便于进行推广使用。

Description

一种可变形仿生陶瓷/聚合物复合防护材料及其制备方法
技术领域
本发明涉及仿生材料领域，特别是涉及一种可变形仿生陶瓷/聚合物复合防护材料及其制备方法。
背景技术
公安人员在执行防爆、反恐、缉毒等任务时，经常处于苛刻严峻的工作环境中，生命安全容易受到不同程度的威胁，进而，公安人员穿戴的防护装备的材料与结构对于保障生命安全、提高任务完成度有重要意义。
现有技术中，公安人员使用的安全防护装备主要分为“刚性”和“柔性”两类。其中，刚性防护装备为将高强度合金片、陶瓷片等刚性插板装备在防护背心内，可以有效保护人体躯干中的重要器官免受子弹、钝器等带来的极端伤害。然而，刚性插板通常无法装备在四肢等运动状态频繁改变的位置，不能为人体提供全方位保护。并且，刚性防护材料的密度通常较大，一定程度上会降低公安人员的行动能力。轻质柔性纺织防护服更多地被用作公安人员的常规防护服，相比于刚性插板，柔性防护服能包裹全身，一定程度上能避免人体被常规小型锐器袭击。但是，柔性防护服的防护能力相当有限，对钝器打击或突发极端环境下的子弹无能为力。
因此，如何提供一种能够对公安人员进行全身高效防护、保障公安人员在复杂极端环境中的生命安全，且便于公安人员运动的防护用具是本领域技术人员亟需解决的技术问题。
发明内容
本发明的目的是提供一种可变形仿生陶瓷/聚合物复合防护材料，以解决现有刚性防护材料防护范围有限及柔性防护材料防护效果不佳等问题。
为实现上述目的，本发明提供了如下方案：
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，具体包括以下步骤：
(1)将第一聚合物涂覆于片状仿生陶瓷材料表面，置于烘箱养护后，得到片状陶瓷/聚合物复合材料；
(2)将第二聚合物倒入模具后刮平表面，置于烘箱中养护后，得到仿生柔性聚合物基板；
(3)将所述片状陶瓷/聚合物复合材料在仿生柔性聚合物基板上排列并粘结后，置于烘箱中养护，得到仿生陶瓷/聚合物复合防护材料。
优选的，步骤(1)中所述第一聚合物为聚甲基丙烯酸甲酯、环氧树脂和改性聚脲弹性体中的任意一种；
所述片状仿生陶瓷材料为与生物鳞片的宏观形貌相同或近似相同的结构；
所述生物鳞片包括鱼或蛇的体表鳞片；
更为优选的，所述片状仿生陶瓷材料的长、宽和高与生物鳞片无等比例关系，可以在图1中x、y和z三个方向以不同的比例放大或缩小；所述片状仿生陶瓷材料与生物鳞片表面起伏及粗糙度无相等要求。
有益效果：本发明以高强度的陶瓷和高韧性的聚合物为原料，设计并制备了仿生陶瓷/聚合物复合防护材料。该复合防护材料中，涂覆有聚合物涂层的片状陶瓷/聚合物复合材料为刚性承载结构，韧性聚合物薄层为连接片状陶瓷/聚合物复合材料的基板。通过设计片状陶瓷/聚合物复合材料的排列方式能改变仿生陶瓷/聚合物复合防护材料的可变形程度，最终得到的仿生陶瓷/聚合物复合防护材料在较大变形范围内表现出可靠的承载能力，实现对人体的全身防护。
优选的，所述片状仿生陶瓷材料的制备方法包括以下步骤：
(1-1)生物鳞片结构及排列方式确定：通过x射线断层扫描技术确定生物鳞片结构及排列方式；
(1-2)片状仿生陶瓷材料的结构设计：对步骤(1)生物鳞片结构及排列方式进行抽象设计，并利用三维建模软件绘制生物鳞片状结构模型；
(1-3)3D打印片状仿生陶瓷材料：配制陶瓷浆料，根据所述生物鳞片状结构模型进行3D打印，去除生坯上的支撑材料并依次进行醇洗、干燥、排脂、烧结处理，得到3D打印的片状仿生陶瓷材料。
有益效果：本发明通过设计片状仿生陶瓷材料的形状实现对其力学性能的设计，同时通过选择不同的陶瓷材料改变片状仿生陶瓷材料的力学性能，另外，本发明中的片状仿生陶瓷材料的尺寸并无具体限定，能够适应不同的工作空间。
优选的，步骤(1-3)中所述陶瓷浆料包括以下原料：陶瓷粉体体积含量35～60vol.％，光敏树脂含量40～65vol.％；分散剂添加量为陶瓷粉体用量的0.5～5wt％，光引发剂添加量为光敏树脂用量的0.5～4wt％，烧结助剂用量为陶瓷粉体用量的0.5～5wt％。
有益效果：本发明通过改变陶瓷浆料中原料粉的比例，得到低粘度、均匀分散的陶瓷浆料，有利于得到成分均匀的片状仿生陶瓷材料。
优选的，所述陶瓷粉体为氧化铝、氧化锆、氧化硅、碳化硅、氮化硅和氮化铝中的任意一种；
所述分散剂为KOS110分散剂或路博润超分散剂17000；
所述光敏树脂为1,6-己二醇二丙烯酸酯和三羟甲基丙烷三丙烯酸酯中的任意一种；
所述光引发剂为TPO光引发剂；
所述烧结助剂为二氧化钛、氧化钇和氧化镁中的一种或几种。
有益效果：本发明中通过改变分散剂和光敏树脂的种类和含量，可以得到稳定、均匀分散的陶瓷浆料；改变陶瓷浆料中陶瓷粉体的种类，可以得到不同力学性能的片状仿生陶瓷材料以适应不同的工作条件。
优选的，步骤(1-3)中所述醇洗为利用无水乙醇清洗；
所述干燥为室温干燥10h；
所述排脂为400～600℃排脂1～5h，升温速度为0.5～5℃/min；
所述烧结为1400～1800℃烧结1～5h，升温速度为0.5～10℃/min。
有益效果：本发明中通过设定排脂和烧结的温度及时间，有益于得到致密、力学性能优异的片状仿生陶瓷材料。
优选的，步骤(1-3)中所述3D打印为立体光刻成型技术和数字光处理成型技术中的一种。
有益效果：本发明中使用的立体光刻成型技术和数字光处理成型技术能实现陶瓷材料复杂结构的制备，且有较高的成型精度。
优选的，步骤(2)中所述第二聚合物为聚甲基丙烯酸甲酯、环氧树脂和改性聚脲弹性体中的任意一种；
所述养护为室温～100℃养护6～72h。
有益效果：本发明中使用的聚合物具有高韧性和优秀的变形能力，有益于实现具有大变形能力的仿生陶瓷/聚合物复合防护材料的制备。
优选的，步骤(3)中所述排列方式与生物鳞片排列方式相同或近似；
所述粘结为利用第三聚合物粘结，且所述第三聚合物为聚甲基丙烯酸甲酯、环氧树脂和改性聚脲弹性体中的任意一种。
有益效果：本发明中使用的聚合物具有高韧性和优秀的变形能力，有益于实现片状陶瓷/聚合物复合材料与聚合物基板间的紧密结合。
一种如上述制备方法制备得到的可变形仿生陶瓷/聚合物复合防护材料。
有益效果：本发明中通过结合3D打印技术和聚合物涂覆技术得到了一种可变形仿生陶瓷/聚合物复合防护材料，同时具有高强度及大的变形能力，能够对公安人员进行全身高效防护、保障公安人员在复杂极端环境中的生命安全，且便于公安人员运动。
本发明公开了一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，本发明使用陶瓷材料3D打印技术制备片状仿生陶瓷材料，将聚合物涂覆在片状仿生陶瓷材料表面形成片状陶瓷/聚合物复合材料；参考鳞片在生物体表排列方式，将仿生复合片状结构镶嵌在柔性聚合物基板上，最终得到的可变形仿生陶瓷/聚合物复合防护材料可实现对全身的高效防护。另外，本发明中陶瓷浆料制备方法简单、易操作，采用光固化3D打印成型技术，如立体光刻成型技术(SLA)、数字光处理成型技术(DLP)，可实现多种复杂结构的高精度成型。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例1中片状陶瓷/聚合物复合材料制备过程示意图；
图2为本发明实施例1中仿生陶瓷/聚合物复合防护材料示意图；
图3为本发明实施例2中仿生陶瓷/聚合物复合防护材料示意图；
图4为本发明实施例3中仿生陶瓷/聚合物复合防护材料示意图；
图5为本发明实施例1中片状仿生陶瓷材料的SEM电镜扫描图。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和具体实施方式对本发明作进一步详细的说明。
实施例1
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，包括以下步骤：
(1)片状仿生陶瓷材料设计：绘制图1所示片状仿生陶瓷材料的三维模型，该模型在x、y和z方向的尺寸分别为10mm、8mm和1mm，将stl格式的片状仿生陶瓷材料的三维模型导入10dim软件中切片得到tdp文件，切片厚度为75μm；
(2)3D打印片状仿生陶瓷材料：
(2-1)配制陶瓷浆料：陶瓷浆料包括以下原料：氧化铝陶瓷粉体体积分数为55vol.％，光敏树脂体积分数为45vol.％，分散剂KOS110添加量为氧化铝陶瓷粉体用量的5wt.％，光引发剂TPO添加量为光敏树脂用量的3wt.％，烧结助剂二氧化钛用量为氧化铝陶瓷粉体用量的2wt.％，烧结助剂氧化镁用量为氧化铝陶瓷粉体用量的3wt.％，将上述原料混合后用氧化锆球磨珠以400转/分钟的速度球磨48h，即可得陶瓷浆料；
(2-2)片状仿生陶瓷材料的生坯制备：将步骤(1)所得tdp文件导入3D打印机，并将步骤(2-1)所得陶瓷浆料输送到物料罐中，设置紫外光功率为8500μW/cm2，单层曝光时间为4s，打印完成后去除生坯上的支撑材料并用无水乙醇清洗，获得片状仿生陶瓷材料的生坯；
(2-3)片状仿生陶瓷材料烧结：将上述生坯依次在室温下干燥10h、以0.5℃/min的升温速率升温至550℃排脂4h，然后以10℃/min的升温速率升温至1550℃烧结2h，得到3D打印的氧化铝片状仿生陶瓷材料；由图5可以看出，该氧化铝片状仿生陶瓷材料具有致密的微观结构；
(3)片状陶瓷/聚合物复合材料：将改性聚脲弹性体涂覆0.5mm于上述所得到的氧化铝片状仿生陶瓷材料，置于70℃烘箱中养护24h，得到图1所示氧化铝片状陶瓷/聚合物复合材料；
(4)仿生柔性聚合物基板的制备：将改性聚脲弹性体倒入预先准备好的200mm×100mm×1mm的模具，并刮平表面，置于70℃烘箱中养护24h，得到尺寸为200mm×100mm1mm的仿生改性聚脲弹性体基板；
(5)仿生陶瓷/聚合物复合防护材料的制备：将氧化铝片状陶瓷/聚合物复合材料沿x方向间隔11mm排列第一排氧化铝片状陶瓷/聚合物复合材料；将第一排结构沿x方向平移5.5mm、沿y方向平移4mm排列第二排结构；将其余氧化铝片状陶瓷/聚合物复合材料以与第一、第二排相同的方式沿y方向以8mm的间距排列仿生柔性基板上，用改性聚脲弹性体将排列好的复合片状结构粘在仿生柔性基板上，置于70℃烘箱中养护24h后得到图2所示平整的仿生氧化铝陶瓷/改性聚脲弹性体复合防护材料。
实施例2
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，与实施例1的不同之处在于：
陶瓷浆料中陶瓷粉体体积为40vol.％，光敏树脂含量为60vol.％，分散剂添加量为陶瓷粉体用量的2wt.％，光引发剂添加量为光敏树脂用量的0.5wt.％。
片状仿生陶瓷材料生坯的排脂、烧结制度分别为：500℃排脂5h、1700℃烧结5h。
将平整仿生氧化铝陶瓷/改性聚脲弹性体复合防护材料扭转120°，得到图3所示扭转仿生氧化铝陶瓷/改性聚脲弹性体复合防护材料。
实施例3
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，与实施例1的不同之处在于：
将平整仿生氧化铝陶瓷/改性聚脲弹性体复合防护材料弯曲180°，得到图4所示弯曲仿生氧化铝陶瓷/改性聚脲弹性体复合防护材料。
实施例4
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，与实施例2的不同之处在于：
将氧化铝替换为氧化锆，紫外光功率设置为6000μW/cm2，单层固化厚度为50μm，单层曝光时间为4s；烧结条件改为1650℃烧结4h。
实施例5
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，与实施例2的不同之处在于：
将聚合物1替换为聚甲基丙烯酸甲酯，在室温下养护48h。
实施例6
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，与实施例3的不同之处在于：
将聚合物1替换为环氧树脂，将聚合物替换为聚甲基丙烯酸甲酯，在50℃养护20h。
对比例1
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，与实施例3的不同之处在于：
片状仿生材料不是陶瓷材料，而是酚醛塑料。
对比例2
一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，与实施例3的不同之处在于：
片状仿生陶瓷材料表面没有涂覆聚合物。
技术效果
通过万能试验机测定变形后仿生陶瓷/聚合物复合防护材料的抗压强度，加载速度为0.2mm/min。以仿生陶瓷/聚合物复合防护材料的变形终态与初始状态间的角度度量其变形量。
表1
抗压强度 变形量
实施例1 15.8MPa 0°
实施例2 14.6MPa 扭转120°
实施例3 17.1MPa 弯曲180°
实施例4 18.6MPa 扭转120°
实施例5 10.9MPa 扭转120°
实施例6 10.5MPa 弯曲180°
对比例1 5.8MPa 弯曲180°
对比例2 7.3MPa 弯曲180°
由表1中试验数据可以看出，本发明使用陶瓷材料3D打印技术制备片状仿生陶瓷材料，通过聚合物包覆片状仿生陶瓷材料实现了陶瓷材料的增韧效果；片状陶瓷/聚合物复合材料排列并粘于柔性聚合物基板上，最终制备得到的仿生陶瓷/聚合物复合防护材料具有高强度及大范围可变形等特性。
以上所述的实施例仅是对本发明的优选方式进行描述，并非对本发明的范围进行限定，在不脱离本发明设计精神的前提下，本领域普通技术人员对本发明的技术方案做出的各种变形和改进，均应落入本发明权利要求书确定的保护范围内。

Claims (10)

1.一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，具体包括以下步骤：
(1)将第一聚合物涂覆于片状仿生陶瓷材料表面，置于烘箱养护后，得到片状陶瓷/聚合物复合材料；
(2)将第二聚合物倒入模具后刮平表面，置于烘箱中养护后，得到仿生柔性聚合物基板；
(3)将所述片状陶瓷/聚合物复合材料在仿生柔性聚合物基板上排列并粘结后，置于烘箱中养护，得到仿生陶瓷/聚合物复合防护材料。
2.根据权利要求1所述的一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，步骤(1)中所述第一聚合物为聚甲基丙烯酸甲酯、环氧树脂和改性聚脲弹性体中的任意一种；
所述片状仿生陶瓷材料为与生物鳞片完全相同或近似相同的结构；
所述生物鳞片包括鱼或蛇的体表鳞片；
所述第一聚合物的涂覆厚度为0.05～3mm；
所述养护为室温～100℃养护6-72h。
3.根据权利要求2所述的一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，所述片状仿生陶瓷材料的制备方法包括以下步骤：
(1-1)生物鳞片结构及排列方式确定：通过x射线断层扫描技术确定生物鳞片结构及排列方式；
(1-2)片状仿生陶瓷材料的结构设计：对步骤(1)生物鳞片结构及排列方式进行抽象设计，并利用三维建模软件绘制生物鳞片状结构模型；
(1-3)3D打印片状仿生陶瓷材料：配制陶瓷浆料，根据所述生物鳞片状结构模型进行3D打印，去除生坯上的支撑材料并依次进行醇洗、干燥、排脂、烧结处理，得到3D打印的片状仿生陶瓷材料。
4.根据权利要求3所述的一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，步骤(1-3)中所述陶瓷浆料包括以下原料：陶瓷粉体35～60vol.％，光敏树脂40～65vol.％；
分散剂为陶瓷粉体用量的0.5～5wt.％，光引发剂为光敏树脂用量的0.5～4wt.％，烧结助剂为陶瓷粉体用量的0.5～5wt.％。
5.根据权利要求4所述的一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，所述分散剂为KOS110分散剂或路博润超分散剂17000；
所述陶瓷粉体为氧化铝、氧化锆、氧化硅、碳化硅、氮化硅和氮化铝中的任意一种；
所述光敏树脂为1,6-己二醇二丙烯酸酯和三羟甲基丙烷三丙烯酸酯中的任意一种；
所述光引发剂为TPO光引发剂；
所述烧结助剂为二氧化钛、氧化钇和氧化镁中的一种或几种。
6.根据权利要求3所述的一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，步骤(1-3)中所述醇洗为利用无水乙醇清洗；
所述干燥为室温干燥10h；
所述排脂为400～600℃排脂1～5h，升温速度为0.5～5℃/min；
所述烧结为1400～1800℃烧结1～5h，升温速度为0.5～10℃/min。
7.根据权利要求3所述的一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，步骤(1-3)中所述3D打印为立体光刻成型技术和数字光处理成型技术中的一种。
8.根据权利要求1所述的一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，步骤(2)中所述第二聚合物为聚甲基丙烯酸甲酯、环氧树脂和改性聚脲弹性体中的任意一种；
所述养护为室温～100℃养护6～72h。
9.根据权利要求1所述的一种可变形仿生陶瓷/聚合物复合防护材料的制备方法，其特征在于，步骤(3)中所述排列方式与生物鳞片排列方式相同或近似；
所述粘结为利用第三聚合物粘结，且所述第三聚合物为聚甲基丙烯酸甲酯、环氧树脂和改性聚脲弹性体中的任意一种；
所述养护为室温～100℃养护6～72h。
10.一种如权利要求1-9任一项所述的制备方法制备得到的可变形仿生陶瓷/聚合物复合防护材料。
CN202210869904.2A 2022-07-22 2022-07-22 一种可变形仿生陶瓷/聚合物复合防护材料及其制备方法 Pending CN115093208A (zh)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104776755A (zh) * 2015-04-17 2015-07-15 山东天意高科技有限公司 仿生柔性防护装备
CN110645836A (zh) * 2019-10-25 2020-01-03 湖南大学 仿生柔性躯干防护装具及其制备方法
CN113754412A (zh) * 2021-09-15 2021-12-07 北京理工大学 一种高强吸能陶瓷-聚合物复合结构的制备方法及其产品
CN114228283A (zh) * 2021-12-02 2022-03-25 南京航空航天大学 仿中华鲟背部骨鳞及鱼皮的多层级柔性防护结构

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104776755A (zh) * 2015-04-17 2015-07-15 山东天意高科技有限公司 仿生柔性防护装备
CN110645836A (zh) * 2019-10-25 2020-01-03 湖南大学 仿生柔性躯干防护装具及其制备方法
CN113754412A (zh) * 2021-09-15 2021-12-07 北京理工大学 一种高强吸能陶瓷-聚合物复合结构的制备方法及其产品
CN114228283A (zh) * 2021-12-02 2022-03-25 南京航空航天大学 仿中华鲟背部骨鳞及鱼皮的多层级柔性防护结构

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