CN111620695A - 一种层状结构的陶瓷材料 - Google Patents

一种层状结构的陶瓷材料 Download PDF

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CN111620695A
CN111620695A CN202010437255.XA CN202010437255A CN111620695A CN 111620695 A CN111620695 A CN 111620695A CN 202010437255 A CN202010437255 A CN 202010437255A CN 111620695 A CN111620695 A CN 111620695A
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ceramic
layer
layers
interface
interface layer
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杨金晶
黄政仁
刘学建
陈忠明
黄毅华
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Shanghai Prospective Innovation Research Institute Co ltd
Shanghai Institute of Ceramics of CAS
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Shanghai Prospective Innovation Research Institute Co ltd
Shanghai Institute of Ceramics of CAS
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Abstract

本发明提供一种层状结构的陶瓷材料，由共烧结的两层以上的堆叠陶瓷层及陶瓷层间的界面层构成，所述陶瓷层的厚度为0.2mm～20mm，所述界面层的厚度小于1mm，所述界面层的材料采用能使相邻陶瓷层之间不连续地结合的材料。

Description

一种层状结构的陶瓷材料
技术领域
本发明涉及人员及装备防护用陶瓷材料领域，具体涉及一种陶瓷材料，可用于陶瓷装甲。
背景技术
陶瓷防护装甲是高等级防护优秀材料，用于制备防弹背心插板、车船或飞行器的防弹板。目前，陶瓷防护装甲大都采用均质陶瓷制备，高速弹丸冲击陶瓷装甲后形成冲击波，弹着面受压应力影响，冲击波会迅速扩展至背面形成张应力。由于陶瓷抗压强度高、抗拉强度低，因此较低的张应力即会破坏陶瓷装甲，导致防护能力下降。
发明内容
针对上述问题，本发明的目的在于提供一种具有层状结构特征的陶瓷材料，具有轻质、抗冲击性能优异(高防护系数)的优点。
在此，一方面，本发明提供一种层状结构的陶瓷材料，由共烧结的两层以上的堆叠陶瓷层及陶瓷层间的界面层构成，所述陶瓷层的厚度为0.2mm～20mm，所述界面层的厚度小于1mm，所述界面层的材料采用能使相邻陶瓷层之间不连续地结合的材料。
本发明的陶瓷材料，由共烧结的堆叠陶瓷层及陶瓷层间的界面层构成，陶瓷层的厚度为0.2mm～20mm，界面层的厚度小于1mm，能通过界面层使相邻陶瓷层之间不连续地结合。高速冲击能量在陶瓷受冲击面形成压应力，并以冲击波的形式在陶瓷结构内部传递至反面形成张应力，由于陶瓷材料具有抗压强度高但抗拉强度低的特点，冲击波形成的张应力破坏陶瓷结构。如采用均质块体陶瓷材料，冲击波能量完整传递直至陶瓷均质块体反面，引起整体破碎；本发明通过叠层陶瓷结构与弱界面(共烧结后的各陶瓷层之间形成弱结合界面)结合，可以有效阻隔、分散冲击波，防止冲击波集中造成的破坏，提高质量防护能力。本发明的陶瓷材料可用于陶瓷装甲等。用于陶瓷装甲的情况下，通过该层状结构可以防止陶瓷装甲的整体破坏，缩小第一次打击后的碎裂区域，提高陶瓷装甲的抗打击次数。
较佳地，所述界面层具有第一类界面层和/或第二类界面层，所述第一类界面层的材料为打孔或不连续的纸片、打孔或不连续的塑料膜的至少一种，所述第二类界面层的材料为石墨烯、碳纳米管、碳纤维、碳化硅纤维、碳化硅晶须、氧化铝纤维、玻璃纤维、石棉中的至少一种。
所述陶瓷层的材料可以为氧化铝陶瓷、碳化硅陶瓷、碳化硼陶瓷、镁铝硼化物陶瓷及以上类型陶瓷的纤维增强复合材料中的至少一种。
所述陶瓷层的厚度可以为1mm～15mm。
所述界面层的厚度可以为0.02mm～1mm。
所述界面层占陶瓷层面积比可以为10％～90％。
较佳地，所述界面层占陶瓷层面积比为70％～80％。
所述陶瓷层的层数可以为2层以上。
较佳地，在所述界面层同时具有第一类界面层和第二类界面层的情况下，所述第二类界面层至少包括与最表层陶瓷层结合的第二类界面层及与最底层陶瓷层结合的第二类界面层。
较佳地，所述陶瓷层的层数为三层以上，最表层陶瓷层及最底层陶瓷层的厚度大于其余陶瓷层。
另一方面，本发明还提供上述任一种层状结构的陶瓷材料的制备方法，包括：使用陶瓷层材料与界面层材料，形成陶瓷层与界面层相互交错层叠的多层结构，并使该多层结构的最顶层及最底层为陶瓷层；将所述多层结构压制成型后烧结，得到所述陶瓷材料。
可采用例如流延、挤出、浇注以及压制成型等方法制备陶瓷层的坯体。
附图说明
图1示意性示出本发明一实施形态的陶瓷材料的结构。
具体实施方式
以下结合附图和下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
本公开涉及一种陶瓷材料，可适用于人员及装备的防护，可用于陶瓷装甲。本公开的层状结构陶瓷材料，由多层陶瓷及界面层堆叠后共烧结，形成具有层状结构的陶瓷材料；通过层状结构设计以及弱连接界面复合，阻碍冲击波在陶瓷材料内部的传递，防止整体破碎。例如，用于陶瓷装甲时，可阻碍弹丸冲击波在装甲材料内部的传递，防止整体破碎，提高陶瓷装甲防弹性能。
本公开的层状结构陶瓷材料由共烧结的两层以上的堆叠陶瓷层及陶瓷层间的界面层构成。这里，“两层以上的堆叠陶瓷层及陶瓷层间的界面层”表示陶瓷层(两层以上的陶瓷层)与界面层相互交错层叠的多层结构，且该多层结构的最顶层及最底层为陶瓷层(如图1)。
陶瓷层材料可以为氧化铝(Al2O3)陶瓷、碳化硅(SiC)陶瓷、碳化硼(B4C)陶瓷、镁铝硼化物陶瓷(AlMgBn)陶瓷以及以上类型陶瓷(Al2O3陶瓷、SiC陶瓷、B4C陶瓷、AlMgBn陶瓷)的纤维增强复合材料。可根据不同抗冲击性(防护)需求，通过调整陶瓷原料组成及组分，调整不同叠层之间的材料性能，使叠层烧结后的陶瓷材料具有最佳性能。在一个示例中，陶瓷层材料可以为碳化硅、碳化硼、镁铝硼化物陶瓷，可用于例如人员与飞行器防护时，以获得优异的质量防护系数。在另一个示例中，陶瓷层材料可以为氧化铝、碳化硅，可用于例如车船装备用防护时，在较低的防护成本下具有较优的质量防护系数。
界面层的材料采用能使相邻陶瓷层之间不连续地结合的材料。“不连续地结合”表示陶瓷层与界面层共烧结得到的陶瓷材料中，相邻的陶瓷层之间形成不连续结合的界面，形成整体结合完整但具有不连续界面的层状陶瓷材料。陶瓷材料烧结后上下陶瓷层之间不连续结合，形成弱结合界面。这里的“上下陶瓷层”也可称相邻陶瓷层，“上下”并非限定陶瓷层排布方向。界面层可以包括薄膜空隙层(第一类界面层)和/或复合物隔层(第二类界面层)，在烧结后各相邻陶瓷层之间形成弱结合界面，使冲击波在陶瓷材料传递时被阻隔、分散。薄膜空隙层可采用打孔或不连续薄膜隔层为材料，例如均匀分布的打孔纸片、打孔塑料膜等，此类材料在陶瓷成型过程中可不连续阻隔上下陶瓷层，在烧结时阻碍上下层陶瓷扩散结合，并在陶瓷烧结过程中被烧失形成空隙，从而在整体结构上形成具有空隙的弱结合界面，同时可以低成本制备陶瓷材料。打孔纸片(打孔塑料膜)的孔均匀分布，孔内接圆直径较佳的不小于5mm，使相邻陶瓷层能有效扩散结合。孔面积占纸片(塑料膜)总体面积的比率可以为15％～90％，较小的孔面积可形成较大的弱界面区域，但可能不利于烧结，从便于整体烧结方面考虑，理想的是湿法和半湿法陶瓷成型工艺不低于10％的孔面积以及干法成型不低于15％的孔面积；另一方面，较大的孔面积会减少弱界面区，考虑到使烧结后抗冲击性能优于以往的致密的块体材料，理想的是不超过85％的孔面积。界面层的厚度可以为0.02mm～1mm。优选界面层的厚度在0.5mm以下，从而可以容易地获得本公开的陶瓷材料。一实施形态中，纸片(塑料膜)的厚度可以为0.02mm～0.5mm，为了在烧失后能形成明显的空隙层，理想的是厚度不小于0.02mm的纸片(塑料膜)。复合物隔层可采用复合物填充材料，例如石墨烯、碳纳米管、碳纤维、碳化硅纤维、碳化硅晶须、氧化铝纤维、玻璃纤维、石棉等。利用石墨烯、纤维等材料的高拉伸强度，可以在陶瓷碎裂时更有效地防止裂纹扩展。石墨烯或纤维等材料应铺设均匀，铺设密度可以为15％～90％(即10％～85％的空隙)。铺设密度是指可以阻隔上下陶瓷层、防止烧结扩散、形成空隙层的隔层材料面积，占单层界面层总面积的百分比。在相同陶瓷层材料的情况下，由复合物隔层制备界面层的层状材料总是比薄膜隔层制备界面层的层状材料具有更优的抗冲击性能，但制备工艺较复杂成本较高，可根据不同抗冲击性需求及成本控制调整采用一种或同时具有两种界面层。采用界面层同时具有薄膜空隙层和复合物隔层的情况下，可至少包括与最表层(如图1中最靠近弹丸的层)陶瓷层结合的复合物隔层及与最底层(如图1中最远离弹丸的层)陶瓷层结合的复合物隔层。在一个示例中，界面层材料可以为碳纤维、石墨烯，可用于例如人员与飞行器防护时，从而获得较优的防护效果。在另一个示例中，界面层材料可以为薄膜材料，可用于例如车船装备用防护时，从而降低成本。
陶瓷堆叠层数大于等于2。一般在相同的工艺条件下，提高层数总是可以提高抗冲击能力。根据目前以防护化学动能为主体的应用背景，从结构带来的防护提升相比工艺成本的提升方面考虑，理想的是2～15层。每一层陶瓷层的厚度可为0.2mm～20mm，优选陶瓷层的厚度为1mm～15mm。界面层的厚度可小于0.5mm，优选为0.02mm～0.5mm。可根据不同抗冲击性需求调整陶瓷层的层数及陶瓷层与界面层的厚度等。例如，在下表中分别示出用于人员与飞行器防护时的一例以及用于车船装备用防护时的一例；
Figure BDA0002502754330000041
各层厚度可以根据不同抗冲击性需求，采用等厚或不等厚设计。例如，陶瓷层的层数为三层以上时，可设为表面层(最表层陶瓷层及最底层陶瓷层)的厚度大于其余陶瓷层(中间层)。
界面层占陶瓷层面积比可以为10％～85％。这里，“界面层占陶瓷层面积比”表示界面层与陶瓷层接触部分的面积。控制界面层与陶瓷层的接触面积可控制上下陶瓷层间烧结后的结合强度。
本公开的层状结构陶瓷材料的制备
首先，根据要求的厚度、层数、面积比等，使用相应陶瓷层材料与界面层材料，形成陶瓷层与界面层相互交错层叠的多层结构，并使该多层结构的最顶层及最底层为陶瓷层。可根据抗冲击性(防护)需求，设计、制备一定厚度、一定层数的片状陶瓷坯体，堆叠陶瓷坯体，层间不连续铺设复合物隔层或纸片、塑料薄膜片材料(薄膜空隙层)。可以在堆叠(铺设)前，使用陶瓷层原料制备要求的厚度的坯体。陶瓷层原料可以采用Al2O3、SiC、B4C、AlMgBn。可采用湿法、半湿法、干压等成型方法制备陶瓷层的坯体。例如，在一些实施形态中，成型方法为流延、挤出、浇铸、干压、等静压成型工艺。陶瓷层的成型可采用通用成型方法。另外，可如通用烧结工艺决定陶瓷烧结助剂、添加剂等的使用。
接着，将多层结构压制成型后烧结，得到所述陶瓷材料。将堆叠后的陶瓷坯体高温烧结，形成整体结合完整但具有不连续界面的层状陶瓷装甲。烧结制度与该类型的陶瓷烧结制度一致。可采用通用方式烧结。
本发明采用叠层陶瓷结构与弱界面结合的方式制备陶瓷材料，可以有效阻隔、分散冲击波，防止冲击波集中造成的破坏，提高质量防护能力；层状结构可以防止陶瓷材料的整体破坏，缩小第一次打击后的碎裂区域，提高陶瓷材料的抗打击次数。可以根据不同防护需求，通过调整陶瓷原料组成及组分，调整不同叠层之间的材料性能，使叠层烧结后的陶瓷材料具有最佳性能。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
在下述实施例中，所使用到的试剂、材料以及仪器如没有特殊的说明，均为常规试剂、常规材料以及常规仪器，均可商购获得，其中所涉及的试剂也可通过常规合成方法合成获得。
实施例1
通过半湿法成型工艺，5MPa压力挤出制备3层碳化硅(添加碳化硼、碳烧结助剂)塑性泥料坯体；
表层(着弹层)坯体厚度5mm，主要原料采用0.2微米碳化硅粉体；中间层坯体厚度2.5mm，主要原料采用90％的0.2微米与10％的5微米碳化硅粉体；底层坯体厚度5mm，主要原料采用0.2微米碳化硅粉体。堆叠3层陶瓷坯体并在层间铺设打孔纸片，孔面积约占纸片总体面积30％，厚度约0.2mm，界面层占陶瓷层面积比为70％。纸片尺寸小于坯体，铺设后距离坯体四边空余5mm。将堆叠后的坯体放入压机加压，加压5MPa，使3层坯体贴合，并压制成曲面形状。将坯体放入窑具中干燥、脱粘，2180℃烧结18小时，烧结后碳化硅陶瓷装甲厚度10mm，具有层状结构。
实施例2
通过干压成型工艺，30MPa压力制备2层碳化硼(添加碳烧结助剂)坯体；
着弹层坯体厚度6mm，底层坯体厚度6mm。堆叠2层坯体并在层间铺设T300型碳纤维编制布，编织布厚度约0.5mm，编织密度10％，界面层占陶瓷层面积比为10％。将堆叠后的坯体放入窑具中30MPa热压2150℃烧结18小时，烧结后碳化硼陶瓷装甲厚度9.5mm，具有2层结构。
实施例3
通过等静压成型工艺，150MPa压力制备2层氧化铝坯体，厚度为15mm，分别为第一层及第十二层；
通过湿法成型工艺具体为流延成型制备10层1mm厚氧化铝坯体作为中间层；堆叠12层坯体，第一层与第二层以及第十一层与第十二层间铺设0.1mm厚氧化铝纤维，铺设密度约70％；其余层间铺设10％孔面积、0.05mm厚打孔纸片，界面层占陶瓷层面积比分别为70％与10％。加压0.5MPa，使12层坯体贴合，将堆叠后的坯体放入窑具中20MPa热压1500℃烧结12小时，烧结后氧化铝陶瓷装甲厚度35mm，具有12层结构。
实施例4
通过干压成型工艺，30MPa压力制备5层2mm厚度镁铝硼化物陶瓷坯体。堆叠5层坯体，层间铺设50％孔面积、0.1mm厚打孔塑料膜，界面层占陶瓷层面积比为50％。将堆叠后的坯体放入窑具中30MPa热压2150℃烧结18小时，烧结后镁铝硼化物陶瓷装甲厚度8mm，具有5层结构。

Claims (10)

1.一种层状结构的陶瓷材料，其特征在于，由共烧结的两层以上的堆叠陶瓷层及陶瓷层间的界面层构成，所述陶瓷层的厚度为0.2mm～20mm，所述界面层的厚度小于1mm，所述界面层的材料采用能使相邻陶瓷层之间不连续地结合的材料。
2.根据权利要求1所述的陶瓷材料，其特征在于，所述界面层具有第一类界面层和/或第二类界面层，所述第一类界面层的材料为打孔或不连续的纸片、打孔或不连续的塑料膜中的至少一种，所述第二类界面层的材料为石墨烯、碳纳米管、碳纤维、碳化硅纤维、碳化硅晶须、氧化铝纤维、玻璃纤维、石棉中的至少一种。
3.根据权利要求1或2所述的陶瓷材料，其特征在于，所述陶瓷层的材料为氧化铝陶瓷、碳化硅陶瓷、碳化硼陶瓷、镁铝硼化物陶瓷及以上类型陶瓷的纤维增强复合材料中的至少一种。
4.根据权利要求1至3中任一项所述的陶瓷材料，其特征在于，所述陶瓷层的厚度为1mm～15mm。
5.根据权利要求1至4中任一项所述的陶瓷材料，其特征在于，所述界面层的厚度为0.02mm～1mm。
6.根据权利要求1至5中任一项所述的陶瓷材料，其特征在于，所述界面层占陶瓷层面积比为10%～90%。
7.根据权利要求1至6中任一项所述的陶瓷材料，其特征在于，所述陶瓷层的层数为2层以上。
8.根据权利要求1至7中任一项所述的陶瓷材料，其特征在于，在所述界面层同时具有第一类界面层和第二类界面层的情况下，所述第二类界面层至少包括与最表层陶瓷层结合的第二类界面层及与最底层陶瓷层结合的第二类界面层。
9.根据权利要求1至8中任一项所述的陶瓷材料，其特征在于，所述陶瓷层的层数为三层以上，最表层陶瓷层及最底层陶瓷层的厚度大于其余陶瓷层。
10.一种权利要求1至9中任一项所述的层状结构的陶瓷材料的制备方法，其特征在于，包括：
使用陶瓷层材料与界面层材料，形成陶瓷层与界面层相互交错层叠的多层结构，并使该多层结构的最顶层及最底层为陶瓷层；
将所述多层结构压制成型后烧结，得到所述陶瓷材料。
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