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CN115448723A - 一种镁铝水滑石修饰碳化硼基陶瓷的制备方法及其应用 - Google Patents

一种镁铝水滑石修饰碳化硼基陶瓷的制备方法及其应用 Download PDF

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CN115448723A
CN115448723A CN202210809026.5A CN202210809026A CN115448723A CN 115448723 A CN115448723 A CN 115448723A CN 202210809026 A CN202210809026 A CN 202210809026A CN 115448723 A CN115448723 A CN 115448723A
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boron carbide
magnesium
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aluminum hydrotalcite
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童裳慧
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Zhongjing Chengkang Resources Recycling Technology Co ltd
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Abstract

本发明提供一种镁铝水滑石修饰碳化硼的制备方法，包括如下步骤：将硝酸镁和硝酸铝混合得到硝酸盐水溶液；将氢氧化钠溶液滴定至L‑组氨酸溶液中，得到L‑组氨酸底液；将酸纯化的碳纳米管置于氮气环境中、剧烈搅拌，同时逐滴加入硝烟酸水溶液和L‑组氨酸底液，恒温搅拌进行插层浸渍反应，反应结束后进行晶化处理，晶化处理结束后依次进行离心、洗涤、干燥和煅烧处理，将其与碳化硼微粉均匀混合，依次进行球磨、压片、真空加热处理，通入惰性气体后冷却至室温，得到镁铝水滑石修饰碳化硼；通过上述技术方案，解决现有技术中缺乏能够有效改性碳化硼陶瓷的增韧与致密化程度、得到具有较强的耐高温高压及耐腐蚀能力的碳化硼陶瓷材料的问题。

Description

一种镁铝水滑石修饰碳化硼基陶瓷的制备方法及其应用
技术领域
本发明涉及复合材料领域，特别是涉及一种镁铝水滑石修饰碳化硼基陶瓷的制备方法及其应用。
背景技术
碳化硼基陶瓷是一种新型材料，具有低比重、高硬度、高强度的优异性能，因而被广泛应用于个人防护装备、保护陆地车辆、飞机和直升机、防护小口径炮弹等领域中。然而，碳化硼由于是一种具有强共价键的化合物，其晶体中的扩散过程比氧化物慢的多，因此在使用时会收到粉末团结和难形成具有高机械特性致密材料的限制，此外还需要极高的温度或者需要施加外部压力。
综上所述，现有技术中缺乏能够有效改性碳化硼陶瓷的增韧与致密化程度、得到具有制备简单，较强的耐高温高压及耐腐蚀能力的碳化硼陶瓷材料的方法。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种镁铝水滑石修饰碳化硼基陶瓷的制备方法，用于解决现有技术中缺乏能够有效改性碳化硼陶瓷的增韧与致密化程度、得到具有制备简单，较强的耐高温高压及耐腐蚀能力的碳化硼陶瓷材料方法的问题，同时，本发明还将提供镁铝水滑石修饰碳化硼基陶瓷的新用途。
为实现上述目的及其他相关目的，
本发明的第一方面，提供一种镁铝水滑石修饰碳化硼的制备方法，包括如下步骤：
S1、将硝酸镁和硝酸铝混合得到硝酸盐水溶液；
S2、将氢氧化钠溶液滴定至L-组氨酸溶液中，直至pH为8.9～10.2，得到L-组氨酸底液；
S3、将酸纯化的碳纳米管置于氮气环境中、在20～40℃的温度条件下剧烈搅拌，同时逐滴加入硝烟酸水溶液和L-组氨酸底液，恒温搅拌进行插层浸渍反应，反应结束后得到悬浮液；
S4、对悬浮液进行晶化处理，晶化处理结束后依次进行离心、洗涤、干燥和煅烧处理，得到镁铝水滑石修饰的碳纳米管复合金属氧化物；
S5、将镁铝水滑石修饰的碳纳米管复合金属氧化物与碳化硼微粉均匀混合，依次进行球磨、压片、真空加热处理，通入惰性气体后冷却至室温，得到镁铝水滑石修饰碳化硼。
通过上述技术方案，采用硝酸根插层的镁铝水滑石修饰碳纳米管材料作用于碳化硼增韧及致密性能的改性，L-组氨酸作为一种绿色，无毒的化学原料，在高温高压的条件下，分解产生硝酸根，插层到负有碳纳米管的镁铝水滑石层板间，通过水热过程保证晶体的稳定成型过程，再经焙烧得到具有层板结构的碳纳米管复合金属氧化物，从根源上改进了碳纳米管的有效分散结构，同时有利于碳化硼体内的晶体扩散。
于本发明的一实施例中，所述步骤S1中的硝酸盐水溶液中硝酸镁的浓度为1～2.5mol/L，硝酸铝的浓度为0.5～0.8mol/L。
于本发明的一实施例中，所述步骤S2中氢氧化钠溶液的浓度为1～1.5mol/L、L-组氨酸溶液的浓度为0.25～0.5mol/L。
于本发明的一实施例中，所述步骤S3中悬浮液的固液比为1g：40～70ml。
于本发明的一实施例中，所述步骤S3中，碳纳米管为在流化床反应器中，700℃的温度条件、Fe-Ni/Al2O3催化剂的催化条件下，通过甲烷催化裂解合成的多壁碳材料，再通过HCl 煮沸、洗涤、干燥，得到多壁碳纳米管。
于本发明的一实施例中，所述步骤S4中晶化温度为120～200℃、晶化时间18～24h；干燥温度为80～150℃，干燥时间为5～8h；煅烧温度为500～750℃，煅烧时间为5～7h。
于本发明的一实施例中，所述步骤S4中的晶化在水热合成釜中进行。
于本发明的一实施例中，所述步骤S5中镁铝水滑石修饰的碳纳米管复合金属氧化物与碳化硼微粉的质量比0.08～0.5：1。
于本发明的一实施例中，所述步骤S5中球磨转速为120～350r/min，球磨时间为1-2h；真空加热温度为1500～2200℃，升温速率每分钟2～7℃/min，加热时间为3～6h。
本发明的第二方面，提供一种镁铝水滑石修饰碳化硼的应用，具体为在防护小口径炮弹方面上的应用。
如上所述，本发明的镁铝水滑石修饰碳化硼的制备方法及其应用，具有以下有益效果：
1、在陶瓷基体的制备中引入添加碳纳米管可以通过纤维拔出、裂纹侨联和裂纹偏转等增韧机制显著提高断裂韧性，无论是在结构或力学方面都显著优于其他纤维材料；而镁铝水滑石具有良好的阴离子交换能力，热稳定性强，有着可控的层板间距，作为纳米容器能提供较强的耐蚀性能与自修复能力同时极大的有助于负载载体的有效扩散。
2、采用硝酸根插层的镁铝水滑石修饰碳纳米管材料作用于碳化硼增韧及致密性能的改性， L-组氨酸在高温高压的条件下，分解产生硝酸根，插层到负有碳纳米管的镁铝水滑石层板间，有效增大其结构的层板间距，通过水热过程保证晶体的稳定成型过程，再经焙烧得到具有层板结构的碳纳米管复合金属氧化物(MgAl-LDO@CNT)。从根源上改进了碳纳米管的有效分散结构，同时加快了碳化硼体内的晶体扩散，不仅有效降低碳化硼材料的烧结温度并且使材料的致密化程度提高，进而导致弯曲强度提高。
附图说明
图1显示为本发明实施例中公开的一种镁铝水滑石修饰碳化硼中的步骤S3、S4的原理流程示意图。
图2显示为本发明实施例中公开的一种镁铝水滑石修饰碳化硼中的步骤S3、S4的微观流程示意图。
具体实施方式
以下由特定的具体实施例说明本发明的实施方式，熟悉此技术的人士可由本说明书所揭露的内容轻易地了解本发明的其他优点及功效。
下列实施例1～3中制得的镁铝水滑石修饰碳化硼基陶瓷可用于防护小口径炮弹的制备。
实施例1
一种镁铝水滑石修饰碳化硼基陶瓷的制备方法，包括如下步骤：
S1、将硝酸镁和硝酸铝混合得到硝酸盐水溶液100ml，其中硝酸盐水溶液中硝酸铝的浓度为0.5mol/L，硝酸镁的浓度为1mol/L；
S2、将浓度为1mol/L的氢氧化钠溶液滴定至浓度为0.3mol/L的L-组氨酸溶液中，直至 pH为8.9～9.2，得到L-组氨酸底液；
S3、称取2g酸纯化后的碳纳米管，将酸纯化的碳纳米管置于氮气环境中、在35℃的温度条件下剧烈搅拌，同时逐滴加入硝烟酸水溶液和L-组氨酸底液，恒温搅拌进行插层浸渍反应，反应结束后得到悬浮液；
S4、将悬浮液纺织物水热合成釜中，在160℃的温度条件下晶化处理20h，晶化处理结束后依次进行离心、洗涤、于120℃的温度下干燥8h后于600℃的温度条件下煅烧处理，煅烧时间为5h，得到镁铝水滑石修饰的碳纳米管复合金属氧化物(MgAl-LDO@CNT)；
S5、将镁铝水滑石修饰的碳纳米管复合金属氧化物与碳化硼微粉以1：0.2的质量比均匀混合，以300r/min球磨2h、压片，1600℃真空加热，加热时间为3h，通入惰性气体后冷却至室温，得到镁铝水滑石修饰碳化硼基陶瓷。
实施例2
一种镁铝水滑石修饰碳化硼基陶瓷的制备方法，包括如下步骤：
S1、将硝酸镁和硝酸铝混合得到硝酸盐水溶液120ml，其中硝酸盐水溶液中硝酸铝的浓度为0.5mol/L，硝酸镁的浓度为1mol/L；
S2、将浓度为1mol/L的氢氧化钠溶液滴定至浓度为0.3mol/L的L-组氨酸溶液中，直至 pH为8.9～9.2，得到L-组氨酸底液；
S3、称取3g酸纯化后的碳纳米管，将酸纯化的碳纳米管置于氮气环境中、在35℃的温度条件下剧烈搅拌，同时逐滴加入硝烟酸水溶液和L-组氨酸底液，恒温搅拌进行插层浸渍反应，反应结束后得到悬浮液；
S4、将悬浮液纺织物水热合成釜中，在200℃的温度条件下晶化处理18h，晶化处理结束后依次进行离心、洗涤、于120℃的温度下干燥8h后于600℃的温度条件下煅烧处理，煅烧时间为5h，得到镁铝水滑石修饰的碳纳米管复合金属氧化物(MgAl-LDO@CNT)；
S5、将镁铝水滑石修饰的碳纳米管复合金属氧化物与碳化硼微粉以1：0.3的质量比均匀混合，以250r/min球磨2h、压片，1600℃真空加热，加热时间为3h，通入惰性气体后冷却至室温，得到镁铝水滑石修饰碳化硼基陶瓷。
实施例3
一种镁铝水滑石修饰碳化硼基陶瓷的制备方法，包括如下步骤：
S1、将硝酸镁和硝酸铝混合得到硝酸盐水溶液160ml，其中硝酸盐水溶液中硝酸铝的浓度为0.5mol/L，硝酸镁的浓度为1mol/L；
S2、将浓度为1mol/L的氢氧化钠溶液滴定至浓度为0.3mol/L的L-组氨酸溶液中，直至 pH为8.9～9.2，得到L-组氨酸底液；
S3、称取4g酸纯化后的碳纳米管，将酸纯化的碳纳米管置于氮气环境中、在35℃的温度条件下剧烈搅拌，同时逐滴加入硝烟酸水溶液和L-组氨酸底液，恒温搅拌进行插层浸渍反应，反应结束后得到悬浮液；
S4、将悬浮液纺织物水热合成釜中，在220℃的温度条件下晶化处理22h，晶化处理结束后依次进行离心、洗涤、于120℃的温度下干燥8h后于600℃的温度条件下煅烧处理，煅烧时间为5h，得到镁铝水滑石修饰的碳纳米管复合金属氧化物(MgAl-LDO@CNT)；
S5、将镁铝水滑石修饰的碳纳米管复合金属氧化物与碳化硼微粉以1：0.5的质量比均匀混合，以350r/min球磨2h、压片，1600℃真空加热，加热时间为4h，通入惰性气体后冷却至室温，得到镁铝水滑石修饰碳化硼基陶瓷。
对比例1
将碳化硼微粉以300r/min球磨2h、压片，1600℃真空加热，加热时间为3h，通入惰性气体冷却至室温，得到碳化硼基陶瓷。
性能测试
实施例1-3及对比例1中工艺参数如表1所示。
表1
Figure BDA0003739717070000051
实施例1-3及对比例1中材料的性能特征如表2所示。
表2
材料密度(g/cm<sup>3</sup>) 弯曲强度(MPa)
实施例1 2.97 480
实施例2 3.15 497
实施例3 2.86 467
对比例1 2.37 350
参阅表1和表2可知，
对比例1中没有引入镁铝水滑石修饰，直接以碳化硼微粉以主要原料得到的碳化硼基陶瓷其材料密度相较于实施例1-3制得的镁铝水滑石修饰碳化硼基陶瓷，其材料密度较小，弯曲强度较弱，这是因为硝酸根插层的镁铝水滑石修饰碳纳米管材料作用于碳化硼增韧及致密性能的改性，L-组氨酸在高温高压的条件下，分解产生硝酸根，插层到负有碳纳米管的镁铝水滑石层板间，有效增大其结构的层板间距，通过水热过程保证晶体的稳定成型过程，再经焙烧得到具有层板结构的碳纳米管复合金属氧化物(MgAl-LDO@CNT)。从根源上改进了碳纳米管的有效分散结构，同时加快了碳化硼体内的晶体扩散。
综上所述，本发明在陶瓷基体的制备中引入添加碳纳米管可以通过纤维拔出、裂纹侨联和裂纹偏转等增韧机制显著提高断裂韧性，无论是在结构或力学方面都显著优于其他纤维材料；而镁铝水滑石具有良好的阴离子交换能力，热稳定性强，有着可控的层板间距，作为纳米容器能提供较强的耐蚀性能与自修复能力同时极大的有助于负载载体的有效扩散。所以，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (10)

1.一种镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于，包括如下步骤：
S1、将硝酸镁和硝酸铝混合得到硝酸盐水溶液；
S2、将氢氧化钠溶液滴定至L-组氨酸溶液中，直至pH为8.9～10.2，得到L-组氨酸底液；
S3、将酸纯化的碳纳米管置于氮气环境中、在20～40℃的温度条件下剧烈搅拌，同时逐滴加入硝烟酸水溶液和L-组氨酸底液，恒温搅拌进行插层浸渍反应，反应结束后得到悬浮液；
S4、对悬浮液进行晶化处理，晶化处理结束后依次进行离心、洗涤、干燥和煅烧处理，得到镁铝水滑石修饰的碳纳米管复合金属氧化物；
S5、将镁铝水滑石修饰的碳纳米管复合金属氧化物与碳化硼微粉均匀混合，依次进行球磨、压片、真空加热处理，通入惰性气体后冷却至室温，得到镁铝水滑石修饰碳化硼。
2.根据权利要求1所述的镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于：所述步骤S1中的硝酸盐水溶液中硝酸镁的浓度为1～2.5mol/L，硝酸铝的浓度为0.5～0.8mol/L。
3.根据权利要求1所述的镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于：所述步骤S2中氢氧化钠溶液的浓度为1～1.5mol/L、L-组氨酸溶液的浓度为0.25～0.5mol/L。
4.根据权利要求1所述的镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于：所述步骤S3中悬浮液的固液比为1g：40～70ml。
5.根据权利要求1所述的镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于：所述步骤S3中，碳纳米管为在流化床反应器中，700℃的温度条件、Fe-Ni/Al2O3催化剂的催化条件下，通过甲烷催化裂解合成的多壁碳材料，再通过HCl煮沸、洗涤、干燥，得到多壁碳纳米管。
6.根据权利要求1所述的镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于：所述步骤S4中晶化温度为120～200℃、晶化时间18～24h；干燥温度为80～150℃，干燥时间为5～8h；煅烧温度为500～750℃，煅烧时间为5～7h。
7.根据权利要求1所述的镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于：所述步骤S4中的晶化在水热合成釜中进行。
8.根据权利要求1所述的镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于：所述步骤S5中镁铝水滑石修饰的碳纳米管复合金属氧化物与碳化硼微粉的质量比0.08～0.5：1。
9.根据权利要求1所述的镁铝水滑石修饰碳化硼基陶瓷的制备方法，其特征在于：所述步骤S5中球磨转速为120～350r/min，球磨时间为1-2h；真空加热温度为1500～2200℃，升温速率每分钟2～7℃/min，加热时间为3～6h。
10.一种如权利要求1-9任一项所述镁铝水滑石修饰碳化硼基陶瓷的应用，其特征在于，
在防护小口径炮弹方面上的应用。
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