CN108546105A - 一种高强韧性石墨烯复合陶瓷 - Google Patents

一种高强韧性石墨烯复合陶瓷 Download PDF

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CN108546105A
CN108546105A CN201810511548.0A CN201810511548A CN108546105A CN 108546105 A CN108546105 A CN 108546105A CN 201810511548 A CN201810511548 A CN 201810511548A CN 108546105 A CN108546105 A CN 108546105A
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林荣铨
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Abstract

本发明公开了一种高强韧性石墨烯复合陶瓷，包括坯体：氧化铁、钙长石、钾长石、凹凸棒土、锂辉石、石墨烯、纳米二氧化钛纤维粉末、碳化硅晶须、硫酸钡、玻璃微珠；釉料：高岭土、石墨烯、纳米二氧化钛纤维粉末、竹炭粉、碳化硅晶须、硫酸钡、玻璃微珠、钾长石、石英砂、滑石粉、橄榄石、竹炭粉、氧化铁、氧化铝、氧化镁、硅酸锆、氧化锌、氧化镥。本发明通过引入纤维强化技术，结合石墨烯的使用，同时复配以硫酸钡和玻璃微珠改善石墨烯的分散性，各组分按照合适的配比可发挥明显的协同增效作用，显著增强陶瓷的强韧性；而且所得陶瓷材料对空气污染物也具有显著的吸附去除能力，耐蚀性能优异；应用范围更广阔，且制备方法简单，适宜工业化生产。

Description

一种高强韧性石墨烯复合陶瓷
技术领域
本发明属于陶瓷技术领域。更具体地，涉及一种高强韧性石墨烯复合陶瓷。
背景技术
陶瓷材料具有高熔点、高硬度、高耐磨性、高化学稳定性等优点，但是脆性是其致命的缺点，限制了陶瓷材料的应用范围，因此，陶瓷材料的强韧化一直是材料学家长期关注的问题。
另外，对于传统结构陶瓷来说，往往强度的增加会伴随着材料的断裂韧性下降，陶瓷材料的硬度与韧性之间的矛盾也是陶瓷材料的一大问题，限制了它的推广应用。
发明内容
本发明要解决的技术问题是克服现有陶瓷材料的强韧化问题不足，提供一种复配石墨烯结合纤维强化技术制备高强韧性石墨烯复合陶瓷的方法。
本发明的目的是提供一种高强韧性石墨烯复合陶瓷。
本发明上述目的通过以下技术方案实现：
一种高强韧性石墨烯复合陶瓷，由如下组分制成：
坯体：氧化铁、钙长石、钾长石、凹凸棒土、锂辉石、石墨烯、纳米二氧化钛纤维粉末、碳化硅晶须、硫酸钡、玻璃微珠；
釉料：高岭土、石墨烯、纳米二氧化钛纤维粉末、竹炭粉、碳化硅晶须、硫酸钡、玻璃微珠、钾长石、石英砂、滑石粉、橄榄石、竹炭粉、氧化铁、氧化铝、氧化镁、硅酸锆、氧化锌、氧化镥。
优选地，所述高强韧性石墨烯复合陶瓷由如下重量份的组分制成：
(1)坯体：氧化铁3～8份、钙长石4～8份、钾长石5～10份、凹凸棒土 4～8份、锂辉石10～15份、石墨烯5～7份、纳米二氧化钛纤维粉末3～6份、碳化硅晶须2～5份、硫酸钡3～5份、玻璃微珠2～5份；
(2)釉料：高岭土4～10份、石墨烯2～5份、纳米二氧化钛纤维粉末1～ 3份、竹炭粉1～2份、碳化硅晶须2～5份、硫酸钡1～3份、玻璃微珠1～4份、钾长石5～10份、石英砂3～8份、滑石粉4～9份、橄榄石3～8份、竹炭粉2～ 5份、氧化铁1～3份、氧化铝5～9份、氧化镁3～7份、硅酸锆4～8份、氧化锌2～5份、氧化镥2～6份。
更优选地，所述高强韧性石墨烯复合陶瓷由如下重量份的组分制成：
(1)坯体：氧化铁5份、钙长石6份、钾长石8份、凹凸棒土6份、锂辉石13份、石墨烯6份、纳米二氧化钛纤维粉末4份、碳化硅晶须3份、硫酸钡 4份、玻璃微珠3份；
(2)釉料：高岭土7份、石墨烯3份、纳米二氧化钛纤维粉末2份、竹炭粉2份、碳化硅晶须3份、硫酸钡2份、玻璃微珠3份、钾长石7份、石英砂6 份、滑石粉7份、橄榄石6份、竹炭粉4份、氧化铁2份、氧化铝7份、氧化镁5份、硅酸锆6份、氧化锌3份、氧化镥4份。
另外，所述高强韧性石墨烯复合陶瓷的制备方法如下：
S1.将坯体原料烘干粉碎后过160～180目，然后按比例混合后，以乙醇和水混合物为介质磨球球磨1～2.5h，得到混合均一的浆料，浆料经沉淀，去除上清液，沉淀物晒干，放入炼泥机中进行炼泥，将炼泥通过拉坯装置进行拉坯，形成坯体，烘干后陈化，再800～850℃下素烧0.5～1h；
S2.将釉料原料按比例混合后，以乙醇和水混合物为介质磨球球磨0.5～ 1.5h，得到混合均一的釉料；
S3.把釉料喷淋于坯体表面，1250～1350℃烧成6～15h，得到高强韧性石墨烯复合陶瓷。
其中优选地，步骤S1中坯体原料烘干粉碎后过170目。
优选地，步骤S1中烘干温度为50～60℃。
优选地，步骤S1中陈化的条件为室温陈化1～2天。
优选地，步骤S3中釉料喷淋于坯体表面的厚度为0.6～2mm。
本发明具有以下有益效果：
本发明在陶瓷原料中引入纤维强化技术，结合石墨烯的使用，同时复配以硫酸钡和玻璃微珠改善石墨烯的分散性，各组分按照合适的比例配入陶瓷原料中，可发挥明显的协同增效作用，显著增强陶瓷材料的强韧性，使得陶瓷材料的机械性能和力学性能得到显著提升，解决了传统陶瓷材料硬度与韧性的矛盾问题。而且所得陶瓷材料对空气污染物的吸附去除能力也得到显著的提升。
本发明的陶瓷较常规陶瓷具有更耐磨、强韧性更好的性能，耐蚀性、耐高温、耐磨性能优异，能有效地吸附甲醛、苯等有害气体，净化空气质量，能够满足大量工业和生活需要，较普通陶瓷而言具有更广阔的应用范围，适用于更加恶劣的使用环境；并且制备方法简单，适宜工业化生产。
具体实施方式
以下结合具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，本发明所用试剂和材料均为市购。
实施例1
1、一种高强韧性石墨烯复合陶瓷，由如下重量份的组分制成：
(1)坯体：氧化铁5份、钙长石6份、钾长石8份、凹凸棒土6份、锂辉石13份、石墨烯6份、纳米二氧化钛纤维粉末4份、碳化硅晶须3份、硫酸钡 4份、玻璃微珠3份；
(2)釉料：高岭土7份、石墨烯3份、纳米二氧化钛纤维粉末2份、竹炭粉2份、碳化硅晶须3份、硫酸钡2份、玻璃微珠3份、钾长石7份、石英砂6 份、滑石粉7份、橄榄石6份、竹炭粉4份、氧化铁2份、氧化铝7份、氧化镁5份、硅酸锆6份、氧化锌3份、氧化镥4份。
2、所述高强韧性石墨烯复合陶瓷的制备方法如下：
S1.将坯体原料烘干粉碎后过170目，然后按比例混合后，以乙醇和水混合物为介质磨球球磨2.5h，得到混合均一的浆料，浆料经沉淀，去除上清液，沉淀物晒干，放入炼泥机中进行炼泥，将炼泥通过拉坯装置进行拉坯，形成坯体， 60℃烘干后陈化2天，再800℃下素烧1h；
S2.将釉料原料按比例混合后，以乙醇和水混合物为介质磨球球磨1.5h，得到混合均一的釉料；
S3.把釉料喷淋于坯体表面，喷淋厚度为1mm，1300℃烧成12h，得到高强韧性石墨烯复合陶瓷。
实施例2
1、一种高强韧性石墨烯复合陶瓷，由如下重量份的组分制成：
(1)坯体：氧化铁3份、钙长石4份、钾长石5份、凹凸棒土4份、锂辉石10份、石墨烯7份、纳米二氧化钛纤维粉末6份、碳化硅晶须5份、硫酸钡 5份、玻璃微珠5份；
(2)釉料：高岭土10份、石墨烯5份、纳米二氧化钛纤维粉末3份、竹炭粉2份、碳化硅晶须5份、硫酸钡3份、玻璃微珠4份、钾长石5份、石英砂3份、滑石粉4份、橄榄石3份、竹炭粉2份、氧化铁1份、氧化铝5份、氧化镁3份、硅酸锆4份、氧化锌2份、氧化镥2份。
2、制备方法同实施例1。
实施例3
1、一种高强韧性石墨烯复合陶瓷，由如下重量份的组分制成：
(1)坯体：氧化铁8份、钙长石8份、钾长石10份、凹凸棒土8份、锂辉石15份、石墨烯5份、纳米二氧化钛纤维粉末3份、碳化硅晶须2份、硫酸钡3份、玻璃微珠2份；
(2)釉料：高岭土4份、石墨烯2份、纳米二氧化钛纤维粉末1份、竹炭粉1份、碳化硅晶须2份、硫酸钡1份、玻璃微珠1份、钾长石10份、石英砂 8份、滑石粉9份、橄榄石8份、竹炭粉5份、氧化铁3份、氧化铝9份、氧化镁7份、硅酸锆8份、氧化锌5份、氧化镥6份。
2、制备方法同实施例1。
实施例4
以实施例1的高强韧性石墨烯复合陶瓷为例，研究复合陶瓷的性能。
1、实验分组
(1)实验组：实施例1制备的高强韧性石墨烯复合陶瓷。
(2)对比组1：将实施例1坯体和釉料中的石墨烯、纳米二氧化钛纤维粉末、碳化硅晶须、硫酸钡、玻璃微珠全部省去；
(3)对比组2：将实施例1坯体和釉料中的纳米二氧化钛纤维粉末替换为钢化纤维；
(4)对比组3：将实施例1坯体和釉料中的纳米二氧化钛纤维粉末替换为硅酸铝纤维；
(5)对比组4：将实施例1坯体和釉料中的碳化硅晶须替换为硅酸铝纤维；
(6)对比组5：将实施例1坯体和釉料中的碳化硅晶须替换为钢化纤维；
(7)对比组6：将实施例1坯体和釉料中的硫酸钡省去；
(8)对比组7：将实施例1坯体和釉料中的玻璃微珠省去。
(9)对比组8：将实施例1坯体和釉料中的硫酸钡、玻璃微珠全部省去。
2、测试各组陶瓷的机械性能和力学性能，结果如表1所示。
表1各组陶瓷的强韧性能
结果显示，与对比组1相比，本发明在陶瓷原料中引入纤维强化技术，结合石墨烯的使用，同时复配以硫酸钡和玻璃微珠改善石墨烯的分散性，使得陶瓷材料的机械性能和力学性能得到显著提高，具有很好的断裂韧性和抗弯强度。
而与其他对比组相比，本发明的陶瓷机械性能和力学性能也有显著性的提高，表明石墨烯、纳米二氧化钛纤维粉末、碳化硅晶须，以及硫酸钡和玻璃微珠，按照合适的比例配入陶瓷原料中，可发挥明显的协同增效作用，显著增强陶瓷材料的强韧性，解决了传统陶瓷材料硬度与韧性的矛盾问题。
3、测试各组陶瓷的吸附性能
分别在密闭容器中放入各组陶瓷材料，各组通入等量的甲醛、苯、氨、TVOC，封闭容器，静置30天后，测试容器内的有害物质的含量。计算污染物去除率，结果如表2所示。
去除率＝(污染物末浓度-污染物初始浓度)/污染物初始浓度×100％
表2各组陶瓷污染物吸附能力
结果显示，与对比组1相比，本发明在陶瓷原料中引入纤维强化技术，结合石墨烯的使用，同时复配以硫酸钡和玻璃微珠改善石墨烯的分散性，使得陶瓷材料对污染物的去除能力提高幅度达到了60％以上。
而与其他对比组相比，本发明对污染物的去除能力提高幅度也达到了10％以上，表明石墨烯、纳米二氧化钛纤维粉末、碳化硅晶须，以及硫酸钡和玻璃微珠，按照合适的比例配入陶瓷原料中，可发挥明显的协同增效作用。
4、测试各组陶瓷的抑菌性能
测试方法：按照JC/T897-2002的规定测试各组陶瓷的大肠杆菌平均菌数和金黄色葡萄球菌平均菌数，以及抗菌率。检测结果如表3所示，本发明的陶瓷具有非常好的抑菌性能。
表3各组陶瓷的抑菌性能
另外经测试可知，本发明所得陶瓷还具有优异的耐蚀性、耐高温、耐磨性能。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (8)

1.一种高强韧性石墨烯复合陶瓷，其特征在于，由如下组分制成：
坯体：氧化铁、钙长石、钾长石、凹凸棒土、锂辉石、石墨烯、纳米二氧化钛纤维粉末、碳化硅晶须、硫酸钡、玻璃微珠；
釉料：高岭土、石墨烯、纳米二氧化钛纤维粉末、竹炭粉、碳化硅晶须、硫酸钡、玻璃微珠、钾长石、石英砂、滑石粉、橄榄石、竹炭粉、氧化铁、氧化铝、氧化镁、 硅酸锆、氧化锌、氧化镥。
2.根据权利要求1所述高强韧性石墨烯复合陶瓷，其特征在于，由如下重量份的组分制成：
坯体：氧化铁3～8份、钙长石4～8份、钾长石5～10份、凹凸棒土4～8份、锂辉石10～15份、石墨烯5～7份、纳米二氧化钛纤维粉末3～6份、碳化硅晶须2～5份、硫酸钡3～5份、玻璃微珠2～5份；
釉料：高岭土4～10份、石墨烯2～5份、纳米二氧化钛纤维粉末1～3份、竹炭粉1～2份、碳化硅晶须2～5份、硫酸钡1～3份、玻璃微珠1～4份、钾长石5～10份、石英砂3～8份、滑石粉4～9份、橄榄石3～8份、竹炭粉2～5份、氧化铁1～3份、氧化铝5～9份、氧化镁3～7份、 硅酸锆4～8份、氧化锌2～5份、氧化镥2～6份。
3.根据权利要求1所述高强韧性石墨烯复合陶瓷，其特征在于，由如下重量份的组分制成：
坯体：氧化铁5份、钙长石6份、钾长石8份、凹凸棒土6份、锂辉石13份、石墨烯6份、纳米二氧化钛纤维粉末4份、碳化硅晶须3份、硫酸钡4份、玻璃微珠3份；
釉料：高岭土7份、石墨烯3份、纳米二氧化钛纤维粉末2份、竹炭粉2份、碳化硅晶须3份、硫酸钡2份、玻璃微珠3份、钾长石7份、石英砂6份、滑石粉7份、橄榄石6份、竹炭粉4份、氧化铁2份、氧化铝7份、氧化镁5份、 硅酸锆6份、氧化锌3份、氧化镥4份。
4.根据权利要求1～3任一所述高强韧性石墨烯复合陶瓷，其特征在于，由如下方法制备得到：
S1. 将坯体原料烘干粉碎后过160～180目，然后按比例混合后，以乙醇和水混合物为介质磨球球磨1～2.5h，得到混合均一的浆料，浆料经沉淀，去除上清液，沉淀物晒干，放入炼泥机中进行炼泥，将炼泥通过拉坯装置进行拉坯，形成坯体，烘干后陈化，再800～850℃下素烧0.5～1h；
S2. 将釉料原料按比例混合后，以乙醇和水混合物为介质磨球球磨0.5～1.5h，得到混合均一的釉料；
S3. 把釉料喷淋于坯体表面，1250～1350℃烧成6～15h，得到高强韧性石墨烯复合陶瓷。
5.根据权利要求4所述高强韧性石墨烯复合陶瓷，其特征在于，步骤S1中坯体原料烘干粉碎后过170目。
6.根据权利要求4所述高强韧性石墨烯复合陶瓷，其特征在于，步骤S1中烘干温度为50～60℃。
7.根据权利要求4所述高强韧性石墨烯复合陶瓷，其特征在于，步骤S1中陈化的条件为室温陈化1～2天。
8.根据权利要求4所述高强韧性石墨烯复合陶瓷，其特征在于，步骤S3中釉料喷淋于坯体表面的厚度为0.6～2mm。
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