CN110698198A - 一种石墨烯增强陶瓷基复合材料及其制备方法 - Google Patents
一种石墨烯增强陶瓷基复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种石墨烯增强陶瓷基复合材料及其制备方法，所述复合材料的增强体包含具有定向排列的石墨烯，所述石墨烯在复合材料中的体积分数为0.125‑1vol％；所述复合材料的基体选自氧化锆、氮化硅、氧化铝中的至少一种，所述复合材料通过3D光固化成型。本发明首创的提供了一种由3D光固化成型的具有定向排列的石墨烯增强的陶瓷基复合材料，所得石墨烯增强氧化锆陶瓷，致密度高达99％以上，较同等工艺未添加石墨烯性能提高25％以上。
Description
技术领域
本发明属于片式结构成型范围，具体涉及一种石墨烯增强陶瓷基复合材料及其制备方法。
背景技术
增材制造(AM)技术将传统的“等体积切削去除”制造变化为“切片逐层叠加”制造，具有开发周期短、不需模具、成本低等许多优势。它是基于分层-叠加原理，首先在三维造型软件中生成零件的三维模型，然后对其进行切片处理，把每层的信息输入到制造设备，通过材料的逐层堆积获得最终任意复杂的三维实体零件。
目前，陶瓷增材制造技术可分为4类：1)包括三维打印(3DP)、激光选区烧结(SLS)、激光选区熔化(SLM)等的基于粉材的AM技术；2)包括熔融沉积造型(FDM)的基于丝材的AM技术；3)包括分层实体制造(LOM)的基于片材的AM技术；4)包括光固化成型(SLA)的基于液体的AM技术。这其中，具备制造精度高(±0.1mm)、表面质量好和具有复杂几何形状零件的光固化陶瓷增材制造(SLA)技术是相关研究的热点。
SLA技术是将陶瓷粉末加入光敏树脂中，通过高速搅拌使陶瓷粉末在光敏树脂中分散均匀，获得高固相含量、低粘度的陶瓷浆料。然后使浆料逐层固化堆积成形得到陶瓷坯体，完成干燥、脱脂及烧结等工艺后得到陶瓷件。这种方法能简捷、全自动地制造出表面质量和尺寸精度较高、几何形状较复杂的原型，已成功应用于医学与生物领域、微技术领域及机械耐热结构领域等。
结构陶瓷不同的化学组成和组织结构决定了它不同的特殊性质和功能应用常应用于严酷环境和苛刻负载条件。但遗憾的是，除了陶瓷本身固有的脆性大大削弱了其与传统金属材料的竞争优势，限制了大规模开发与应用。
为此国内外针对低韧性弱点采取了一系列研究，复合化是解决此问题的有限途径。纳米碳材料衍生物(如石墨烯，碳纳米管等)具有高的抗拉强度和大的弹性模量，能作为第二相对裂纹扩展起到抑制作用，而成为此方法的研究热点。但由于纳米碳材料衍生物大的比表面和范德华力而易团聚的特性以及传统固态成型中增强相在陶瓷基体中排布混乱导致增韧效果不明显的问题，使得其如何在基体中解团聚，实现均匀平行分布成为在实验过程重点和难点。
发明内容
针对现有技术的不足，本发明目的在于提供一种光固化成型的定向平行排列的石墨烯增强陶瓷基复合材料及其制备方法。所述复合材料强度、韧性好；所述制备方法工艺简单、成本低、且能可控的获得复杂异形件。
本发明一种石墨烯增强陶瓷基复合材料，所述复合材料的增强体包含具有定向排列的石墨烯，所述石墨烯在复合材料中的体积分数为0.125-1vol％；所述复合材料的基体选自氧化锆、氮化硅、氧化铝中的至少一种，所述复合材料通过3D光固化成型。
优选的方案，所述石墨烯在复合材料中的体积分数为0.125-0.5vol％。进一步优选为0.25-0.5vol％。
当石墨烯在该优选范围时，可对陶瓷基体达到最佳的增韧效果，断裂韧性较同等工艺未添加石墨烯性能的陶瓷材料提高25％以上。
优选的方案，所述复合材料的基体为氧化锆。
本发明一种石墨烯增强陶瓷基复合材料的制备方法，包括如下步骤：
步骤1、浆料的配取
将石墨烯、光固化树脂、光引发剂混合，然后再加入陶瓷粉体，分散剂混合即得陶瓷浆料，所述陶瓷浆料中，陶瓷粉体的固含量(质量分数)为60-80wt％；
步骤2、3D光固化成型
根据设计的三维结构，将步骤一所得陶瓷浆料通过3D光固化设备逐层打印切片、固化，即获得光固化三维结构；
步骤3：固化裂解
将步骤2所得光固化三维结构依次进行脱脂、烧结即得复合材料。
优选的方案，所述步骤1中，所述光固化树脂按质量百分比计其成份组成如下：双酚A环氧丙烯酸酯10～30wt％，三羟甲基丙烷三丙烯酸酯10～40wt％，二缩三丙二醇二丙烯酸酯15～40wt％，甲基丙烯酸异冰片酯15～40wt％。本发明提供的光固化树脂可以合适的流动性用于配取高固含量的陶瓷浆料，又具有高的交联密度，两方面的协同下意料之外的制备出石墨烯具有定向排列，且高致密度的陶瓷材料。
优选的方案，步骤1中，所述光引发剂选自二苯基(2，4，6-三甲基苯甲酰基)氧化膦(TPO)，所述光引发剂的加入量为光固化树脂质量的1-5wt％。
优选的方案，步骤1中，石墨烯、光固化树脂、光引发剂混合的方式为：先于1500-2000r/min的转速下搅拌2-5min，再超声80-100min。
优选的方案，步骤1中，加入陶瓷粉体，分散剂混合的方式为：于500-2000r/min的转速下搅拌2-5min。
在实际操作过程中，上述搅拌均于真空搅拌除泡剂机进行搅拌，发明人发现，先将石墨烯、光固化树脂、光引发剂在高转速下搅拌，再超声可确保石墨烯在浆料中的分散，若一起加入物料，若分散剂先加入，均会导致石墨烯分散效果不好的问题。
优选的方案，步骤1中，所述分散剂为聚乙烯吡络烷酮(PVP)。
优选的方案，步骤1中，所述分散剂的加入量为陶瓷粉体质量的0.2-5wt％。
优选的方案，步骤1中，所述陶瓷粉体的粒径为亚微米级。
优选的方案，步骤1中，所述陶瓷浆料在剪切速率为10s-1时，粘度为25-35Pa·s。
优选的方案，步骤1中，所述陶瓷浆料中，陶瓷粉体固含量为70-75wt％；
优选的方案，步骤2中，切片层厚为20μm-50μm，固化时间为10-30s。切片层厚以及固化时间会对材料的性能产生一定的影响，切片层过厚影响石墨烯平行程度，过薄影响工作效率，并对浆料提出更高要求，固化时间短导致固化深度不够，过长造成比预计区域大，对精度产生影响。
优选的方案，步骤3中，在空气气氛下进行脱脂，所述脱脂程序为以0.5-2℃/min的速率的升温到200-250℃，保温40-80min，再以0.5-2℃/min的速率的升温到280-320℃，保温100-150min，然后以1.0-5.0℃/min的速率的升温到450-550℃，保温100-150min。
优选的方案，步骤3中，所述烧结为在真空或保护气氛下的放电等离子体(SPS)烧结，所述烧结温度为1400-1500℃，烧结时间为10-15min，升温速率为100-150℃/min，烧结压力为50-60MPa。采用等离子体快速烧结致密，有助于石墨烯的定向排布。
有益效果
本发明首创的提供了一种由3D光固化成型的具有定向排列的石墨烯增强的陶瓷基复合材料，所得石墨类增强氧化锆陶瓷，致密度高达99％以上，较同等工艺未添加石墨烯性能提高25％以上。
本发明通过优化浆料配方，浆料配方中所用的光固化树脂可以合适的流动性用于配取高固含量的陶瓷浆料，又具有高的交联密度，两方面的协同下即可制备出高致密度的陶瓷，而高固含量，而高固含量、高致密度也是使得石墨烯定向排布的必要条件。
另外本发明在烧结过程中，采用了SPS烧结，SPS烧结有助于快速烧结致密以及石墨烯的定向排列。
附图说明
图1本发明实施例3所得石墨烯陶瓷坯体脱脂微观形貌，
图2本发明实施例3石墨烯增韧氧化锆陶瓷烧结样品微观形貌。
具体实施方式
实施例1(石墨烯0.5vol％％)
取石墨烯、双酚A环氧丙烯酸酯(BAEA)，三羟甲基丙烷三丙烯酸酯(TMPTA)，二缩三丙二醇二丙烯酸酯(TPGDA)，甲基丙烯酸异冰片酯(IBMA)，引发剂二苯基(2,4,6-三甲基苯甲酰基)氧化膦(TPO)，置于高速真空搅拌除泡剂机中搅拌均匀，转速1800rap，时间3min。之后利用超声震荡来解决石墨烯团聚问题，功率100％，时间90min、脱泡获得预混液，预混液中加入粉末ZrO2、PVP在进行高速真空搅拌除泡剂机中搅拌均匀，转速1800，时间3min。混匀，即得陶瓷浆料，
陶瓷浆料中的各组份加入量如下：
以该成分浆料进行光固化成型，固化成型过程中，切片层厚20μm，时间为20s；
在空气气氛下进行脱脂-烧结，脱脂参数为0.5℃/min到200℃，保温60min，0.5℃/min到300℃，保温120min，1.0℃/min到500℃，保温120min。脱脂完成后，随炉冷却。后续进行SPS烧结，升温速率100℃/min,，烧结温度1450℃，保温时间10min,烧结压力50MPa,，石墨烯增韧氧化锆陶瓷致密度均在99％以上。石墨烯增韧氧化锆陶瓷中，石墨烯的体积分数为0.5vol％。扫描电子显微镜揭示了基体中石墨烯分散良好且呈有序平行排列。压痕法测量0.5vol％石墨烯增韧氧化锆陶瓷断裂韧性Kic达到5.89MPa·m0.5以上。较同等工艺未添加石墨烯性能提高34％。这表明了相关技术能够解决固型中石墨烯在氧化锆陶瓷基体内的空间排布混乱，进而导致的材料韧性低等难题。
实施例2(石墨烯0.125vol％)
取石墨烯、双酚A环氧丙烯酸酯(BAEA)，三羟甲基丙烷三丙烯酸酯(TMPTA)，二缩三丙二醇二丙烯酸酯(TPGDA)，甲基丙烯酸异冰片酯(IBMA)，引发剂二苯基(2,4,6-三甲基苯甲酰基)氧化膦(TPO)，置于高速真空搅拌除泡剂机中搅拌均匀，转速1800rap，时间3min。之后利用超声震荡来解决石墨烯团聚问题，功率100％，时间90min、脱泡获得预混液，预混液中加入粉末ZrO2、PVP在进行高速真空搅拌除泡剂机中搅拌均匀，转速1800，时间3min。混匀，即得陶瓷浆料，
陶瓷浆料中的各组份加入量如下：
以该成分浆料进行光固化成型，固化成型过程中，切片层厚20μm，时间为20s；在空气气氛下进行脱脂-烧结，脱脂参数为0.5℃/min到200℃，保温60min，0.5℃/min到300℃，保温120min，1.0℃/min到500℃，保温120min。脱脂完成后，随炉冷却。后续进行SPS烧结，升温速率100℃/min,，烧结温度1450℃，保温时间10min,烧结压力50MPa,，石墨烯增韧氧化锆陶瓷致密度均在99％以上。石墨烯增韧氧化锆陶瓷中，石墨烯的体积分数为0.125vol％，扫描电子显微镜揭示了基体中石墨烯分散良好且呈有序平行排列。压痕法测量0.125vol％石墨烯增韧氧化锆陶瓷断裂韧性Kic达到5.53MPa·m0.5以上。较同等工艺未添加石墨烯性能提高26％。这表明了相关技术能够解决固型中石墨烯在氧化锆陶瓷基体内的空间排布混乱，进而导致的材料韧性低等难题。
实施例3(石墨烯0.25vol％％)
取双酚A环氧丙烯酸酯(BAEA)，三羟甲基丙烷三丙烯酸酯(TMPTA)，二缩三丙二醇二丙烯酸酯(TPGDA)，甲基丙烯酸异冰片酯(IBMA)，二苯基(2,4,6-三甲基苯甲酰基)氧化膦(TPO)，石墨烯搅拌、脱泡获得预混液，超声分散解团聚，预混液中加入粉末ZrO2、PVP混匀，即得陶瓷浆料。
陶瓷浆料中的各组份加入量如下：
BAEA：2.00g
TMPTA：2.00g
TPGDA：3.00g
IBMA：4.50g
TPO：0.2000g
ZrO2：30.0000g
PVP：0.1500g
石墨烯0.027g
以该成分浆料进行光固化成型，固化成型过程中，切片层厚50μm，固化时间为20s，在空气气氛下进行脱脂-烧结，脱脂参数为0.5℃/min到200℃，保温60min，0.5℃/min到300℃，保温120min，1.0℃/min到500℃，保温120min。脱脂完成后，随炉冷却。后续进行SPS烧结，升温速率100℃/min,烧结温度1450℃,保温时间10min,烧结压力50MPa,。石墨烯增韧氧化锆陶瓷致密度均在99％以上。；图1与图2中的扫描电子显微镜揭示了基体中石墨烯分散良好且呈有序平行排列。压痕法测量的最佳石墨烯增韧氧化锆陶瓷断裂韧性Kic为7.21MPa·m0.5。较同等工艺未添加石墨烯性能提高64％。这表明了相关技术能够解决固型中石墨烯在氧化锆陶瓷基体内的空间排布混乱，进而导致的材料韧性低等难题。
对比例1
其他条件与实施例1相同，仅不加入石墨烯，压痕法测量增韧样品为Kic4.39MPa·m0.5。
对比例2
其他条件与实施例1相同，仅是浆料配取过程中，未加入二缩三丙二醇二丙烯酸酯(TPGDA)，结果显示材料致密度仅为95％，且石墨烯未形成优异的定向排列。
对比例3
其他条件与实施例1相同，仅是未采用SPS烧结，结果显示材料致密度仅为96.7％，且石墨烯未形成优异的定向排列。
Claims (10)
1.一种石墨烯增强陶瓷基复合材料，其特征在于：所述复合材料的增强体包含具有定向排列的石墨烯，所述石墨烯在复合材料中的体积分数为0.125-1vol％；所述复合材料的基体选自氧化锆、氮化硅、氧化铝中的至少一种，所述复合材料通过3D光固化成型。
2.制备如权利要求1所述的一种石墨烯增强陶瓷基复合材料的方法，其特征在于：包括如下步骤：
步骤1、浆料的配取
将石墨烯、光固化树脂、光引发剂混合，然后再加入陶瓷粉体，分散剂混合即得陶瓷浆料，所述陶瓷浆料中，陶瓷粉体的固含量为60-80wt％；
步骤2、3D光固化成型
根据设计的三维结构，将步骤一所得陶瓷浆料通过3D光固化设备逐层打印切片、固化，即获得光固化三维结构；
步骤3、固化裂解
将步骤2所得光固化三维结构依次进行脱脂、烧结即得复合材料。
3.根据权利要求2所述的一种石墨烯增强陶瓷基复合材料的制备方法，其特征在于：所述步骤1中，所述光固化树脂按质量百分比计其成份组成如下：双酚A环氧丙烯酸酯10～30wt％，三羟甲基丙烷三丙烯酸酯10～40wt％，二缩三丙二醇二丙烯酸酯15～40wt％，甲基丙烯酸异冰片酯，15～40wt％；步骤1中，所述光引发剂选自二苯基(2，4，6-三甲基苯甲酰基)氧化膦，所述光引发剂的加入量为光固化树脂质量的1-5wt％。
4.根据权利要求2所述的一种石墨烯增强陶瓷基复合材料的制备方法，其特征在于：步骤1中，石墨烯、光固化树脂、光引发剂混合的方式为：先于1500-2000r/min的转速下搅拌2-5min，再超声80-100min；步骤1中，加入陶瓷粉体，分散剂混合的方式为：于500-2000r/min的转速下搅拌2-5min。
5.根据权利要求2所述的一种石墨烯增强陶瓷基复合材料的制备方法，其特征在于：步骤1中，所述分散剂为聚乙烯吡络烷酮；所述分散剂的加入量为陶瓷粉体质量的0.2-5wt％。
6.根据权利要求2所述的一种石墨烯增强陶瓷基复合材料的制备方法，其特征在于：步骤1中，所述陶瓷粉体的粒径为亚微米级。
7.根据权利要求2所述的一种石墨烯增强陶瓷基复合材料的制备方法，其特征在于：所述陶瓷浆料在剪切速率为10s-1时，粘度为25-35Pa.s。
8.根据权利要求2所述的一种石墨烯增强陶瓷基复合材料的制备方法，其特征在于：步骤2中，切片层厚为20μm-50μm，固化时间为10-30s。
9.根据权利要求2所述的一种石墨烯增强陶瓷基复合材料的制备方法，其特征在于：步骤3中，在空气气氛下进行脱脂，所述脱脂程序为以0.5-2℃/min的速率的升温到200-250℃，保温40-80min，再以0.5-2℃/min的速率的升温到280-320℃，保温100-150min，然后以1.0-5.0℃/min的速率的升温到450-550℃，保温100-150min。
10.根据权利要求2所述的一种石墨烯增强陶瓷基复合材料的制备方法，其特征在于：步骤3中，所述烧结为在真空或保护气氛下的放电等离子体烧结，所述烧结温度为1400-1500℃，烧结时间为10-15min，升温速率为100-150℃/min，烧结压力为50-60MPa。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111643725A (zh) * | 2020-06-01 | 2020-09-11 | 四川大学 | 修补骨缺损的人工骨材及人工骨颗粒的制备方法 |
| CN112456987A (zh) * | 2020-12-14 | 2021-03-09 | 齐鲁工业大学 | 仿生叠层石墨烯复合陶瓷刀具及其制备方法 |
| CN113307618A (zh) * | 2021-06-15 | 2021-08-27 | 中国科学院上海硅酸盐研究所 | 仿贝壳结构织构生物陶瓷及制备方法和其在成骨方面的应用 |
| WO2022087085A1 (en) * | 2020-10-21 | 2022-04-28 | Arkema France | A method of making a three-dimensional printed carbon-bonded composite article |
| CN114409426A (zh) * | 2022-02-09 | 2022-04-29 | 山东大学第二医院 | 一种3d打印氧化石墨烯-羟基磷灰石基生物陶瓷浆料、制备方法及应用 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106810215A (zh) * | 2017-01-18 | 2017-06-09 | 深圳摩方新材科技有限公司 | 一种陶瓷浆料的制备及3d打印光固化成型方法 |
| CN107963882A (zh) * | 2017-11-14 | 2018-04-27 | 清华大学 | 具有平行排列石墨烯/陶瓷复合材料及低成本制备方法 |
| CN108712960A (zh) * | 2016-01-15 | 2018-10-26 | 马克弗巨德有限公司 | 3d打印零件中的连续和随机增强 |
| CN108821752A (zh) * | 2018-07-24 | 2018-11-16 | 合肥岑遥新材料科技有限公司 | 一种耐高温陶瓷基复合材料及其制备方法 |
| US20190090352A1 (en) * | 2014-11-19 | 2019-03-21 | Vorbeck Materials Corp. | Transfer print circuitry |
| CN110395991A (zh) * | 2019-07-25 | 2019-11-01 | 西安增材制造国家研究院有限公司 | 一种光固化氮化硅陶瓷膏料及其制备方法 |
-
2019
- 2019-11-06 CN CN201911078707.3A patent/CN110698198B/zh active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190090352A1 (en) * | 2014-11-19 | 2019-03-21 | Vorbeck Materials Corp. | Transfer print circuitry |
| CN108712960A (zh) * | 2016-01-15 | 2018-10-26 | 马克弗巨德有限公司 | 3d打印零件中的连续和随机增强 |
| CN106810215A (zh) * | 2017-01-18 | 2017-06-09 | 深圳摩方新材科技有限公司 | 一种陶瓷浆料的制备及3d打印光固化成型方法 |
| CN107963882A (zh) * | 2017-11-14 | 2018-04-27 | 清华大学 | 具有平行排列石墨烯/陶瓷复合材料及低成本制备方法 |
| CN108821752A (zh) * | 2018-07-24 | 2018-11-16 | 合肥岑遥新材料科技有限公司 | 一种耐高温陶瓷基复合材料及其制备方法 |
| CN110395991A (zh) * | 2019-07-25 | 2019-11-01 | 西安增材制造国家研究院有限公司 | 一种光固化氮化硅陶瓷膏料及其制备方法 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111643725A (zh) * | 2020-06-01 | 2020-09-11 | 四川大学 | 修补骨缺损的人工骨材及人工骨颗粒的制备方法 |
| WO2022087085A1 (en) * | 2020-10-21 | 2022-04-28 | Arkema France | A method of making a three-dimensional printed carbon-bonded composite article |
| CN112456987A (zh) * | 2020-12-14 | 2021-03-09 | 齐鲁工业大学 | 仿生叠层石墨烯复合陶瓷刀具及其制备方法 |
| CN113307618A (zh) * | 2021-06-15 | 2021-08-27 | 中国科学院上海硅酸盐研究所 | 仿贝壳结构织构生物陶瓷及制备方法和其在成骨方面的应用 |
| CN113307618B (zh) * | 2021-06-15 | 2022-06-14 | 中国科学院上海硅酸盐研究所 | 仿贝壳结构织构生物陶瓷及制备方法和其在成骨方面的应用 |
| CN114409426A (zh) * | 2022-02-09 | 2022-04-29 | 山东大学第二医院 | 一种3d打印氧化石墨烯-羟基磷灰石基生物陶瓷浆料、制备方法及应用 |
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