WO2018068491A1 - 纤维素纳米晶改性陶瓷坯体及其制备方法 - Google Patents

纤维素纳米晶改性陶瓷坯体及其制备方法 Download PDF

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WO2018068491A1
WO2018068491A1 PCT/CN2017/080186 CN2017080186W WO2018068491A1 WO 2018068491 A1 WO2018068491 A1 WO 2018068491A1 CN 2017080186 W CN2017080186 W CN 2017080186W WO 2018068491 A1 WO2018068491 A1 WO 2018068491A1
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ceramic
cellulose
ceramic body
cellulose nanocrystal
green body
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PCT/CN2017/080186
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English (en)
French (fr)
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邓腾飞
王艳娟
林宁
徐晓虹
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武汉理工大学
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Priority to US15/750,178 priority Critical patent/US10906840B2/en
Publication of WO2018068491A1 publication Critical patent/WO2018068491A1/zh

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Abstract

一种纤维素纳米晶改性陶瓷坯体及其制备方法。陶瓷坯体注凝成型加入了纤维素纳米晶，含有纤维素纳米晶、有机凝胶和陶瓷粉料；按重量份数计纤维素纳米晶0.1～10份，有机凝胶0.1～30份，陶瓷粉料70～99份。纤维素纳米晶长度为100～300nm，直径为10～20nm，长径比为10～15，弹性模量100‑150GPa。

Description

纤维素纳米晶改性陶瓷坯体及其制备方法 技术领域
本发明涉及无机非金属材料制备领域，具体涉及一种高性能陶瓷坯体及其制备方法。
背景技术
陶瓷材料具有较大的硬度和脆性，难以进行后期的加工处理，所以陶瓷坯体的成型方法较少，而对于形状复杂、尺寸要求精密的特种陶瓷而言，其成型方法就变得复杂、不易操作，极大影响着陶瓷产品的质量与产率。注凝成型技术是20世纪90年代初由美国橡树岭国家实验室发明的一种近净尺寸的精密成型技术(U.S.Patent:4894194；U.S.Patent:5028362)，其将高分子化学理论与陶瓷注浆成型方法相结合，利用有机单体在引发剂、催化剂的条件下聚合形成三维网络结构，使得高固含量、低黏度的陶瓷料浆能原位固化成型且干燥成型后坯体强度高。该成型方法具有工艺简单，投资费用少，成型出的坯体结构致密、尺寸精确，且有机物含量低，不影响烧结后产品性能等优点。丙烯酰胺是目前注凝成型中最常用的有机单体，其可适用于不同陶瓷粉料体系、制得的陶瓷生坯性能优良，是目前应用较为普遍的体系，但由于丙烯酰胺具有一定的神经毒性，因此近年来一些低毒与无毒的凝胶剂相继被开发出来。无毒凝胶剂如海藻酸盐、蛋白及葡萄糖提取物等已被报道用于陶瓷材料的注凝成型。这些凝胶体系虽然无毒，但制得的生坯机械强度低，同时这些凝胶剂多需要从原料中提取，使成本增加。低毒凝胶剂如N’N-二甲基丙烯酰胺、N-羟甲基丙烯酸酰胺等具有和丙烯酰胺体系类似的特性，但其制备的陶瓷生坯力学性能难以达到工业上陶瓷成型要求。因此，提高现有注凝体系所制备陶瓷坯体的强度与韧性是当前亟需解决的关键技术问题，对陶瓷产业的发展具有深远的影响。
发明内容
本发明目的在于提供一种注凝成型高性能陶瓷坯体及其制备方法，能显著提高各类凝胶体系制备的陶瓷坯体的力学性能，适应性广。
为达到上述目的，采用技术方案如下：
纤维素纳米晶改性陶瓷坯体，注凝成型加入了纤维素纳米晶，纤维素纳米晶含量在0.01-15wt％。
上述纤维素纳米晶改性陶瓷坯体，含有纤维素纳米晶、有机凝胶和陶瓷粉料；按重量份数计纤维素纳米晶0.1～10份；有机凝胶0.1～30份；陶瓷粉料70～99份。
按上述方案，所述纤维素纳米晶长度为100～300nm，直径为10～20nm，长径比为10～15，弹性模量100-150GPa。
按上述方案，所述纤维素纳米晶按以下方法制备而来：
棉短绒经碱处理、硫酸水解、离心洗涤、透析后得到纤维素纳米晶悬浮液，将悬浮液冷冻干燥之后得到粉末状纤维素纳米晶。
按上述方案，所述有机凝胶为单体与交联剂反应聚合形成，表面含有羰基。
按上述方案，所述陶瓷粉料为氧化铝、氧化锆、莫来石、熔融石英、氮化硼的任意一种或混合。
上述纤维素纳米晶改性陶瓷坯体的制备方法，包括以下步骤：
1)配置纤维素纳米晶/水悬浮液，依次加入单体、交联剂、分散剂，混匀后用氨水调节pH＝8～11，得到预混液；
2)向预混液中加入陶瓷粉料，加入研磨球，球磨处理得到浆料；
3)向浆料中加入引发剂，搅拌均匀后，除泡，注入模具，在30～80℃下加热固化20～90min；
4)脱模，机械加工，干燥得到纤维素纳米晶改性陶瓷坯体。
按上述方案，步骤2向预混液中加入陶瓷粉料按固液体积比计算为1：(0.3-2.4)。
按上述方案，所述单体为所述单体为丙烯酰胺、N’N-二甲基丙烯酰胺、N-羟甲基丙烯酸酰胺或壳聚糖大分子；交联剂为N,N-亚甲基双丙烯酰胺，分散剂为聚丙烯酸类化合物。
按上述方案，球磨时间为30～120min，转速为200～600r/min，球料质量比为(1～3):1。
按上述方案，所述的引发剂占单体质量的0.1％～20％。
按上述方案，坯体的干燥过程为20～80℃下干燥10～24h；然后在80～120℃下干燥12～48h。
纤维素纳米晶是从天然纤维素纤维中通过酸水解等方法提取的生物质基纳米粒子，具备来源广泛、高结晶度、高弹性模量、高强度、棒状形貌等特性，加之具有生物质材料的轻质、可降解、生物相容性及可再生等特性，适合填充于高性能复合材料。
从硫酸水解提取的纤维素纳米晶表面富含负电荷磺酸基团，促进其以静电排斥效应在水溶液中的良好分散性。由于纤维素纳米晶为棒状刚性材料，且表面含有大量羟基，同时有机凝胶表面含有羰基(含氧官能团)，可形成氢键，增强相互作用，使凝胶网络结构更交错复杂，可提高陶瓷坯体的力学性能。
本发明首次将其引入陶瓷体系，通过水基注凝成型技术将纤维素纳米晶良好分散于陶瓷浆料，显著改性陶瓷坯体的韧性及干燥后坯体强度。不仅具有工艺简便、成本低廉、环境友好等优点，同时能显著提高各类凝胶体系制备的陶瓷坯体的力学性能，适应性广，改变了陶瓷传统的脆性和难加工性，并且拓宽了纤维素纳米晶的应用范围，为陶瓷坯体的成型工艺提 供了新的方法。
相对于现有技术，本发明有益效果如下：
本发明首次采用添加纤维素纳米晶的方法来提高注凝成型陶瓷坯体的力学性能。纤维素纳米晶为细棒状刚性材料，具有高强度与高弹性模量，当其直接与有机凝胶网络结构和陶瓷材料进行物理掺杂复合，可有效抑制坯体微裂纹的扩展，使生坯三点抗弯强度提高到30MPa(纤维素纳米晶占预混液质量0.45％)，可直接进行机械加工。
由于纤维素纳米晶结构中含有大量羟基，具有较强的亲水性，使得坯体锁水性增强，干燥1～3小时后凝胶坯体(75mm×11mm×6mm)的三点弯曲形变量提高到10.8mm，韧性明显提高，且具有一定抗折强度，克服了凝胶坯体在冲切加工中容易粘模的难题，可直接对凝胶坯体进行造型，大大简化了工业生产过程。
纤维素纳米晶提取工艺成熟，原料来源丰富、天然无毒，为可再生资源，首次将其应用于陶瓷领域，赋予陶瓷优良的性能，提高产品附加值，进一步拓宽其应用领域。该发明为提高注凝成型坯体的力学性能提供了一种新方法，可进行工业化推广应用。
具体实施方式
以下实施例进一步阐释本发明的技术方案，但不作为对本发明保护范围的限制。
纤维素纳米晶制备过程如下：
棉短绒经碱处理除去杂质和木质素、半纤维素等成分，采用65％(质量分数)的硫酸水溶液对纯化后棉短绒纤维素进行强酸水解，除去纤维素中的无定型区域，保留其刚性结晶区，水解时间控制在1小时。水解后纤维素纳米晶悬浮液经过去离子水离心洗涤3～5次，去离子水透析后得到纤维素纳米晶悬浮液，将悬浮液冷冻干燥之后得到粉末状纤维素纳米晶。
制备得到的纤维素纳米晶具有棒状形貌，长度在100～300nm，直径在10～20nm，长径比在10～15，弹性模量在100-150GPa。
实施例1
①准确称取质量分数1.5％的纤维素纳米晶悬浮液3.75g，向悬浮液中依次加入N,N-二甲基丙烯酰胺3.75g，N,N-亚甲基双丙烯酰胺0.075g，聚丙烯酸铵0.3g，搅拌10分钟后用氨水调节pH值9.3，制得预混液；
②将氧化铝粉(球形α-Al2O3，白色粉末，d50≈5μm，α-Al2O3含量＞99.8％。)与预混液按固液体积比1:1混合；按球料质量比1.5:1加入研磨球，球磨30min，转速500rpm，制得浆料；
③向浆料中加入0.0375g引发剂过硫酸铵，搅拌15分钟后进行真空除泡，然后注入模 具中，在70℃下加热固化；
④固化后的湿坯经脱模、机械加工、将坯体在40℃温度下干燥12h，90℃温度下真空干燥24h，得到高强度的陶瓷生坯。
对比例1
准确称取水3.75g替换纤维素纳米晶悬浮液，其余重复实施例1的制备过程，制得陶瓷生坯。
经测试，实施例1中纤维素纳米晶改性的陶瓷坯体干燥后的抗折强度为30.19MPa，较对比例1中的陶瓷坯体干燥强度提高了51％；实施例1中经纤维素纳米晶改性的陶瓷坯体在自然干燥两小时后三点弯曲形变量为3mm，较同等状态下对比例1中的陶瓷坯体三点弯曲形变量提高了71％。
实施例2
①准确称取质量分数1.5％的纤维素纳米晶悬浮液15g，加入蒸馏水25g，搅拌10分钟；向溶液中依次加入N,N-二甲基丙烯酰胺7.5g，N,N-亚甲基双丙烯酰胺0.15g，聚丙烯酸铵0.6g，搅拌10分钟后用氨水调节pH值9，制得预混液；
②将氧化铝粉(球形α-Al2O3，白色粉末，d50≈5μm，α-Al2O3含量＞99.8％。)与预混液按固液体积比1:1混合；按球料质量比1.5:1加入研磨球，球磨30min，转速400rpm，制得浆料；
③向浆料中加入引发剂过硫酸铵，其固体质量为0.075g，搅拌15分钟后进行真空除泡，然后注入模具中，在70℃下加热固化。
④固化后的湿坯经脱模、机械加工、将坯体在40℃温度下干燥12h，90℃温度下真空干燥24h，得到高强度的陶瓷生坯。
对比例2
准确称取水15g替换纤维素纳米晶悬浮液，其余重复实施例2的制备过程，制得陶瓷生坯。
经测试，实施例2中纤维素纳米晶改性的陶瓷坯体干燥后的抗折强度为30.9MPa，较对比例2中的陶瓷坯体干燥强度提高了55％；实施例2中经纤维素纳米晶改性的陶瓷坯体在自然干燥两小时后三点弯曲形变量为2.5mm，较同等状态下对比例2中的陶瓷坯体三点弯曲形变量提高了43％。
实施例3
①准确称取质量分数1.5％纤维素纳米晶悬浮液30g，加入蒸馏水10g，搅拌10分钟； 向溶液中依次加入N,N-二甲基丙烯酰胺7.5g，N,N-亚甲基双丙烯酰胺0.15g，聚丙烯酸铵0.6g，搅拌10分钟后用氨水调节pH值9.2，制得预混液；
②将氧化铝粉(球形α-Al2O3，白色粉末，d50≈5μm，α-Al2O3含量＞99.8％。)与预混液按固液体积比1:1混合；按球料质量比1.5:1加入研磨球，球磨30min，转速400rpm，制得浆料；
③向浆料中加入引发剂过硫酸铵，其固体质量为0.075g，搅拌15分钟后进行真空除泡，然后注入模具中，在70℃下加热固化。
④固化后的湿坯经脱模、机械加工、将坯体在40℃温度下干燥12h，90℃温度下真空干燥24h，得到高强度的陶瓷生坯。
对比例3
准确称取水30g替换纤维素纳米晶悬浮液，其余重复实施例3的制备过程，制得陶瓷生坯。
经测试，实施例3中纤维素纳米晶改性的陶瓷坯体干燥后的抗折强度为24.7MPa，较对比例3中的陶瓷坯体干燥强度提高了25％；实施例3中经纤维素纳米晶改性的陶瓷坯体在自然干燥两小时后三点弯曲形变量为2.9mm，较同等状态下对比例3中的陶瓷坯体三点弯曲形变量提高了66％。
实施例4
①准确称取质量分数1.5％纤维素纳米晶悬浮液40g；向溶液中依次加入N,N-二甲基丙烯酰胺7.5g，N,N-亚甲基双丙烯酰胺0.15g，聚丙烯酸铵0.6g，搅拌10分钟后用氨水调节pH值9.4，制得预混液；
②将氧化铝粉(球形α-Al2O3，白色粉末，d50≈5μm，α-Al2O3含量＞99.8％。)与预混液按固液体积比1:1混合；按球料质量比1.5:1加入研磨球，球磨30min，转速400rpm，制得浆料；
③向浆料中加入引发剂过硫酸铵，其固体质量为0.075g，搅拌15分钟后进行真空除泡，时间为10分钟，然后注入模具中，在70℃下加热固化，时间为60分钟。
④固化后的湿坯经脱模、机械加工、将坯体在40℃温度下干燥12h，90℃温度下真空干燥24h，得到高强度的陶瓷生坯。
对比例4
准确称取水40g替换纤维素纳米晶悬浮液，其余重复实施例4的制备过程，制得陶瓷生坯。
经测试，实施例4中纤维素纳米晶改性的陶瓷坯体干燥后的抗折强度为27.8MPa，较对比例4中的陶瓷坯体干燥强度提高了39％；实施例4中经纤维素纳米晶改性的陶瓷坯体在自然干燥两小时后三点弯曲形变量为3.9mm，较同等状态下对比例4中的陶瓷坯体三点弯曲形变量提高了124％。
实施例5
①准确称取质量分数2％的纤维素纳米晶悬浮液10g，加入蒸馏水30g，搅拌10分钟；向溶液中依次加入丙烯酰胺7.5g，N,N-亚甲基双丙烯酰胺0.15g，聚丙烯酸铵0.6g，搅拌10分钟后用氨水调节pH值9，制得预混液；
②将氧化铝粉(球形α-Al2O3，白色粉末，d50≈5μm，α-Al2O3含量＞99.8％。)与预混液按固液体积比1:1混合；按球料质量比1.5:1加入研磨球，球磨30min，转速400rpm，制得浆料；
③向浆料中加入引发剂过硫酸铵，其固体质量为0.075g，搅拌15分钟后进行真空除泡，然后注入模具中，在70℃下加热固化。
④固化后的湿坯经脱模、机械加工、将坯体在40℃温度下干燥12h，90℃温度下真空干燥24h，得到高强度的陶瓷生坯。
对比例5
准确称取水10g替换纤维素纳米晶悬浮液，其余重复实施例5的制备过程，制得陶瓷生坯。
经测试，对比例5中由丙烯酰胺注凝体系制备的的陶瓷坯体干燥强度为46.62MPa，在实施例5中经纤维素纳米晶改性的陶瓷坯体干燥后的抗折强度为58.85MPa，提高了26.2％；实施例5中经纤维素纳米晶改性的陶瓷坯体在自然干燥两小时后三点弯曲形变量为3.1mm，较同等状态下对比例5中的陶瓷坯体三点弯曲形变量提高了77％。
本发明利用纤维素纳米晶改性水基注凝成型陶瓷坯体力学性能的效果显著，所制备的陶瓷坯体易于加工。其他实施例比较对比例在力学性能上均有明显提升，在此不再一一描述。
本发明所列举的各原料，以及本发明各原料的上下限、区间取值，以及工艺参数(如干燥温度、球磨转速等)的上下限、区间取值都能实现本发明，在此不一一列举实施例。

Claims (10)

  1. 一种陶瓷坯体，其特征在于注凝成型加入了纤维素纳米晶，纤维素纳米晶含量在0.01-15wt％。
  2. 一种陶瓷坯体，其特征在于所述陶瓷坯体含有纤维素纳米晶、有机凝胶和陶瓷粉料；按重量份数计纤维素纳米晶0.1～10份；有机凝胶0.1～30份；陶瓷粉料70～99份。
  3. 如权利要求1或2所述陶瓷坯体，其特征在于所述纤维素纳米晶长度为100～300nm，直径为10～20nm，长径比为10～15，弹性模量100-150GPa。
  4. 如权利要求1或2所述陶瓷坯体，其特征在于所述纤维素纳米晶按以下方法制备而来：
    棉短绒经碱处理、硫酸水解、离心洗涤、透析后得到纤维素纳米晶悬浮液，将悬浮液冷冻干燥之后得到粉末状纤维素纳米晶。
  5. 如权利要求2所述陶瓷坯体，其特征在于所述陶瓷粉料为氧化铝、氧化锆、莫来石、熔融石英、氮化硼的任意一种或混合。
  6. 权利要求1或2所述陶瓷坯体的制备方法，其特征在于包括以下步骤：
    1)配置纤维素纳米晶/水悬浮液，依次加入单体、交联剂、分散剂，混匀后用氨水调节pH＝8～11，得到预混液；
    2)向预混液中加入陶瓷粉料，加入研磨球，球磨处理得到浆料；
    3)向浆料中加入引发剂，搅拌均匀后，除泡，注入模具，在30～80℃下加热固化20～90min；
    4)脱模，机械加工，干燥得到纤维素纳米晶改性陶瓷坯体。
  7. 如权利要求6所述陶瓷坯体的制备方法，其特征在于步骤2向预混液中加入陶瓷粉料按固液体积比计算为1：(0.3～2.4)。
  8. 如权利要求6所述陶瓷坯体的制备方法，其特征在于所述单体为所述单体为丙烯酰胺、N’N-二甲基丙烯酰胺、N-羟甲基丙烯酸酰胺或壳聚糖大分子；交联剂为N,N-亚甲基双丙烯酰胺，分散剂为聚丙烯酸类化合物。
  9. 如权利要求6所述陶瓷坯体的制备方法，其特征在于球磨时间为30～120min，转速为200～600r/min，球料质量比为(1～3):1。
  10. 如权利要求6所述陶瓷坯体的制备方法，其特征在于坯体的干燥过程为20～80℃下干燥10～24h；然后在80～120℃下干燥12～48h。
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