CN114477966A - 一种细晶氧化物陶瓷的制备方法 - Google Patents
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Abstract
本发明公开了一种电场辅助下快速烧结制备细晶氧化物陶瓷的方法，包括以下步骤：步骤1：通过水解沉淀法制备包覆粉体并经模压得到坯体；步骤2：将步骤1中的坯体加热到预设温度T，其中300℃≤T≤1300℃；步骤3：将步骤2加热后的坯体放入直流电场内，在预设电场强度E和交电流密度J下发生闪烧；其中60V/cm≤E≤1500V/cm，5mA/mm2≤J≤200mA/mm2；步骤4：发生闪烧后保持电流密度J一段时间t；去掉施加直流电场，将坯体冷却到室温，即可得到细晶氧化物陶瓷块体；本发明具有有效抑制陶瓷烧结过程中晶粒长大的优点，为细晶氧化物陶瓷的制备提供了新的途径。
Description
技术领域
本发明涉及细晶氧化物陶瓷的制备方法，具体涉及一种氧化物粉体表面经包覆处理后在电场辅助下烧结细晶陶瓷的制备方法，属于陶瓷制备领域。
背景技术
先进结构陶瓷由于具有高强度、高硬度、耐高温、耐腐蚀、耐磨损等优异性能而受到人们的广泛关注。相比于功能陶瓷，结构陶瓷更受关注的是其力学性能的优劣。陶瓷晶粒的细化是结构陶瓷具有更优越力学性能的关键因素之一。工业上将通过细化晶粒以提高材料强度的方法称为细晶强化。通常陶瓷是由许多晶粒组成的多晶体，晶粒越细，晶界面积越大，晶界越曲折，越不利于裂纹的扩展，根据Hall-Petch关系式，晶粒的平均尺寸越小，材料的屈服强度越高。
然而，由于传统烧结方法需要在高温下长时间的保温，促进了陶瓷烧结过程中晶粒的长大，造成晶粒粗大且粒径分布不均匀等问题，严重影响了结构陶瓷的力学性能。因此控制陶瓷晶粒在烧结过程中的长大对于结构陶瓷的研究至关重要。Chen等人提出的两步法烧结在一定程度上抑制了晶粒生长。然而，通过该方法烧结的氧化铝陶瓷晶粒尺寸仍然达到500-730nm，约为初始粒度的3-5倍，对于两步法烧结氧化锆陶瓷而言，3YSZ的晶粒尺寸约为初始粒度的3倍，而8YSZ则达到初始粒度的9-12倍。放电等离子烧结(SPS)是另一种制备细晶陶瓷的技术。Makino等人使用初始尺寸约为100-230nm的氧化铝粉体，通过SPS烧结的氧化铝陶瓷的晶粒尺寸约为300-500nm。尽管两步法烧结和SPS等技术都能在一定程度上抑制晶粒长大，但是烧结过程中的晶粒生长仍然较为明显。因此烧结工艺的改善对于细晶陶瓷的制备具有重大意义。
发明内容
本发明的目的是为了解决现有氧化物陶瓷烧结后晶粒粗大的问题，提供一种细晶氧化物陶瓷的制备方法；该方法通过在氧化物粉体表面包覆一层异质物，通过电场辅助烧结得到细晶氧化物陶瓷；
本发明的目的是通过下述技术方案实现的。
一种细晶氧化物陶瓷的制备方法，包括以下步骤：
步骤一、将经过表面包覆的氧化物粉体成型后得到坯体；
步骤二、将步骤一中的坯体加热到预设温度T，并保温10min，其中300℃≤T≤1300℃；
步骤三、将步骤二加热后的坯体放入直流电场内，在预设电场强度E和交电流密度J下发生闪烧；其中60V/cm≤E≤1500V/cm，5mA/mm2≤J≤200mA/mm2；
步骤四、发生闪烧后保持电流密度J一段时间t；去掉施加直流电场，将坯体冷却到室温，即得到细晶氧化物陶瓷块体；其中时间t的范围不超过10s。
经过包覆处理后的氧化物粉体，在经过电场辅助烧结后能够得到几乎全致密的细晶氧化物陶瓷。
所述细晶氧化物陶瓷的晶粒尺寸与初始粉体粒径相近。
所述包覆粉体采用不同晶型的两种异质氧化物进行包覆处理，其中基体粉体为其中基体粉体为氧化铝(Al2O3)，氧化锆(ZrO2)，钛酸钡(BaTiO3)，氧化钇(Y2O3)，氧化镁(MgO)中的一种，包覆层粉体氧化铝(Al2O3)，氧化锆(ZrO2)中的一种。
所述表面包覆处理的氧化物粉体通过固相法、液相法或气相法中的任意一种制备得到。
所述细晶氧化物陶瓷块体通过对粉体进行表面包覆，抑制了氧化物陶瓷在电场辅助烧结条件下晶粒的长大。
有益效果：
(1)本发明方法在电场辅助下的快速烧结，解决了传统陶瓷烧结中，长时间保温带来的晶粒粗化，既高效节能又能抑制粗大晶粒的形成，粉体在经包覆后进行闪烧有效抑制了晶粒的长大；
(2)本发明方法在外加电场作用下进行烧结，可通过调节外加电场参数：电场强度、电流密度等闪烧参数，实现对陶瓷烧结过程的有效控制，最终控制样品密度及晶粒尺寸；
(3)本发明制备方法简单、易于操作，无需大型仪器协助，有利于细晶氧化物陶瓷的快速制备；
(4)本发明制备得到的细晶氧化物陶瓷，具有较高的密度及与初始粉体粒径相近的晶粒尺寸，可作为细晶氧化物陶瓷材料的在制备方法。
附图说明
图1为本发明制备方法流程示意图。
图2为本发明实施例1闪烧的电流变化图。
图3为本发明实施例1的SEM图像。
图4为本发明对照例1的SEM图像。
图5为本发明对照例2的SEM图像。
图6为本发明对照例3的SEM图像。
图7为本发明实施例2的SEM图像；其中图a电流密度为80mA/mm2，图b电流密度为100mA/mm2；
具体实施方式
下面结合附图和具体实施例对本发明做进一步说明。
实施例1
采用包覆粉体烧结氧化铝陶瓷按照以下方法制备：
步骤1：氧化锆包覆氧化铝粉体的制备
采用醇盐水解沉淀法制备ZrO2包覆Al2O3粉体。纯度为99.99％的Al2O3(初始粒径170nm)、无水乙醇、正丁醇锆(C16H36O4Zr)和2mol/L的醋酸作为原料。利用超声分散将氧化铝粉体均匀的分散在无水乙醇中，超声分散时间为1h。随后在磁力搅拌下将正丁醇锆缓慢加入到分散后的液体中，持续搅拌并缓慢滴加2mol/L的醋酸。将搅拌后的混合液静置、抽滤，并在90℃下干燥，将干燥粉体在1100℃下热处理2h，得到包覆粉体。
步骤2：闪烧制备氧化铝陶瓷块体
将5wt％PVA水溶液加入到上述粉体中造粒并过筛，过筛所得粉体在10MPa模压60s之后，再在200MPa冷等静压2min，得到陶瓷坯体。将该陶瓷坯体加热至500℃并保温2h，再缓慢冷却至200℃后自然降至室温，从而去除其中的PVA。
将去除PVA的陶瓷坯体置于闪烧炉中加热至1300℃并保温10min。在陶瓷坯体两端施加直流电场，电场强度为700V/cm。闪烧发生后样品到达预设电流密度13mA/mm2，并保持电场10s，关闭电源并降至室温，得到烧结后的氧化铝陶瓷块体。图2为闪烧过程中电流的变化图。
对本实施例1闪烧后氧化铝陶瓷块体进行SEM表征，图3为闪烧后氧化铝陶瓷样品的SEM图像，表明在经过包覆处理后进行闪烧的氧化铝陶瓷具有与初始粒径相近的细晶结构。
对照例1
采用包覆粉体烧结氧化铝陶瓷按照以下方法制备：
步骤1：氧化锆包覆氧化铝粉体的制备
采用醇盐水解沉淀法制备ZrO2包覆Al2O3粉体。纯度为99.99％的Al2O3(初始粒径170nm)、无水乙醇、正丁醇锆(C16H36O4Zr)和2mol/L的醋酸作为原料。利用超声分散将氧化铝粉体均匀的分散在无水乙醇中，超声分散时间为1h。随后在磁力搅拌下将正丁醇锆缓慢加入到分散后的液体中，持续搅拌并缓慢滴加2mol/L的醋酸。将搅拌后的混合液静置、抽滤，并在90℃下干燥，将干燥粉体在1100℃下热处理2h，得到包覆粉体。
步骤2：传统烧结制备氧化铝陶瓷块体
将5wt％PVA水溶液加入到上述粉体中造粒并过筛，过筛所得粉体在10MPa模压60s之后，再在200MPa冷等静压2min，得到陶瓷坯体。将该陶瓷坯体加热至500℃并保温2h，再缓慢冷却至200℃后自然降至室温，从而去除其中的PVA。
将去除PVA的陶瓷坯体置于管式炉中加热至1600℃并保温2h，随后待炉温降至室温，得到烧结后的氧化铝陶瓷块体。
对上述制备得到的氧化铝陶瓷块体进行SEM表征，如图4所示。
对照例2
采用未包覆粉体烧结氧化铝陶瓷按照以下方法制备：
步骤1：氧化铝粉体预处理
纯度为99.99％Al2O3和MgO作为原料。利用高纯氧化锆磨球对上述原料粉体进行球磨混合12h。其中，球磨介质为去离子水，转速为250r/min；球磨后的浆料经过冷冻干燥得到0.25wt％MgO掺杂Al2O3粉体。
步骤2：闪烧制备氧化铝陶瓷块体
将5wt％PVA水溶液加入到上述粉体中造粒并过筛，过筛所得粉体在10MPa模压60s之后，再在200MPa冷等静压2min，得到陶瓷坯体。将该陶瓷坯体加热至500℃并保温2h，再缓慢冷却至200℃后自然降至室温，从而去除其中的PVA。
将去除PVA的陶瓷坯体置于闪烧炉中加热至1300℃并保温10min。在陶瓷坯体两端施加直流电场，电场强度为700V/cm。闪烧发生后样品到达预设电流密度13mA/mm2，并保持电场10s，关闭电源并降至室温，得到烧结后的氧化铝陶瓷块体。
对制备得到的氧化铝陶瓷块体进行SEM表征。如图5所示。
对照例3
采用未包覆粉体烧结氧化铝陶瓷按照以下方法制备：
步骤1：氧化铝粉体预处理
纯度为99.99％Al2O3和MgO作为原料。利用高纯氧化锆磨球对上述原料粉体进行球磨混合12h。其中，球磨介质为去离子水，转速为250r/min；球磨后的浆料经过冷冻干燥得到0.25wt％MgO掺杂Al2O3粉体。
步骤2：传统烧结制备氧化铝陶瓷块体
将5wt％PVA水溶液加入到上述粉体中造粒并过筛，过筛所得粉体在10MPa模压60s之后，再在200MPa冷等静压2min，得到陶瓷坯体。将该陶瓷坯体加热至500℃并保温2h，再缓慢冷却至200℃后自然降至室温，从而去除其中的PVA。
将去除PVA的陶瓷坯体置于管式炉中加热至1600℃并保温2h，随后待炉温降至室温，得到烧结后的氧化铝陶瓷块体。
对上述制备得到的氧化铝陶瓷块体进行SEM表征，如图6所示。
实施例2
采用包覆粉体烧结氧化锆陶瓷按照以下方法制备：
步骤1：氧化铝包覆氧化锆粉体的制备
称取一定量ZrO2粉体，溶于无水乙醇中，加入聚丙烯酰胺(C3H5NO)n作为分散剂，超声分散制得氧化锆悬浮液；称取一定量的无水AlCl3加入悬浮液中，使其浓度为0.3mol/L，搅拌得到混合溶液；将氨水(NH3·H2O)缓慢滴加到混合溶液中，同时控制搅拌速度并用HCl调节溶液的pH＝5；待反应结束后静置2h，然后过滤洗涤；将所得沉淀放入烘箱中干燥，将干燥后的粉体研磨；最后对粉体进行煅烧得到氧化铝包覆氧化锆粉体。
步骤2：闪烧制备氧化铝锆陶瓷块体
将5wt％PVA水溶液加入到上述粉体中造粒并过筛，过筛所得粉体在10MPa模压60s之后，再在200MPa冷等静压2min，得到陶瓷坯体。将该陶瓷坯体加热至500℃并保温2h，再缓慢冷却至200℃后自然降至室温，从而去除其中的PVA。
将去除PVA的陶瓷坯体置于闪烧炉中加热至1000℃并保温10min。在陶瓷坯体两端施加直流电场，电场强度为300V/cm。闪烧发生后样品到达预设电流密度100-200mA/mm2，并保持电场10s，关闭电源并降至室温，得到烧结后的氧化锆陶瓷块体。
图7为闪烧后氧化锆样品的SEM图像。
本发明在氧化物陶瓷粉体表面包覆一层不同晶型的异质层，经过成型并加热到预设温度，对成型坯体施加直流电场，得到几乎全致密且晶粒尺寸与初始粉体粒径相近的陶瓷块体。该制备方法能在较传统烧结温度低的条件下实现陶瓷的快速烧结，并且能够有效抑制陶瓷烧结过程中的晶粒长大，从而改善陶瓷的性能，为细晶陶瓷的制备提供了一种方法。
Claims (5)
1.一种细晶氧化物陶瓷的制备方法，其特征在于：包括以下步骤：
步骤一、将经过表面包覆的氧化物粉体成型后得到坯体；
步骤二、将步骤一中的坯体加热到预设温度T；
步骤三、将步骤二加热后的坯体放入直流电场内，在预设电场强度E和交电流密度J下发生闪烧；
步骤四、发生闪烧后保持电流密度J一段时间t；去掉施加直流电场，将坯体冷却到室温，即得到细晶氧化物陶瓷块体。
2.如权利要求1所述的一种细晶氧化物陶瓷的制备方法，其特征在于：所述包覆粉体采用不同晶型的两种异质氧化物进行包覆处理；其中基体粉体为氧化铝(Al2O3)，氧化锆(ZrO2)，钛酸钡(BaTiO3)，氧化钇(Y2O3)，氧化镁(MgO)中的一种，包覆层粉体为氧化铝(Al2O3)，氧化锆(ZrO2)中的一种。
3.如权利要求1所述的一种细晶氧化物陶瓷的制备方法，其特征在于：步骤二所述T的范围为300℃≤T≤1300℃。
4.如权利要求1所述的一种细晶氧化物陶瓷的制备方法，其特征在于：步骤三所述电场强度E和交电流密度J的范围为：60V/cm≤E≤1500V/cm，5mA/mm2≤J≤200mA/mm2。
5.如权利要求1所述的一种细晶氧化物陶瓷的制备方法，其特征在于：步骤四所述时间t的范围0≤t≤10s。
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