CN117447197A - 一种高熵假板钛矿钛酸盐陶瓷的制备方法 - Google Patents
一种高熵假板钛矿钛酸盐陶瓷的制备方法 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 75
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000011812 mixed powder Substances 0.000 claims abstract description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000000498 ball milling Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 23
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims 2
- 150000001768 cations Chemical class 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005469 granulation Methods 0.000 abstract description 3
- 230000003179 granulation Effects 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 description 31
- 239000010936 titanium Substances 0.000 description 30
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000000739 chaotic effect Effects 0.000 description 2
- LFSBSHDDAGNCTM-UHFFFAOYSA-N cobalt(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Co+2] LFSBSHDDAGNCTM-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- -1 titanium ions Chemical class 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
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Abstract
本发明属于假板钛矿钛酸盐陶瓷制备技术领域，公开了一种高熵假板钛矿钛酸盐陶瓷的制备方法，包括：按照化学式(α0.75β0.5)Ti1.75O5称取相应的二价金属氧化物粉体αO、三价金属氧化物粉体β2O3和TiO2粉末，球磨混合均匀得到初始混合粉末；在初始混合粉末中加入PVA溶液作为粘结剂进行造粒，得二次混合粉末；将二次混合粉末进行干压成型，得到坯体，高温烧结，获得高熵假板钛矿钛酸盐陶瓷。本发明将二价和三价金属阳离子同时在八面体Wyckoff‑4c位和Wyckff‑8f位的混乱分布，极大地增加了假板钛矿钛酸盐陶瓷的构型熵，提高了假板钛矿钛酸盐陶瓷的高温热稳定性。
Description
技术领域
本发明属于假板钛矿钛酸盐陶瓷制备技术领域，尤其是涉及一种具有优异热稳定性的高熵假板钛矿钛酸盐陶瓷的制备方法。
背景技术
钛酸盐陶瓷主要可以分为两种：具有钙钛矿晶体结构的钛酸盐陶瓷和具有假板钛矿晶体结构的钛酸盐陶瓷。与钙钛矿钛酸盐陶瓷相比，假板钛矿钛酸盐陶瓷，例如钛酸镁、钛酸铁、钛酸铝等具有较低的热导率和热膨胀系数，以及较高的熔点和优异的抗热震性，是一种优良的高温隔热材料和高温过滤材料。假板钛矿钛酸盐陶瓷的优异性能在很大程度上归因于其特殊的晶体结构，其晶体结构由两种不同的畸变八面体组成，阳离子分别位于两种八面体的Wyckoff-4c位和Wyckff-8f位。然而假板钛矿钛酸盐最大的缺点是其热稳定性较差，在400~1200℃容易分解，这严重限制了其进一步的应用。
高熵材料的概念首先出现在合金领域。随后，科研人员将高熵材料的概念以及高构型熵、严重的晶格畸变、缓慢扩散、鸡尾酒效应四大效应进一步拓展至陶瓷领域，陆续开发出具有各种优异性能的高熵陶瓷。一般来说，高熵陶瓷内部的一个阳离子晶格点位由多个阳离子主元所共享，这个混乱分布赋予了高熵陶瓷较高的构型熵。这一高构型熵赋予了材料各类优良的特性，例如高强度、高硬度、低热导率以及优良的结构稳定性。
因此，如能将高熵概念引入到钛酸盐陶瓷中，则可大幅度提高钛酸盐陶瓷的结构稳定性，解决其中高温度段易分解的问题。一般来说只是单一阳离子位点的掺杂提供的构型熵有限，而阴离子的尺寸较大，一般难以形成高熵位点，所以为了大幅度增加钛酸盐陶瓷的构型熵，就需提出一种新的高熵陶瓷设计理念，从而提高其结构稳定性。此外，由于材料的热导率与其晶体结构的复杂程度成反比，因此，所设计的具有高构型熵的钛酸盐陶瓷也将具有极低的本征热导率。
发明内容
本发明的目的在于克服现有技术的不足，提供一种高熵假板钛矿钛酸盐陶瓷的制备方法，将高熵概念引入到假板钛矿钛酸盐陶瓷中来提高假板钛矿钛酸盐陶瓷的高温稳定性，克服了现有假板钛矿钛酸盐陶瓷高温易分解的问题。
本发明是通过如下技术方案予以实现：
一种高熵假板钛矿钛酸盐陶瓷的制备方法，包括下述步骤：
（1）按照化学式(α0.75β0.5)Ti1.75O5称取相应的二价金属氧化物混合粉体αO、三价金属氧化物混合粉体β2O3和TiO2粉末，随后球磨混合均匀得到初始混合粉末；所述的二价金属氧化物混合粉体αO是MgO、CoO、NiO、CuO、ZnO中的任意三种，且称取的三者粉体的摩尔数相同；所述的三价金属氧化物混合粉体β2O3是Al2O3、Fe2O3、Ga2O3中的任意两种，且称取的两者粉体的摩尔数相同；
（2）在初始混合粉末中，加入质量浓度4wt%~10wt%的PVA溶液作为粘结剂进行造粒，获得二次混合粉末；所述初始混合粉末、加入的PVA溶液的质量比为15：(1~4)；
（3）将二次混合粉末进行干压成型，得到坯体；
（4）将坯体进行烧结，获得高熵假板钛矿钛酸盐陶瓷。
进一步地，所述初始混合粉末、加入的PVA溶液的质量比为15：(1~2)。
进一步地，所述的PVA溶液的质量浓度为6wt%~8wt%。
进一步地，所述的干压成型的压力为100~200MPa。
进一步地，所述的烧结具体为：先以1~2℃/min的速度升温至650℃并保温1~4h，而后以5~10℃/min的速度升温至1300~1400℃，保温2~6h。
中高温相稳定性差是限制假板钛矿钛酸盐陶瓷广泛应用的一个重要原因。假板钛矿钛酸盐陶瓷是一个典型的熵稳定陶瓷，由于单相陶瓷的构型熵不高，所以其在400~1200℃极易分解。为此，本发明拟将高熵概念引入到假板钛矿钛酸盐陶瓷中，通过增加其构型熵来提高其相稳定性。但传统的高熵都是在同一阳离子位点引入不同元素，其熵增效果有限，难以满足假板钛矿钛酸盐高温热稳定的需求。假板钛矿钛酸盐的晶体结构由两种不同的畸变八面体组成，阳离子分别位于两种八面体的Wyckoff-4c位和Wyckff-8f位。研究发现，对于二价金属假板钛矿钛酸盐来说（如钛酸镁、钛酸钴等），二价金属离子处于在八面体的Wyckoff-4c位，钛离子处于八面体的Wyckff-8f位，引入高熵概念后大量的二价金属离子依然混乱分布在Wyckoff-4c位中；对于三价金属假板钛矿钛酸盐来说（如钛酸铝、钛酸铁等），三价金属离子处于八面体的Wyckff-8f位，而钛离子处于八面体的Wyckoff-4c位，引入高熵概念后大量的三价金属离子会混乱分布在Wyckff-8f位中。因此，如果在假板钛矿钛酸盐中同时引入二价和三价过渡金属离子，则可以使二价和三价过渡金属离子同时在Wyckoff-4c位和Wyckff-8f位中混乱分布，从而获得极高的构型熵。
本发明的优点和积极效果是：
本发明首次提出基于双异价阳离子的高熵假板钛矿钛酸盐的制备工艺，二价和三价金属阳离子在八面体的Wyckoff-4c位和Wyckff-8f位的同时混乱分布，极大地增加了假板钛矿钛酸盐陶瓷的构型熵，从而进一步提高假板钛矿钛酸盐陶瓷的高温热稳定性。
附图说明
图1为实施例1制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Co0.25Ni0.25Al0.25Ga0.25)Ti1.75O5放大1000倍的SEM图；
图2为实施例1制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Co0.25Ni0.25Al0.25Ga0.25)Ti1.75O5的XRD谱图以及其在1200℃下热处理50h后的XRD谱图；
图3为实施例2制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Al0.25Fe0.25)Ti1.75O5放大1000倍的SEM图；
图4为实施例2制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Al0.25Fe0.25)Ti1.75O5的XRD谱图以及其在1200℃下热处理50h后的XRD谱图；
图5为对比例1制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Co0.25Ni0.25)Ti1.75O55的XRD谱图以及其在1200℃下热处理50h后的XRD谱图；
图6为对比例2制备的高熵假板钛矿钛酸盐陶瓷(Mg0.55Co0.1Ni0.1Al0.4Ga0.1)Ti1.75O5的XRD谱图以及其在1200℃下热处理50h后的XRD谱图。
具体实施方式
为了更好的理解本发明，下面结合附图对本发明进行进一步详述。在不冲突的情况下，案例中的特征可以相互组合。以下实施例中所使用的原料均为市售的分析纯原料。
实施例1
一种具有优异热稳定性的高熵假板钛矿钛酸盐陶瓷的制备方法，包括下述步骤：
（1）按照化学式(Mg0.25Co0.25Ni0.25Al0.25Ga0.25)Ti1.75O5分别称取4.03g的MgO粉末、7.49g的 CoO粉末、7.47g的NiO粉末、5.10g的 Al2O3粉末、9.37g的 Ga2O3粉末和55.93g 的TiO2粉末，并用球磨机混合均匀，得到初始混合粉末；
（2）称取1.50g的初始混合粉末，并加入0.1g质量浓度为6wt%的PVA溶液作为粘结剂，进行造粒，得到二次混合粉末；
（3）将获得的二次混合粉末置于模具中，在120MPa的压力下干压成型，得到坯体；
（4）将坯体置于高温炉中，以1℃/min的速度升至650℃并保温1h，而后以5℃/min的速度升温至1400℃，保温4h，高温烧结后即得高熵假板钛矿钛酸盐陶瓷(Mg0.25Co0.25Ni0.25Al0.25Ga0.25)Ti1.75O5。
实施例1制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Co0.25Ni0.25Al0.25Ga0.25)Ti1.75O5的扫描电镜图如图1所示。实施例1制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Co0.25Ni0.25Al0.25Ga0.25)Ti1.75O5的XRD谱图以及其在1200℃下热处理50h后的XRD谱图如图2所示。
实施例2
一种具有优异热稳定性的高熵假板钛矿钛酸盐陶瓷的制备方法，包括下述步骤：
（1）按照化学式(Mg0.25Cu0.25Zn0.25Al0.25Fe0.25)Ti1.75O5分别称取4.03g的 MgO粉末、7.95g的 CuO粉末、8.14g的ZnO粉末、5.10g的 Al2O3粉末、7.98g的 Fe2O3粉末和55.93g 的TiO2粉末，并用球磨机混合均匀，得到初始混合粉末；
（2）称取1.50g的初始混合粉末，并加入0.15g质量浓度为8wt%的PVA溶液作为粘结剂，进行造粒，得到二次混合粉末；
（3）将获得的二次混合粉末置于模具中，在140MPa的压力下干压成型，得到坯体；
（4）将坯体置于高温炉中，以2℃/min的速度升至650℃并保温3h，而后以8℃/min的速度升温至1300℃，保温6h，高温烧结后即得高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Al0.25Fe0.25)Ti1.75O5。
实施例2制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Al0.25Fe0.25)Ti1.75O5的扫描电镜图如图3所示。实施例2制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Al0.25Fe0.25)Ti1.75O5的XRD谱图以及其在1200℃下热处理50h后的XRD谱图如图4所示。
对比例1
一种具有优异热稳定性的高熵假板钛矿钛酸盐陶瓷的制备方法，制备方法同实施例1，区别仅在于步骤（1）：按照化学式(Mg0.25Cu0.25Zn0.25Co0.25Ni0.25)Ti1.75O5分别称取4.03g的 MgO粉末、7.95g的 CuO粉末、8.14g的ZnO粉末、7.49g的 CoO粉末、7.47g的 NiO粉末和79.9g 的TiO2粉末，并用球磨机混合均匀，得到初始混合粉末。
对比例1制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Co0.25Ni0.25)Ti1.75O5的XRD谱图以及其在1200℃下热处理50h后的XRD谱图如图5所示。
对比例2
一种具有优异热稳定性的高熵假板钛矿钛酸盐陶瓷的制备方法，制备方法同实施例1，区别仅在于步骤（1）：按照化学式(Mg0.55Co0.1Ni0.1Al0.4Ga0.1)Ti1.75O5分别称取8.87g的MgO粉末、3.00g的 CoO粉末、2.99g的NiO粉末、8.16g的 Al2O3粉末、3.75g的 Ga2O3粉末和55.93g 的TiO2粉末，并用球磨机混合均匀，得到初始混合粉末。
对比例2制备的高熵假板钛矿钛酸盐陶瓷(Mg0.55Co0.1Ni0.1Al0.4Ga0.1)Ti1.75O5的XRD谱图以及其在1200℃下热处理50h后的XRD谱图如图6所示。
评价与表征
图1和图3分别为实施例1和实施例2制备的高熵假板钛矿钛酸盐陶瓷放大1000倍的SEM图，可以看出，本发明制备出的高熵假板钛矿钛酸盐陶瓷具有均匀的显微结构及较高的致密度。图2和图4分别为实施例1和实施例2制备的高熵假板钛矿钛酸盐陶瓷的XRD谱图以及其在1200℃下热处理50h后的XRD谱图，可以看出，本发明制备出的高熵假板钛矿钛酸盐陶瓷呈现出单一物相，且衍射峰与单相假板钛矿钛酸钴（PDF73-1631）的衍射峰重合，这证明了制备出的产物为高熵假板钛矿钛酸盐陶瓷。此外，还可以看出，实施例1和实施例2制备的两种产物在1200℃下热处理50h后未发生分解，进而证明制备的高熵假板钛矿钛酸盐具有优良的热稳定性。经测试，高熵假板钛矿钛酸盐还具有较低的室温热导率，其中实施例1制备的(Mg0.25Co0.25Ni0.25Al0.25Ga0.25)Ti1.75O5的室温热导率为1.25W·m-1·K-1，实施例2制备的(Mg0.25Cu0.25Zn0.25Al0.25Fe0.25)Ti1.75O5的室温热导率为1.23 W·m-1·K-1。
图5为对比例1制备的高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Co0.25Ni0.25)Ti1.75O55的XRD谱图以及其在1200℃下热处理50h后的XRD谱图。可以看出，1200℃下50h处理后，高熵假板钛矿钛酸盐陶瓷(Mg0.25Cu0.25Zn0.25Co0.25Ni0.25)Ti1.75O55发生了分解，生成了杂质相。此外，还可以发现与未处理样品的XRD谱图相比，热处理50h后样品的XRD谱图发生了偏移，这是因为高熵假板钛矿钛酸盐陶瓷分解导致了部分元素析出，剩下的高熵陶瓷的晶格常数发生了变化，从而导致其XRD衍射峰的峰位发生了偏移。对比例1选的五种金属元素均为二价金属离子（Mg、Co、Ni、Cu、Zn），所以其形成的高熵假板钛矿钛酸盐陶瓷的构型熵要远低于实施例1和实施例2制备的高熵假板钛矿钛酸盐陶瓷。这就导致其热稳定性较差，高温热处理后会发生分解。此外，(Mg0.25Cu0.25Zn0.25Co0.25Ni0.25)Ti1.75O55陶瓷的热导率为1.56W·m-1·K-1，远高于实施例1和实施例2制备的高熵假板钛矿钛酸盐陶瓷的热导率。
图6为对比例2制备的高熵假板钛矿钛酸盐陶瓷(Mg0.55Co0.1Ni0.1Al0.4Ga0.1)Ti1.75O5的XRD谱图以及其在1200℃下热处理50h后的XRD谱图，可以看出，1200℃下50h处理后，高熵假板钛矿钛酸盐陶瓷(Mg0.55Co0.1Ni0.1Al0.4Ga0.1)Ti1.75O5发生了分解，生成了杂质相，同时高熵陶瓷的XRD衍射峰的峰位也发生了偏移。对比例2选择的二价元素和三价元素的种类与实施例1中相同，但是Mg、Co、Ni、Al、Ga之间的摩尔比变为5.5：1：1：4：1，不是等摩尔元素配比，这就导致高熵假板钛矿钛酸盐陶瓷(Mg0.55Co0.1Ni0.1Al0.4Ga0.1)Ti1.75O5的构型熵也不够高，高温热处理后制备的高熵假板钛矿钛酸盐会发生分解。此外，对比例2制备的(Mg0.55Co0.1Ni0.1Al0.4Ga0.1)Ti1.75O5的热导率为1.72 W·m-1·K-1，远高于实施例1和实施例2制备出的高熵假板钛矿钛酸盐陶瓷的热导率。
以上所述的仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。
Claims (5)
1.一种假板钛矿钛酸盐陶瓷的制备方法，其特征在于，包括下述步骤：
（1）按照化学式(α0.75β0.5)Ti1.75O5称取相应的二价金属氧化物混合粉体αO、三价金属氧化物混合粉体β2O3和TiO2粉末，随后球磨混合均匀得到初始混合粉末；所述的二价金属氧化物混合粉体αO是MgO、CoO、NiO、CuO、ZnO中的任意三种，且称取的三者粉体的摩尔数相同；所述的三价金属氧化物混合粉体β2O3是Al2O3、Fe2O3、Ga2O3中的任意两种，且称取的两者粉体的摩尔数相同；
（2）在初始混合粉末中，加入质量浓度4wt%~10wt%的PVA溶液作为粘结剂进行造粒，获得二次混合粉末；所述初始混合粉末、加入的PVA溶液的质量比为15：(1~4)；
（3）将二次混合粉末进行干压成型，得到坯体；
（4）将坯体进行烧结，获得假板钛矿钛酸盐陶瓷。
2.根据权利要求1所述的制备方法，其特征在于，所述初始混合粉末、加入的PVA溶液的质量比为15：(1~2)。
3.根据权利要求1所述的制备方法，其特征在于，所述PVA溶液的质量浓度为6wt%~8wt%。
4.根据权利要求1所述的制备方法，其特征在于，所述的干压成型的压力为100~200MPa。
5.根据权利要求1所述的制备方法，其特征在于，所述的烧结具体为：先以1~2℃/min的速度升温至650℃并保温1~4h，而后以5~10℃/min的速度升温至1300~1400℃，保温2~6h。
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