CN101258264A - 以超微粒金属氧化粒子涂布于金属氧化物表面的方法及其结构 - Google Patents

以超微粒金属氧化粒子涂布于金属氧化物表面的方法及其结构 Download PDF

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CN101258264A
CN101258264A CNA2006800328927A CN200680032892A CN101258264A CN 101258264 A CN101258264 A CN 101258264A CN A2006800328927 A CNA2006800328927 A CN A2006800328927A CN 200680032892 A CN200680032892 A CN 200680032892A CN 101258264 A CN101258264 A CN 101258264A
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metal oxide
metal
coating
superfine
oxide particles
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CN101258264B (zh
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明岏在
李周衡
宋圭镐
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Hanwha TotalEnergies Petrochemical Co Ltd
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    • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]

Abstract

本发明涉及一种以超微粒金属氧化粒子涂布于金属氧化物表面的方法及其结构，特别是一种利用超微粒金属氧化粒子涂布于金属氧化物表面的方法，此方法包含i)以涂布方式使一金属(M2)盐类水溶液作用于金属(M1)氧化物上，以及ii)连续地将水与所述金属氧化物混合及反应于反应温度范围介于200℃～700℃及反应压力范围介于180巴(bar)～550巴(bar)。

Description

以超微粒金属氧化粒子涂布于金属氧化物表面的方法及其结构
技术领域
本发明是有关于一种以超细微金属氧化粒子涂布于金属氧化物表面的方法及其结构，特别是一种以超微粒金属氧化粒子涂布于金属氧化物表面的方法，与习知的以超细微金属氧化物粒子涂布于金属氧化物的方法及其结构相比，本发明所涂布的粒子是纳米尺寸的超细微粒子。
背景技术
本发明涉及提供一种以超细微金属氧化粒子涂布于金属氧化物表面的方法及其结构。
本发明的方法所制备的涂布层举例来说，包含i)将氧化锆(ZrO2)涂布于氧化钸(CeO2)上，对于毒性物质如含硫物有高的抗性，因此适合用来作为净化柴油运输工具排放气体的触媒，ii)阴极活性材料，如将氧化锆(ZrO2)涂布于锂钴氧化物(LiCoO2)上，具有改善热稳定性及再生性的作用，因此作为锂离子二次电池的阴极活性材料是相当有帮助的，iii)将氧化钙(CaO)涂布于氧化钸(CeO2)上，具有使其更白的作用，因此适合用来作为抗紫外线剂，以及iv)将氧化硅(SiO2)涂布于氧化钸(CeO2)上，可改善分散性，因此适合用来作为半导体晶圆化学机械平坦化用的研磨液。
如习知用来将超细微金属氧化粒子涂布于金属氧化物表面的技术，常用于挥发干燥型态的涂布层制程。至于用在净化运输工具排放废气的触媒，贵金属如铂(Pt)、镨(Pd)或铑(Rh)，为了增加反应效能必须在添加油料时加入尽可能少的氧化铝或氧化钸分散于其中。
美国专利号NO.6,787,500接露了一种在真空状态下经由两种或更多前导溶液的蒸发来将氧化铂(PtO2)涂布于氧化钸上。然而此方法因为必须使用到真空装置并不适合用来量产。
此外，美国专利号NO.6,773,814揭露了一种涂布二氧化硅的技术，经由以水溶液的型态混合金属氧化物、四烷氧硅烷与氨水，接着在干燥此混合物以降低金属氧化微粒(粒径尺寸介于0.1μm～1μm)如氧化钛或氧化锌的触媒活性，可用做抗紫外线剂。
Yuan et al.(Z.Yuan et al，Materials Let ters，46(2000)，249～254)在一国际电子期刊中揭露了一种氧化钸涂布于氧化锆上的制备方法，包含将氧化锆微粒、硝酸钸水溶液与乙醇混合，接着在将溶剂蒸发出以制备更稳定的含有氧化钸的氧化锆产物。
发明内容
技术问题
很显然的在习知技术中，要将其它金属氧化物涂布于金属氧化物表面，涂布层主要在低温下形成。因此，所述涂布层，是非晶形金属氢氧化物或非晶形金属氧化物，应该使其高温处理以氧化或结晶。然而，在这样的例子里，经由增加粒子尺寸或毛细孔的融合会使这具体的表面积发生不期望的效应。
因此，本发明最主要且透彻地研究如何将超细微金属氧化粒子涂布于金属氧化物，由发明人发展涂布技术对避免遭遇习知问题的方法，包含使金属盐水溶液与金属氧化物作用，接着将上述混合溶液与次临界水或超临界水混合以造成次临界反应或超临界反应，如此超细微金属氧化粒子将形成于金属氧化物的表面以产生一具核心层及表层的结构。
本发明的一目的是提供一种以超细微金属氧化粒子涂布于金属氧化物表面的方法及其结构。
技术手段
为了完成上述的目的，本发明提供一种涂布方法，包含i)以涂布方式使一金属(M2)盐类水溶液作用于金属(M1)氧化物上，以及ii)连续地将水与所述金属氧化物混合及反应于反应温度范围介于200℃～700℃及反应压力范围介于180巴(bar)～550巴(bar)。
较佳的是，所述方法更包含在步骤i)与步骤ii)中添加一沉淀剂。
较佳的是，所述沉淀剂是氨水。
而金属(M1)氧化物的金属(M1)成分并未特别限制，且较佳可包含至少为周期表内I A族、IB族、IIA族、IIB族、IIIA族、IIIB族、IVA族、IVB族、VA族、VB族、VIA族、VIB族、VIIA族、VIIB族、VIII族、过渡金属、镧系元素或辐射性元素的其中一种。特别的是，本发明所用较佳的金属至少可为硅(Si)、铝(Al)、锂(Li)、镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、铌(Nb)、镧(La)、钛(Ti)、锆(Zr)、铬(Cr)、钼(Mo)、钨(W)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钸(Ce)及镨(Pr)其中之一。
再者，用于涂布的金属盐类的金属(M2)成分并未特别限制，且较佳可包含至少为周期表内IA族、IB族、IIA族、IIB族、IIIA族、IIIB族、IVA族、IVB族、VA族、VB族、VIA族、VIB族、VIIA族、VIIB族、VIII族、过渡金属、镧系元素或辐射性元素的其中一种。特别的是，本发明所用较佳的金属至少可为硅(Si)、铝(Al)、钪(Sc)、镓(Ga)、锂(Li)、镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、铌(Nb)、镧(La)、钛(Ti)、锆(Zr)、铬(Cr)、钼(Mo)、钨(W)、锰(Mn)、铁(Fe)、铷(Ru)、铑(Rh)、钯(Pd)、铱(Ir)、铂(Pt)、钴(Co)、镍(Ni)、铜(Cu)、银(Ag)、锌(Zn)、镉(Cd)、钸(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)及钆(Gd)其中之一。
较佳的是，所述金属(M2)盐类并未特别限制，只要可为水溶液状态并且包含硝酸盐、草酸盐或柠檬酸盐。
较佳的是，当使所述金属(M1)氧化物与含金属(M2)盐类的水溶液作用时，一界面活性剂可选择性的接枝于用于涂布的金属(M1)氧化物及金属(M2)盐类，或解离于水溶液中的金属(M2)离子，举例来说，丙烯酸、羧酸、氨基酸的聚合物、其盐类或其混合物组成的群组，也许更多。特别的是，含水的聚合物盐类是较好的选择。
较佳的是，所述混合程序及反应程序是利用一线性混合机以不断连续的搅拌所达成。
较佳的是，所述方法更包含预先干燥及锻烧。所述的烘干程序可以是常见的烘干程序，举例来说，在温度为300℃或更低时使用喷雾干燥法、对流干燥法或流体化床干燥法。至于需要增加干燥粒子、晶体或烧结物的粒径尺寸、锻烧程序的氧化与还原反应或者在水的存在下，都可以在温度为400℃～1500℃下进行，都视材料的型态而定。就其本身而言，锻烧效应在温度低于400℃时是较不佳的，反而在超过温度1500℃会发生过度烧结作用。
此外，本发明提供了一种利用所述的方法所制成的涂布层，具有由金属氧化物表面所构成的核心层是涂布上超细微金属氧化粒子的，核心层的金属氧化粒子的粒径大小介于5nm～5μm，且所述超细微金属氧化粒子，构成涂布层，具有粒径大小介于1nm～100nm。
可达的有利结果
与习知将超细微金属氧化粒子涂布于金属氧化物的技术相比，本发明所用的材料是较为有帮助的，因为涂布粒子均匀的都是纳米尺寸超细微粒子。既然本发明用来合成金属盐类的材料为纳米尺寸，所述金属盐类即是用以涂布于金属氧化物表面的，在达到超临界或次临界高温或高压后致使其晶核形成于金属氧化粒子表面，因此长成结晶，结晶的合成皆是以纳米尺寸的超细微粒子存在并且被用来形成一具核心层与表层的结构。
附图说明
图1为表示本发明的实施例一所制备的金属氧化微粒扫描电子显微(SEM)图(放大10万倍)；
图2为表示本发明的实施例二所制备的金属氧化粒子扫描电子显微图(放大10万倍)；
图3为表示本发明用来与实施例一的金属氧化粒子扫描电子显微图(放大10万倍)的比较图；图4为表示本发明用来与实施例二的金属氧化粒子扫描电子显微图(放大10万倍)的比较图。
具体实施方式
以下，将提供本发明的详细叙述。根据本发明的目的，反应是在反应温度范围介于200℃～700℃及反应压力范围介于180巴(bar～550巴(ba r)，而较佳的反应温度范围介于300℃～500℃及反应压力范围介于200巴(bar)～400巴(bar)。假如反应温度在低于200℃而反应压力低于180巴(bar)，反应速率则会下降。而氧化物产物的可溶性也会相对的提高而可沉淀回复度也会因此而下降。换句话说，假如这反应温度跟反应压力过高，却又不符合经济效益。所述金属氧化粒子，用以作为本发明的方法制成的涂布核心层，具有粒子尺寸范围介于5nm～5pm，而较佳范围则在10nm～2pm。假如粒子尺寸小于5nm，那么要将超细微粒子涂布上所述金属粒子表面将会变的很困难。反过来说，假如粒子尺寸大于5pm，那么准备仪器的操作将会变的不容易。此外，用以形成核心层的超细微金属氧化粒子具有粒子尺寸范围介于1nm～100nm，而较佳尺寸范围介于2nm～50nm。当粒子尺寸小于1nm时，将会导致过度的凝聚而使得涂布制程变的相当困难。另一方面，当粒子尺寸尺寸大于100nm时，所形成的涂布层将会变的不均匀，而使得涂布技术的获利下降。
本发明的方法所制备的涂布层，举例来说，包含i)将氧化锆(ZrO2)涂布于氧化钸(CeO2)上，对于毒性物质如含硫物有高的抗性，因此适合用来作为净化柴油运输工具排放气体的触媒，ii)阴极活性材料，如将氧化锆(ZrO2)涂布于锂钴氧化物(LiCoO2)上，具有改善热稳定性及再生性的作用，因此作为锂离子二次电池的阴极活性材料是相当有帮助的，iii)将氧化钙(CaO)涂布于氧化钸(CeO2)上，具有使其更白的作用，因此适合用来作为抗紫外线剂，以及iv)将氧化硅(SiO2)涂布于氧化钸(CeO2)上，使其改善分散性，因此适合用来作为半导体晶圆化学机械平坦化用的研磨液。
实施例
以下依本发明的方法为例参照附图详细说明，特举较佳实施例以使便于理解，但并不对本发明的限制。
实施例一
将表面积为24m2/g重为70g的氧化钸(CeO2)粒子(粒径介于20nm～50nm)溶于水中制备成1千克(kg)的浆液，所述浆液接着与65.1克(g)的硝酸锆(ZrO(NO3)2.2H2O)混合。所述混合浆液是以每分钟8克的速率及外径1/4英寸的管子抽取，并加压到250巴。再者，去离子水是以96g/min及外径1/4英寸的管子抽取，并预热到550℃加压至250巴(bar)。结果，在加压状态下，所述经预热的去离子水跟所述混合浆液被抽到一连续连性反应器立即地混合。反应产物温度维持在400℃。反应后所制备的粒子被冷却并分离出来。如此制得的粒子被过滤、在100℃时干燥十小时并利用X-射线荧光光谱仪(X-ray fluorescence spectrometry)、场散射扫描电子显微镜(FESEM，Field Emission Scanning Electron Microscope)及BET表面积分析仪(BETsurface area analyzer)。如X-射线荧光光谱仪分析的成分结果，氧化钸与氧化锆分别是65.7wt％与34.3wt％。此外，如图1的场散射扫描电子显微镜分析结果，氧化锆粒子可以看到良好的分散于氧化钸结晶的表面。而干燥粒子的表面积在经由BET表面积分析仪量测后为83m2/g，此值被认为是相对的高。而核心层的氧化钸粒径大小介于50nm～200nm，而表层的氧化锆粒径大小介于2nm～10nm。
实施例二
将表面积为24m2/g重为70g的氧化钸(CeO2)粒子(粒径介于20nm～50nm)与5.6g的聚合物界面活性剂(Disperbyk 154，购买自BYK Chemie)均匀的混于水中制成1千克的浆液，接着再与65.1g的硝酸锆(ZrO(NO3)2.2H2O)混合而制得一混合浆液。结果，可获得如实施例一所制成的粒子。如此制得的粒子在经过滤，在温度100℃下干燥10小时的后，并利用X-射线荧光光谱仪、场散射扫描电子显微镜及BET表面积分析仪。经X-射线荧光光谱仪分析的成分结果，氧化钸与氧化锆分别是61.2wt％与38.8wt％。此外，如图2的场散射扫描电子显微镜分析结果，氧化锆粒子可以看到良好的分散于氧化钸结晶的表面。而干燥粒子的表面积在经由BET表面积分析仪量测后为89m2/g，此值被认为是相对的高。而核心层的氧化钸粒径大小介于50nm～200nm，而表层的氧化锆粒径大小介于2nm～10nm。
比较实施例一
将表面积为24m2/g重为70g的氧化钸(CeO2)粒子(粒径介于20nm～50nm)溶于水中制备成1千克(kg)的浆液，所述浆液接着与65.1克(g)的硝酸锆(ZrO(NO3)2.2H2O)混合。所述浆液利用喷雾干燥器进行干燥后可得具有微粒的产物。所述微粒在经600℃锻烧6小时后以致于核心层表面的锆化合物氧化成氧化锆。所述经锻烧后的微粒利用X-射线荧光光谱仪、场散射扫描电子显微镜及BET表面积分析仪来做分析测试。经X-射线荧光光谱仪分析的成分结果，氧化钸与氧化锆分别是68.5wt％与31.5wt％。此外，如图3所示的场散射扫描电子显微镜分析结果，氧化锆层被烧结于氧化钸结晶的表面。具体表面积经量测后达到29m2/g，其与提供的氧化钸表面积相似。因此，需要高表面积涂布上这样的涂布层是相当困难的。再者，所述粒子的核心层及表层粒子大小是很难去分析的，这是由于氧化钸表面的氧化锆过度烧结的关。
比较实施例二
将11.18wt％的硝酸钸水溶液以每分钟8克的速率及外径1/4英寸的管子抽取，并加压到250巴。13wt％的氨水(28wt％的氨)以每分钟13克的速率及外径1/4英寸的管子抽取，同样加压到250巴。将所述经加压的硝酸盐水溶液及氨水抽到管状连续线性混合器1立即混合，在使沉淀时间维持20秒。此外，将4.06wt％的硝酸锆水溶液以每分钟8克的速率及外径1/4英寸的管子抽取，并加压到250巴，再抽取到线性混合器2内以便立即混合由线性混合器1的沉淀物，再让沉淀物沉淀约20秒。
此外，去离子水是以每分钟96克及外径1/4英寸的管子抽取，并预热到550℃加压至250巴(bar)。结果，在加压状态下，经预热及由线性混合器2沉淀所制备的所述去离子水被抽取到连续混合反应器以立即混合。所得的反应产物，温度维持在400℃，使其反应时间在10秒或更少。反应后制得的浆液经冷却且将微粒分离出来。所述的分离出的微粒在烤箱中，以100℃干燥后，以X-射线荧光光谱仪、场散射扫描电子显微镜分析及BET表面积分析仪来做分析测试。经X-射线荧光光谱仪分析的成分结果，氧化钸与氧化锆分别是65wt％与35wt％。具体表面积经量测后达到62m2/g。此外，如图4所示的场散射扫描电子显微镜分析结果，可以看见两种金属氧化物包含氧化钸(大的八边形粒子)与氧化锆(球状结块粒子)是混合却是彼此分离的状态。尽管氧化布粒子尺寸经量测后范围在50nm～600nm，但氧化锆粒子尺寸却因过度烧结而难以测量。
实施例三
由实施例一、实施例二与比较实施例二各取一克样品，每组都具有相对性的高表面积因此适合用来做为触媒使用，分别添加到经搅拌76小时的70％硝酸100毫升(ml)室温水溶液中。将所述经搅拌的溶液注入玻璃滤器，所述滤器需先经干燥及秤重。结果如表1。氧化布渐渐溶解于70％的硝酸水溶液中，反而氧化锆却一点也没有溶解于其中。因此，在氧化钸表面不均匀地涂布上氧化锆的例子中，在经过硝酸水溶液处理后，过滤后残余的量增加了，藉由氧化锆的作用防止了核心层的氧化钸与硝酸水溶液接触。在实施例一及实施例二的样品中，较少的氧化钸溶解归功于涂布层氧化锆的保护，因此残余液的总量才会相对的高。然而在比较实施例二的样品中，部分核心层的氧化钸溶解了而残余液的量也较低。
表1
  实施例一   实施例二   比较实施例二
  残余液(克)   0.91   0.93   0.61

Claims (10)

1.一种以超细微金属氧化粒子涂布于金属氧化物表面的方法，包含：
i)以涂布方式使一金属(M2)盐类水溶液作用于金属(M1)氧化物上；以及
ii)连续地将水与所述金属氧化物混合及反应于反应温度范围介于200℃～700℃及反应压力范围介于180巴(bar)～550巴(bar)。
2.根据权利要求1所述的方法，更包含在步骤i)及ii)添加一沉淀剂。
3.根据权利要求2所述的方法，其中所述沉淀剂是氨水。
4.根据权利要求1所述的方法，其中所述金属(M1)氧化物的金属(M1)成分至少可为硅(Si)、铝(Al)、锂(Li)、镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、铌(Nb)、镧(La)、钛(Ti)、锆(Zr)、铬(Cr)、钼(Mo)、钨(W)、锰(Mn)、铁(Fe)、钴(Co)、镍(Ni)、铜(Cu)、锌(Zn)、钸(Ce)及镨(Pr)其中之一。
5.根据权利要求1所述的方法，其中所述金属(M2)盐类的金属(M2)成分至少可为硅(Si)、铝(Al)、钪(Sc)、镓(Ga)、锂(Li)、镁(Mg)、钙(Ca)、锶(Sr)、钡(Ba)、钇(Y)、铌(Nb)、镧(La)、钛(Ti)、锆(Zr)、铬(Cr)、钼(Mo)、钨(W)、锰(Mn)、铁(Fe)、铷(Ru)、铑(Rh)、钯(Pd)、铱(Ir)、铂(Pt)、钴(Co)、镍(Ni)、铜(Cu)、银(Ag)、锌(Zn)、镉(Cd)、钸(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)及钆(Gd)其中之一。
6.根据权利要求1所述的方法，其中所述金属(M2)盐类是硝酸盐、草酸盐或柠檬酸盐。
7.根据权利要求1所述的方法，其中所述步骤i)更包含加入丙烯酸、羧酸、氨基酸的聚合物、其盐类或其混合物组成的群组。
8.根据权利要求1所述的方法，其中步骤ii)可利用一连续线性搅拌机来实现。
9.根据权利要求1所述的方法，更包含预先烘干及锻烧。
10.一种涂布层，是以权利要求1至9的方法形成且具有一核心层及一皮层，分别包含所述金属氧化物及涂布于所述金属氧化物表面的超细微金属氧化粒子，所述核心层的金属氧化物的平均粒径大小介于5nm到5μm，而所述皮层的超细微金属氧化粒子的平均粒径大小介于1nm到100nm。
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