CN101087732A - 二氧化锆和锆混合氧化物的分散液 - Google Patents

二氧化锆和锆混合氧化物的分散液 Download PDF

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CN101087732A
CN101087732A CNA2005800443348A CN200580044334A CN101087732A CN 101087732 A CN101087732 A CN 101087732A CN A2005800443348 A CNA2005800443348 A CN A2005800443348A CN 200580044334 A CN200580044334 A CN 200580044334A CN 101087732 A CN101087732 A CN 101087732A
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dispersion liquid
zirconium dioxide
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dispersion
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M·奥斯瓦尔德
C·基斯纳
W·洛茨
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Evonik Operations GmbH
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Degussa GmbH
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Abstract

二氧化锆分散液，其固体含量基于分散液的总量为30－75重量％，并且分散液中粒径分布的中值小于200nm，该分散液可以通过如下方法来制得：在基于分散液的总量为0.1－5重量％的表面改性剂的存在下，用小于200KJ/m3的能量输入，在分散剂中预分散二氧化锆粉末和/或ZrO2含量至少为70重量％的锆混合氧化物粉末，该粉末是聚集的初级颗粒形式并且没有内表面且粉末的BET表面积为60±15m2/g；将所得预分散液分成至少两部分液流；在至少500巴的压力下将这些部分液流置于高能磨中并且借助喷嘴使其减压，这些部分液流在填充有气体或液体的反应室中彼此碰撞而被研磨；以及任选地随后用其它的分散剂将分散液调至所需含量。它可以用于陶瓷层、膜和成型物品的生产。

Description

二氧化锆和锆混合氧化物的分散液
本发明涉及二氧化锆的分散液及其制备和用途。
二氧化锆分散液是制备陶瓷模具、涂层及抛光玻璃和金属表面的理想原材料。
分散液所基于的二氧化锆粉末通常是由溶胶/凝胶法或者火焰热解法制成的。
由溶胶/凝胶法制成的粉末通常聚集或团聚程度低，并且BET表面积较低，大约10-30m2/g。在分散液中，常常通过加入添加剂的方法使其稳定，避免再聚合或再团聚。这些添加剂与二氧化锆颗粒表面上的分子基团发生反应。
由火焰热解法制成的粉末通常是聚集形式的。这些粉末制成的分散液通常不是非常稳定。如果发生快速沉积、结块和增稠，一般是不可能再发生重新分散的。如果使用具有高BET表面积的由火焰热解制成的粉末，这种效应就会加强。另外，这些分散液表现出高的粘度，因此对于希望分散液同时具有高填充度和可倾倒性的应用场合是不太合适的。
然而，把伴随火焰热解法制成的二氧化锆粉末颗粒的特定聚集结构的性质利用起来是很理想的，比如用于表面抛光或者陶瓷层的制备。
本发明的目的是提供一种具有高填充度的稳定的、低粘度的、非常细分散的二氧化锆分散液。本发明的目的还在于进一步提供这种分散液的制备方法。
本发明提供一种二氧化锆分散液，其固体含量为分散液总重量的30-75％，且分散液中粒径分布的中值小于200nm，该分散液可以通过如下方法来获得：在基于分散液的总量为0.1-5重量％的表面改性剂的存在下，用小于200KJ/m3的能量输入，在分散剂中预分散二氧化锆粉末和/或ZrO2含量至少为70重量％的锆混合氧化物粉末，该粉末为聚集的初级颗粒形式并且没有内表面，粉末的BET表面积为60±15m2/g；将所得预分散液分成至少两部分液流；在至少500巴的压力下将这部分液流置于高能磨中并且借助喷嘴使其减压，这些部分液流在填充有气体或液体的反应室中彼此碰撞而被研磨；以及任选地随后用其它的分散剂将分散液调至所需含量。
此处，可以优选地使用由火焰热解制备的粉末。
在本文中，火焰热解应理解为意指粉末已由火焰水解或者火焰氧化制得。火焰水解应理解为指例如通过在氢/氧焰中燃烧四氯化锆来形成二氧化锆。火焰氧化应理解为指例如通过在氢/氧焰中燃烧二氧化锆有机前体来形成二氧化锆。
中值应理解为指体积权重(volume-weighted)的粒径分布的d50值。根据本发明的分散液中粒径分布的中值小于200nm。在本文中，颗粒应理解为指例如分散液中存在的初级颗粒、聚集体和团块。d50值可以优选地介于70和200nm之间。
在本发明上下文中，被表面改性应理解为指粉末表面上的至少一部份羟基已经与表面改性剂反应，形成化学键。化学键优选地为表面改性剂和颗粒之间的共价键、离子键或者配位键，以及氢桥键。配位键应理解为指形成了配合物。因此，在改性剂的官能团和颗粒之间可能发生例如布朗司特(Bronsted)或路易斯酸(Lewis)/碱反应形成配合物或者改性剂的官能团与颗粒发生酯化。改性剂包含的官能团优选地为羧酸基、酰氯基、酯基、腈和异腈基、OH基、SH基、环氧基、酸酐基、酰胺基、伯、仲和叔氨基、Si-OH基、硅烷的可水解基团或者C-H酸基，如在β-二羰基化合物中。表面改性剂还可以包含一个以上的这种官能团，如在甜菜碱、氨基酸和EDTA中。适当的表面改性剂可以是：
具有1-24个碳原子的饱和或不饱和的单-和多羧基酸，例如甲酸、乙酸、丙酸、丁酸、戊酸、己酸、丙烯酸、甲基丙烯酸、巴豆酸、柠檬酸、己二酸、琥珀酸、戊二酸、草酸、马来酸、富马酸、衣康酸和硬脂酸，以及相应的酸酐、氯化物、酯和酰胺以及它们的盐，特别是它们的铵盐。那些碳链被O、S或NH基团间隔的化合物，例如醚-羧酸(单和聚醚羧酸以及相应的酸酐、氯化物、酯和酰胺)、氧羧酸如3，6-二氧庚酸和3，6，9-三氧癸酸也是合适的。
通式为Q3-nNHn的单-和聚胺，其中n＝0，1或2，并且基团Q各自独立地为C1-C12-烷基，特别是C1-C6-烷基和特别优选地C1-C4-烷基，例如甲基、乙基、正丙基和异丙基及丁基。此外还可以是具有6-24个碳原子的芳基、烷芳基或者芳烷基，例如苯基、萘基、甲苯基和苄基。
此外，通式为Y2N(-Z-NY)y-Y的聚亚烷基胺，其中Y与Q或N无关，其中Q如上文定义，y是介于1-6，优选地为1-3的整数，Z是具有1-4个，优选2或3个碳原子的亚烷基。实例有甲胺、二甲胺、三甲胺、乙胺、苯胺、N-甲基苯胺、二苯胺、三苯胺、甲苯胺、乙二胺和二亚乙基三胺。
优选具有4-12个，特别是5-8个碳原子的β-二羰基化合物，例如乙酰丙酮、2，4-已二酮、3，5-庚二酮、乙酰乙酸、乙酰乙酸C1-C4-烷基酯，如乙酰乙酸乙酯、双乙酰和丙酮基丙酮。
氨基酸，例如β-丙氨酸、甘氨酸、缬氨酸、氨基己酸、亮氨酸和异亮氨酸。
包含至少一个不可水解的基团或羟基的硅烷，特别是还包含至少一个不可水解的基团的可水解的有机硅烷。通式为RaSiX4-a的硅烷可以优选地用作表面改性剂，其中基团R是相同或不同的，代表不可水解的基团，基团X是相同或不同的并且表示可水解基团或羟基，a等于1、2或3。a值优选为1。
在该通式中，可以彼此相同或不同的可水解的基团X例如是氢或卤素(F，Cl，Br或I)、烷氧基(优选C1-C6-烷氧基，如甲氧基、乙氧基、正丙氧基、异丙氧基和丁氧基)、芳氧基(优选C6-C10-烷氧基，如苯氧基)、酰氧基(优选C1-C6-酰氧基，如乙酰氧基或丙酰氧基)、烷基羰基(优选C2-C7-烷基羰基如乙酰基)、氨基、优选具有1-12，特别是1-6个碳原子的单烷基氨或二烷基氨。优选的可水解基团是卤素、烷氧基和酰氧基。特别优选的可水解基团是C1-C4-烷氧基，特别是甲氧基和乙氧基)。
可以彼此相同或不同的不可水解的基团R可以是具有或不具有官能团的不可水解的基团R。
不具有官能团的不可水解的基团R，例如有烷基(优选C1-C8-烷基如甲基、乙基、正丙基、异丙基、正丁基、仲丁基和叔丁基、戊基、己基、辛基或者环己基)、烯基(优选C2-C6-烯基如乙烯基、1-丙烯基、2-丙烯基和丁烯基)、炔基(优选C2-C6-炔基，例如乙炔基和丙炔基)、芳基(优选C6-C10-炔基如苯基和萘基)以及相应的烷芳基和芳烷基(例如甲苯基、苄基和苯乙基)。基团R和X可以任选地包含一个或更多个常规的取代基，例如卤素或烷氧基。优选的为烷基三烷氧基硅烷。实例有CH3SiCl3、CH3Si(OC2H5)3、CH3Si(OCH3)3、C2H5SiCl3、C2H5Si(OC2H5)3、C2H5Si(OCH3)3、C3H7Si(OC2H5)3、(C2H5O)3SiC3H6Cl、(CH3)2SiCl2、(CH3)2Si(OC2H5)2、(CH3)2Si(OH)2、C6H5Si(OCH3)3、C6H5Si(OC2H5)3、 C6H5CH2CH2Si(OCH3)3、(C6H5)2SiCl2、(C6H5)2Si(OC2H5)2、(i-C3H7)3SiOH、CH2＝CHSi(OOCCH3)3、CH2＝CHSiCl3、CH2＝CH-Si(OC2H5)3、CH2＝CHSi(OC2H5)3、CH2＝CH-Si(OC2H4OCH3)3、CH2＝CH-CH2-Si(OC2H5)3、CH2＝CH-CH2-Si(OC2H5)3、CH2＝CH-CH2Si(OOOCH3)3、n-C6H13-CH2-CH2-Si(OC2H5)3和n-C8H17-CH2CH2-Si(OC2H5)3。
具有一个官能团的不可水解的基团R包括例如环氧化物(例如缩水甘油基或缩水甘油氧基)、羟基、醚、氨基、单烷基氨基、二烷基氨基、任选取代的苯氧基、酰胺、羧基、酰基、酰氧基、甲基丙烯酰基、甲基丙烯酰氧基、巯基、氰基、烷氧基、异氰酸基、醛、烷基羰基、酸酐和磷酸基作为官能团。这些官能团借助可以间隔有氧或NH-基团的亚烷基、亚烯基或亚芳基桥基与硅原子结合。所述桥基优选包含1-18，优选1-8并且特别是1-6个碳原子。
所提到的二价桥基和任选存在的如在烷氨基的情况中的取代基源于例如上述单价烷基、烯基、芳基、烷芳基或芳烷基基团。基团R当然还可以包含一个以上官能团。
具有官能团的不可水解的基团R的优选实例为缩水甘油基或缩水甘油氧基-(C1-C20)-烯烃基，例如β-缩水甘油氧乙基、γ-缩水甘油氧丙基、δ-缩水甘油氧丁基、ε-缩水甘油氧戊基、ω-缩水甘油氧己基和2-(3，4-环氧不已基)已基；(甲基)丙烯酰氧-(C1-C6)-亚烷基基团，例如(甲基)丙烯酰氧甲基、(甲基)丙烯酰氧乙基、(甲基)丙烯酰氧丙基或(甲基)丙烯酰氧丁基；以及3-异氰酸丙基。
相应硅烷的实例有γ-缩水甘油氧丙基三甲氧基硅烷(GPTS)、γ-缩水甘油氧丙基三乙氧基硅烷(GPTES)、3-异氰酸丙基三乙氧基硅烷、3-异氰酸丙基二甲基氯硅烷、3-氨基丙基三甲氧基硅烷(APTS)、3-氨基丙基三乙氧基硅烷(APTES)、N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷、N-[N′-(2′-氨基乙基)-2-氨基乙基]-3-氨基丙基三甲氧基硅烷、羟基甲基三乙氧基硅烷、2-[甲氧基(多亚乙基氧基)丙基]三甲氧基硅烷、双(羟乙基)-3-氨基丙基三乙氧基硅烷、N-羟乙基-N-甲基氨基丙基三甲氧基硅烷、3-(甲基)丙烯酰氧丙基三乙氧基硅烷和3-(甲基)丙烯酰氧丙基三甲氧基硅烷。
用3-氨基丙基三乙氧基硅烷(AMEO)、多羧基酸的铵盐如DolapixCE64(Zschimmer & Schwarz)、或者四烷基氢氧化铵如四甲基氢氧化铵或四乙基氢氧化铵对在根据本发明的分散液中存在的二氧化锆粉末或锆混合氧化物粉末进行表面改性是特别有利的。还可以使用上述化合物的混合物。
根据本发明的分散液的适当的分散剂是水和/或有机溶剂，例如具有1-8个碳原子的醇，特别是甲醇、乙醇、正丙醇和异丙醇、丁醇、辛醇、环己醇；具有1-8个碳原子的酮，特别是丙酮、丁酮和环己酮；酯，特别是乙酸乙酯和乙二醇酯；醚，特别是二乙醚、二丁醚、苯甲醚二噁烷、四氢呋喃和四氢吡喃、二醇醚，特别是单、二、三和聚二醇醚；二醇，特别是乙二醇、二甘醇和丙二醇；酰胺和其它氮化合物，特别是二甲基乙酰胺、二甲基甲酰胺、吡啶、N-甲基吡咯烷和乙腈、亚砜和砜，特别是环丁砜和二甲亚砜、硝基化合物如硝基苯、卤代烃，特别是二氯甲烷、氯仿、四氯化碳、三和四氯乙烯和二氯乙烯、氯氟碳化合物、具有5-15个碳原子的脂肪烃、脂环烃或芳香烃，特别是戊烷、己烷、庚烷和辛烷、环己烷、汽油、石油醚、甲基环已烷、十氢化萘、苯、甲苯和二甲苯。特别优选的有机分散剂是乙醇、正和异丙醇、乙二醇、己烷、庚烷、甲苯和邻-、间-和对-二甲苯。
上述化合物的混合物也可以用作分散剂，在此情况下它们必须是可溶的并且只形成单一相。
水是特别优选的分散剂。
ZrO2含量至少为70重量％的锆混合氧化物粉末应理解为指还包含至少一种其它金属氧化物作为混合氧化物组分的粉末。它可以优选是钇和/或铪。二氧化铪的含量可以优选为1-4重量％，氧化钇的含量可以优选是2-30重量％，在每种情况中均基于粉末的总重量。3-15重量％含量的钇是特别优选的。
例如，可以优选地使用具有下面特征的锆混合氧化物粉末：
-平均初级粒径：＜20nm，优选10-16nm，特别优选12-14nm，
-聚集体参数：平均面积＜10,000nm2，优选5,000-8,000nm2，平均等效直径＜100nm，优选50-90nm，聚集体平均周长＜700nm，优选450-600nm，
-二氧化锆(ZrO2)含量95-99.9重量％，优选＞97重量％，二氧化铪(HfO2)含量0.1-4重量％，优选1-2.5重量％，碳0-0.15重量％，氯0-0.05重量％，在每种情况中都基于粉末的总重量。
聚集体平均最大直径优选小于150nm，特别优选100-150nm，并且平均聚集体最小直径小于100nm，特别优选60-90nm。
在X-射线衍射分析中，粉末优选只表现出单斜和四方相的二氧化锆。优选地，四方相的含量为20％-70％，并且30％-50％的四方相含量是特别优选的。粉末没有内表面。
夯实密度优选为100±20g/l，干燥损失不大于2.0重量％，烧失量不大于3.0重量％，并且在4％浓度的水分散液中测量的pH优选为4.0-6.0。
它可以由如下方法获得：
-雾化包含用于制备锆/铪混合氧化物粉末的原材料的溶液，该溶液通过混合如下成分获得
-一种在有机溶剂或有机溶剂混合物中至少包含羧酸锆、羧酸铪和/或具有锆和铪成分的羧酸盐的溶液
-一种在有机溶剂或有机溶剂混合物中至少包含锆醇盐、铪醇盐和/或具有锆和铪成分的醇盐的溶液
并且其中原料混合物的比例与后面所需的二氧化锆和二氧化铪的比例相对应，并且其中羧酸盐/醇盐的重量比为30∶70-90∶10，
-通过雾化气体形成气溶胶，
-在从燃料气，优选氢气和空气(初级空气)产生的火焰中燃烧所述气溶胶，进入反应室并且还向反应室中引入空气(次级空气)，从而
-λa1，定义为所用总空气中存在的氧气/燃料气燃烧需要的氧气的比例，为1.5-4，且
-λa2，定义为所用总空气中存在的氧气/原材料和燃料气燃烧需要的氧气的比例，大于1或等于1，并且λa1＞λa2，
-原材料在火焰中的停留时间为5-30毫秒，
-冷却热的气体和固体产物并随后从气体中分离固体产物。
可以优选使用的醇盐是乙醇锆(IV)、正丙醇锆(IV)、正丙醇锆(IV)、异丙醇锆(IV)、正丁醇锆(IV)、叔丁醇锆(IV)、乙醇铪(IV)、正丙醇铪(IV)、正丙醇铪(IV)、异丙醇铪(IV)、正丁醇铪(IV)和/或叔丁醇铪(IV)。
包含锆和铪成分的醇盐是特别优选的。
可以优选使用的羧酸盐是乙酸锆、丙酸锆、草酸锆、辛酸锆、2-乙基-己酸锆、癸酸锆和/或硬脂酸锆、乙酸铪、丙酸铪、草酸铪、辛酸铪、2-乙基-己酸铪和/或硬脂酸铪。
包含锆和铪成分的羧酸盐是特别优选的。
锆化合物中通常包含1-5重量％的铪化合物。但是，也可以以99重量％或更高的纯度制备锆化合物和铪化合物。通过任意组合所需原料化合物的铪含量，来达到所需的0.01-4重量％之间的二氧化铪含量。
可以优选地使用甲醇、乙醇、正丙醇、异丙醇、正丁醇、叔丁醇、2-丙酮、2-丁酮、二乙醚、叔丁基甲醚、四氢呋喃、C1-C8-羧酸、乙酸乙酯、甲苯和/或汽油作为有机溶剂或者作为有机溶剂混合物的组分。
在特别优选的实施方案中，包含羧酸锆和/或羧酸铪的溶液同时包含该羧酸盐所基于的羧酸，包含锆醇盐和/或铪醇盐的溶液同时包含该醇盐所基于的醇。
再优选的锆混合氧化物粉末具有以下特征：
它是具有下面物理化学参数的聚集的初级颗粒形式：
-以氧化钇Y2O3计算，由化学分析确定的钇含量占混合氧化物粉末总重量的5-15％，
-以氧化钇Y2O3计算，由TEM-EDX确定的单个初级颗粒的钇含量相当于粉末中的含量±10％，
-室温下，单斜二氧化锆的含量由X-射线衍射确定并且基于混合氧化物粉末为＜1-10重量％，
-含碳量小于0.2重量％。
它可以通过以下方法制得：混合有机二氧化锆前体和无机氧化钇前体，每种前体以相应于后面所需锆和钇的比例溶解在一种有机溶剂或混合有机溶剂中，由空气(雾化空气)或惰性气体雾化该溶液混合物，并且使其与燃料气和空气(初级空气)混合并且在火焰中燃烧混合物进入反应室中。冷却热气体和固体产物并随后把固体产物从气体中分离出来。此处，溶液中二氧化锆前体的含量(以ZrO2计)为至少15重量％并不大于35％。另外，向反应室中引入空气(次级空气)或者惰性气体(每种气体的用量相应于初级空气量的50％-150％)，定义为λ的所用空气中存在的氧气/燃料气燃烧所需的氧气的比例是2-4.5，前体在火焰中的停留时间为5-30毫秒，并且前体溶液在燃料气由空气燃烧后得到的气体量中的含量为0.003-0.006体积％。适当的有机二氧化锆前体是乙醇锆(IV)、正丙醇锆(IV)、正丙醇锆(IV)、异丙醇锆(IV)、正丁醇锆(IV)、叔丁醇锆(IV)和/或2-乙基己酸锆(IV)。适当的无机氧化钇前体是硝酸钇、碳酸钇和/或硫酸钇。
在申请号为DE 102004039139.4且申请日为2004年8月12日的德国专利申请中描述了锆混合氧化物粉末及其制备方法。以参考的形式引入该申请的全部内容。
二氧化锆含量至少为92重量％、氧化钇含量为4.5-5.5重量％并且氯化物含量不大于0.05重量％的二氧化锆粉末是特别优选的。
根据本发明的分散液中存在的粉末没有内表面。通过高分辨TEM获得粉末照片是用于此目的的适当分析方法。
根据本发明的分散液中存在的粉末的BET表面积为60±15m2/g，介于60±5m2/g之间的值是优选的。
此外，基于分散液的总量，根据本发明的分散液中的二氧化锆粉末或锆混合氧化物粉末的含量优选的为50±5重量％。
根据本发明的分散液对沉积、结块和增稠具有优异的稳定性。室温下至少1个月内，通常至少6个月内具有可流动性，而不需事先再分散。
在温度为23℃和剪切梯度为1-1,000s-1的条件下，根据本发明的分散液具有小于1,000mPas，并且特别优选地小于100mPas的粘度。
根据本发明的分散液可以优选是单峰(monomodal)形式的，这意指聚集体直径的分布函数只表现出一个信号。图1显示了根据本发明的分散液(实施例D-2)。
本发明还提供了根据本发明的分散液的制备方法，
-首先用小于200kJ/m3的能量输入在分散条件下，一次全部或者分批地将二氧化锆粉末和/或ZrO2含量至少为70重量％的锆混合氧化物粉末(该粉末是BET表面积为60±15m2/g的聚集的初级颗粒)加入到分散剂(优选为水)中，所述分散剂包含至少一种在该分散剂中可溶的表面改性剂以及任选的用于pH调节的添加剂，
-选择粉末的量，使得粉末含量为30-75重量％，并且选择表面改性剂的量，使得表面改性剂的含量为0.1-5重量％，每种情况均基于预分散液的总量，
-将预分散液分成至少两部分液流，在至少500巴，优选500-1,500巴，特别优选2,000-3,000巴的压力下将这些部分液流置于高能磨中，借助喷嘴使其下行，并且使它们在填充有气体或液体的反应室中彼此碰撞而研磨它们；以及任选地随后用其它的分散剂将分散液调节至所需含量。
可以实施根据本发明的方法，以循环已经研磨过的分散液，并借助高能磨将其再研磨2-6次，从而可以获得具有更小粒径和/或不同分布，例如单峰(monomodal)或双峰(bimodal)的分散液。
此外，优选实施根据本发明的方法，以使高能磨中的压力为2,000-3,000巴。在此措施下，也可以获得具有更小粒径和/或不同分布，例如单峰或双峰的分散液。
此外，优选实施根据本发明的方法，以使(预)分散液的制备期间的最大温度不超过40℃。
根据本发明的分散液可以用来制备陶瓷层、陶瓷膜和成型物品。用于此目的的适当方法是熟悉本领域的技术人员公知的，并且可以提到的实例有凝胶浇铸、冷冻浇铸、粉浆浇铸、真空热浇注、单轴向干压和冷等压再压。此外，根据本发明的分散液可以用于抛光玻璃表面和金属表面。
实施例
分析：
中值由动态光散射法测定。所用仪器：Horiba LB-500
分散液的粘度由Brookfield旋转粘度计在23℃下作为剪切梯度的函数确定。
BET表面积根据DIN 66131确定。
粉末：
粉末P1：在50℃的温度下以90∶10的比例混合溶液1和溶液2。通过一个0.8mm直径的喷嘴，用5Nm3/h的空气雾化1,500g/h所得的均匀溶液。
表1：用于制备锆/铪混合氧化物粉末的溶液
溶液 1 2 3
辛酸锆(以ZrO2计) 24.40 - -
辛酸铪(以HfO2计) 0.30 - -
正丙酸锆(以ZrO2计) - 27.80 -
正丙酸铪(以HfO2计) - 0.50 -
硝酸钇Y(NO3)3·4H2O - - 30.7
辛酸 39.60 - -
正丙醇 - 30.50 -
四正丙醇 - 41.20 -
2-(2-丁氧基乙氧基)乙醇 3.50 - -
石油溶剂油 32.20 - -
丙酮 - - 69.3
表2：P1的物理化学性质
ZrO2的含量   重量％     98.72
HfO2的含量   重量％     1.28
氯化物的含量   ppm     330
BET表面积   m2/g     63
初级颗粒的平均   nm     13
聚集体参数
平均周长   nm     494
平均面积   nm2     5228
平均ECD   nm     66
平均最大直径   nm     112
平均最小直径   nm     69
ZrO2单斜/四方(XRD)     64/36
夯实密度   g/l     95
干燥损失   重量％     1.03
烧失量   重量％     2.08
PH     5.32
将所形成的气溶胶转移入从氢气(5.0Nm3/h)和初级空气(10Nm3/h)形成的火焰中并且燃烧进反应室中。
另外，向该反应室中引入20Nm3/h(次级)空气。然后，在冷却区中冷却热气体和固体产物。制得的锆/铪混合氧化物粉末沉积在过滤器中。
粉束P2：
所用的前体溶液：将312g/h(基于二氧化锆)用量的溶液1和7.0g/h(基于氧化钇)用量的溶液3混合。混合物保持稳定，没有沉淀形成。
然后，用空气(3.5Nm3/h)雾化该混合物(总量为1,300g/h，包括溶剂)。所得的液滴具有5-15μm的滴径光谱d50。液滴在由氢气(1.5Nm3/h)和初级空气(12.0Nm3/h)形成的火焰中燃烧，进入反应室中。另外，再向该反应室中引入15.0Nm3/h(次级)的空气。然后，在冷却区中冷却热气体和固体产物。制得的钇稳定的二氧化锆沉积在过滤器中。
表3：P2的物理化学性质
BET表面积 m2/g     47
初级颗粒的 nm     13.7
平均聚集体直径 nm     111
粉末中ZrO2的含量 重量％     94.6
粉末中Y2O3的含量 重量％     5.4
初级颗粒中Y2O3的含量(TEM/XRD) 重量％     5.2±0.4
ZrO2单斜/四方(XRD) ％     7/93
氯化物含量 重量％     ＜0.05
碳含量 ppm     0.12
分散液
实施例D1(预分散液，比较实施例)：首先向制备罐中加入42.14kg完全软化的水和1.75kg Dolapix CE64(Zschimmer und Schwarz)，然后在Ystral Conti-TDS 3(定子狭缝：4mm环和1mm环，转子/定子距离大约1mm)的吸管的辅助下于剪切条件下加入43.9kg粉末P1。当抽吸结束时，关闭抽吸连接并且使分散液再于3,000rpm下剪切10min。如此获得的(预)分散液的锆混合氧化物粉末含量为50重量％，中值为614nm。它在1个月内沉降。
实施例D2(根据本发明)：用0.3mm直径的金刚石喷嘴，在2,500巴的压力下将该预分散液填入Sugino Ultimaizer HJP-25050高能磨中5次进行研磨。如此获得的分散液的中值为112nm，在100s-1下粘度为27mPas。它至少在6个月内对沉降、结块和增稠是稳定的。
D2的单轴向制备的压缩体(200和300MPa)的烧结在大约1,000℃的温度下已经开始，并且在1,300℃下达到97％的理论密度。
实施例D3(根据本发明)：与实施例D1类似，首先制备预分散液，但是使用0.88kg四甲基氢氧化铵溶液(25重量％的水溶液)而不是Dolapix CE64。然后，与实施例D2类似制备根据本发明的分散液。它的锆混合氧化物粉末含量为50.5重量％，中值为117nm，在1,000s-1下粘度为32mPas。它至少在6个月内对沉降、结块和增稠是稳定的。
实施例D4(根据本发明)：与实施例D1类似，首先制备预分散液，但是使用粉末P2。然后，与实施例D2类似制备根据本发明的分散液。它的锆混合氧化物粉末含量为50重量％，中值为99nm，在1,000s-1下粘度为27mPas。它至少在6个月内对沉降、结块和增稠是稳定的。
实施例D5(比较实施例)：与实施例1类似，试图不使用表面改性剂来制备预分散液。但是，所能实现的最大填充度仅为15重量％。

Claims (15)

1.二氧化锆分散液，其固体含量为分散液总量的30-75重量％，并且分散液中粒径分布的中值小于200nm，该分散液可以通过如下方法来获得：在基于分散液的总量为0.1-5重量％的表面改性剂的存在下，用小于200KJ/m3的能量输入，在分散剂中预分散二氧化锆粉末和/或ZrO2含量至少为70重量％的锆混合氧化物粉末，该粉末为聚集的初级颗粒形式并且没有内表面，粉末的BET表面积为60±15m2/g；将所得预分散液分成至少两部分液流；在至少500巴的压力下将这部分液流置于高能磨中并且借助喷嘴使其减压，这些部分液流在填充有气体或液体的反应室中彼此碰撞而被研磨；以及任选地随后用其它的分散剂将分散液调至所需含量。
2.根据权利要求1的二氧化锆分散液，其特征在于所述表面改性剂是3-氨基丙基三乙氧基硅烷、多羧基酸的铵盐和/或四烷基氢氧化铵。
3.根据权利要求1或2的二氧化锆分散液，其特征在于所述分散剂是水。
4.根据权利要求1-3的二氧化锆分散液，其特征在于所述粉末含有至少95重量％的二氧化锆、0.5-4重量％的二氧化铪和不超过0.05重量％的氯化物。
5.根据权利要求1-4的二氧化锆分散液，其特征在于所述粉末含有至少92重量％的二氧化锆、4.5-5.5重量％的氧化钇和不超过0.05重量％的氯化物。
6.根据权利要求4或5的二氧化锆分散液，其特征在于所述BET表面积为60±5m2/g。
7.根据权利要求4-6的二氧化锆分散液，其特征在于所述粉末具有100±20g/l的夯实密度。
8.根据权利要求1-7的二氧化锆分散液，其特征在于所述固体含量为50±5重量％。
9.根据权利要求1-8的二氧化锆分散液，其特征在于在1-1,000s-1的剪切梯度范围内且23℃下，其粘度小于1,000mPas。
10.根据权利要求1-9的二氧化锆分散液，其特征在于它是双峰分布的。
11.根据权利要求1-10的二氧化锆分散液的制备方法，其特征在于：
-首先用小于200kJ/m3的能量输入在分散条件下，一次全部或者分批地将二氧化锆粉末和/或ZrO2含量至少为70重量％的锆混合氧化物粉末加入到分散剂中，所述粉末是BET表面积为60±15m2/g的聚集的初级颗粒的形式，所述分散剂优选为水并且包含至少一种在该分散剂中可溶的表面改性剂以及任选地用于pH调节的添加剂，并且如此制备预分散液，选择粉末用量，使得固体含量为30-75重量％，并且选择表面改性剂用量，使得表面改性剂的含量为0.1-5重量％，每种情况均基于预分散液的总量，
-将预分散液分成至少两部分液流，在至少500巴的压力下将这些部分液流置于高能磨中，借助喷嘴减压并且使它们在填充有气体或液体的反应室中彼此碰撞而被研磨；以及任选地随后用其它的分散剂将分散液调至所需含量。
12.根据权利要求11的方法，其特征在于循环已经被研磨过的分散液，并借助高能磨将其再研磨2-6次。
13.根据权利要求11或12的方法，其特征在于所述高能磨中的压力为2,000-3,000巴。
14.根据权利要求11-13的分散液，其特征在于预分散液制备期间的最高温度为40℃。
15.根据权利要求1-10的二氧化锆分散液用于制备陶瓷层、陶瓷膜和陶瓷型制品以及用于抛光玻璃表面和金属表面的用途。
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TWI499609B (zh) * 2010-05-10 2015-09-11 School Corp Kansai Univ 硬化性組成物、使用該硬化性組成物之環氧樹脂－無機聚合物複合材料的製造方法及環氧樹脂－無機聚合物複合材料
CN105712399A (zh) * 2016-01-20 2016-06-29 淄博晶泽光学材料科技有限公司 一种二氧化锆抛光粉的制备方法

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