CN101119929A - 用于在热壁反应器中制备球形混合氧化物粉末的方法 - Google Patents
用于在热壁反应器中制备球形混合氧化物粉末的方法 Download PDFInfo
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Abstract
本发明涉及新颖的用于在热壁反应器中制备球形的二元和多元混合氧化物粉末的方法。通过使用具有限定的盐或固体浓度的盐的水溶液或有机溶液或分散体与以表面活性剂和/或具有放热分解反应的无机盐形式的添加剂相结合,可以得到致密的球形颗粒形态,其中其平均颗粒尺寸范围为5nm~<10μm。
Description
本发明涉及新颖的用于在热壁反应器中通过喷雾热解制备球形的二元和多元混合氧化物粉末的方法。
现有技术
气溶胶工艺以及特别是喷雾热解被认为是用于制备高质量和均质多组分粉末的有效方法。
特别地在多元混合氧化物系统中,溶剂蒸发、从这些溶液中分离出的盐的热解和混合氧化物的形成有利地是在由溶液、悬浮液或分散液为原料的单一工艺步骤中实现的。
G.L Messing等在Journal of the American Ceramic Soc.76(1993)11,第2707-2726页中描述了科学和技术基本原理,其中尤其指出形成中空颗粒或壳碎片是该工艺到目前为止没有广泛应用于粉末制备的原因之一。在通常具有较低熔点的廉价的硝酸盐的应用中,新形成的盐颗粒中夹杂的溶剂残留物最终另外会导致不规则形状的多孔氧化物颗粒的形成。
这一缺点通常不能在基于火焰热解的工艺中克服,或者只能通过乳液的喷雾得以克服。例如,在喷雾热解之前,先将具有元素Zn、Sb、Bi、Co、Mn、Cr的混合硝酸盐水溶液在有机相中分散并乳化(DE 4307333)。
在WO90/14307和DE3916643中,通过在作为燃料的有机物质(例如乙醇、丙醇、酒石酸或元素碳)存在下喷雾金属硝酸盐溶液,特别设计了火焰喷雾热解方法,这样在点燃之后进行充分的自承(self-supporting)燃烧。该方法用于制备具有Bi、Mn、Cr、Co、Sb2O3和Bi2Ti2O7粉末添加剂的氧化锌。
Merck的专利申请DE102005002659.1(提交日:2005年1月19日)描述了如何通过在脉动反应器中进行特定的方法设计,可以制备由致密的球形颗粒组成的混合氧化物粉末。为了进行该方法,将原料溶液喷雾到由脉动、无火焰的燃烧产生的热气体流中。
如上所述,如在火焰热解或者在外部电加热热壁反应器的情况中发生的包含在颗粒内部的溶剂以及通过对流或辐射从内向外发生的颗粒加温是不希望的不规则形状的多孔、中空颗粒形成的原因。
因此,本发明的目的在于提供能够以简单方式进行的不具有这些缺点并可以制备致密球形金属氧化物颗粒或相应粉末的方法。特别地,本发明的目的在于由其可以以简单和廉价方式制备二元或多元混合氧化物的相应方法。
根据本发明通过在热壁反应器中将具有限定的盐或固体浓度的通常的盐的水溶液或悬浮液进行喷雾热解实现了该目的,其中将在工艺条件下放热分解并因此促进形成无孔致密球形颗粒的无机盐任选地添加到溶液或分散液中。特别地,本发明还通过添加进一步改进颗粒形态的表面活性剂而实现。
因此,本发明特别涉及通过喷雾热解制备平均颗粒尺寸<10μm的球形的二元或多元混合氧化物粉末的方法,其特征在于:
a)将至少两种以盐、氢氧化物或其混合物形式的原料溶解或分散在水、碱或酸中,或将一种或多种原料分散在盐溶液中,和
b)添加表面活性剂和/或以放热反应分解的无机盐,和
c)将该混合物喷雾到电热热解反应器中、热分解并转变为混合氧化物。
为了进行该方法,所用的原料是溶解或分散在有机溶剂中的有机金属化合物,特别是IIA(IUPAC:2)、IIIA(13)、IIIB(3)和VIB(6)族元素的盐、氢氧化物或有机金属化合物。所用的原料优选可以为硝酸盐、氯化物、氢氧化物、乙酸盐、乙醇盐、丁醇盐或异丙醇盐或其混合物。特别地,适合的原料也为IIA和IIIB族元素的铝酸盐。
为了进行根据本发明的方法,如果使用选自硝酸盐、氯酸盐、高氯酸盐和硝酸铵中的以放热反应分解的无机盐,单独或者以混合物形式使用,并且其添加量是所用原料总量的10~80%,优选25~50%;以及添加选自脂肪醇乙氧基化物、脱水山梨醇油酸酯和两亲聚合物的表面活性剂,并且其用量为溶液总重量的3~15%,优选为6~10%,可以实现特别好的产物性质。
因此,本发明涉及由以上述方法制备的混合氧化物粉末,其平均颗粒尺寸在0.005~<10μm范围内,比表面积(通过BET方法测定)在3~30m2/g,优选5~15m2/g范围内,且其具有致密的球形形态。然而,本发明还涉及具有在0.005~2μm范围内的平均颗粒尺寸,或者为了特别需要,具有在1~5μm范围内的平均颗粒尺寸的混合氧化物粉末。特别地,通过由根据本发明的方法制备的,平均颗粒尺寸在0.1~1μm范围内,比表面积(通过BET方法测定)在10~60m2/g,优选20~40m2/g范围内,具有致密的球形形态的混合氧化物粉末实现了根据本发明的目的。根据本发明制备的,平均颗粒尺寸在0.005~0.um范围内,比表面积(通过BET方法测定)在40~350m2/g,优选50~100m2/g范围内的,混合氧化物粉末具有特别有利的性质。
根据本发明制备的混合氧化物粉末特别适用于制备高密度、高强度和任选透明的陶瓷中,或利用热压技术制备高密度、高强度和任选透明的块状材料(bulk material)。这些混合氧化物特别适用于作为磷光体的基体材料或作为磷光体。然而,其也可以用作聚合物或橡胶中的填料或用作抛光剂。
为了进行根据本发明的方法,通过具有特定空气/进料比的双组分喷嘴将预先制备的溶液、分散体或悬浮液喷雾到外部电加热管中。其原理示于表1的描述中。借助于多孔金属填料,从热气流中将粉末分离出来。
所需的能量输入降低在喷入点紧后面通过溶剂蒸发和流体的低湍流产生的冷却效应自动地发生。
根据本发明通过例如以碱金属硝酸盐或优选以硝酸铵的形式引入的无机盐(例如硝酸盐、氯酸盐或高氯酸盐)的化学分解反应引入另外的能量,其中后者另外具有氧化行为。另外的表面活性剂(例如以脂肪醇乙氧基化物的形式)的添加有效形成了更细和更为球形的颗粒。
使用基于Mg和Y铝酸盐的粉末作为实例,可以看到根据本发明的各种添加物的组合以及使用上述热壁反应器能够制备具有在0.005~2μm范围内平均颗粒尺寸的微细分散的、致密的球形粉末。
此处所用的原料是包含所需化学计量比率的相应元素的混合硝酸盐溶液。优选在这些溶液中添加基于起始溶液中的盐含量10~50%,优选20~40%的硝酸铵作为化学能量载体。进一步通过稀释可以使颗粒尺寸减小25~50%。
令人惊奇地,通过试验确定在长度为1.5m的热壁反应器中在反应器温度仅为约1050℃时,在根据本发明的条件下Mg/Al混合硝酸盐溶液完全转变为MgAl2O4。以此方式制备的颗粒形态为球形,其平均颗粒尺寸为1.8μm(参见图2)。
特别令人惊奇的是,已经证明在如上所述的短时反应器(short timereactor)中不仅通过溶解,而且通过适当的盐或氢氧化物(例如Mg(OH)2)分散在硝酸铝溶液中借助于喷雾热解会形成尖晶石,而不会留下残余的可通过X射线照相法检测到的单一氧化物。通过添加硝酸铵,获得了为3.5μm的平均颗粒尺寸(参见实施例2)。
然而使用此处所述的反应器将例如纳米级分散的Al2O3的氧化物分散在Mg盐溶液中不会导致形成混合氧化物,通过分散在乙酸镁溶液中的Al的氢氧化物(例如以AlO(OH)的形式)的喷雾和热解,可以通过X射线照相法检测到尖晶石相,以及无定形粉末部分。也可以通过在空气存在下在1200℃煅烧将其完全转化为尖晶石(参见实施例3)。可以以此方式制备亚微米或纳米粉末。
使用钇/铝混合硝酸盐溶液也获得了与镁铝氧化物情况中所得到的类似的颗粒尺寸分布和颗粒形态。水、硝酸铵和表面活性剂的组合添加以及反应器中适当的温度条件的设定会对其颗粒形态、尺寸和尺寸分布产生特别的影响。因此,根据本发明制备的粉末具有尺寸不超过约8μm的圆形固体颗粒(参见图3)。
在这种情况中,最初形成的并不是并不是与晶体相Y3Al5O12相对应的化学起始组合物,而是约90%的X射线无定形组分和2~5%的立方晶系Y3Al5O12,约3~6%的YAlO3和约2%的Y2O3。可以通过在900℃~1200℃范围内的温度(优选1100℃)下进一步热处理将该材料完全转变为立方晶系YAG相。
使用Y的氯化物溶液与Al硝酸盐溶液以与随后待制备的产物的适当化学计量对应的化学计量比例混合,可以制备具有类似特征的粉末。在已经提到的长度为约1.5m的热壁反应器中以非常短的产品滞留时间在此形成约80%的无定形粉末部分。除Y3Al5O12目标相之外,晶体相为大约相同比例和高度活性的过渡氧化铝(κ和θ相)以及氧化钇的YAlO3相。同样这种相混合物可以通过在约1000℃煅烧转化为YAG相。
使用如上所述试剂制备的粉末具有非常不同的颗粒尺寸和颗粒尺寸分布,其可以进一步处理并用于各种途径,例如用于制备高密度陶瓷材料、层,用作填料和抛光材料。
掺杂稀土(RE)元素(例如Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Tm、Yb及其混合物)的铝酸镁或铝酸钇及其混合物可以用作磷光体材料,其中上述RE金属作为活化剂元素[Angew.Chem.110(1998);第3250-3272页]。
根据本发明的方法可以有利地制备具有部分替换元素(即使以低的百分比)的粉状物质系统。通过混合和喷雾盐溶液,可以实现颗粒中元素的均匀分布。即使为了建立特定相的组合物需要连续煅烧工艺,为此目的所需的温度也低于并非基于热解原理的所谓的“固态工艺”,对于目的产物仍保持粉末的形态和均质性。
如实施例5和6中所示,可以制备Ce掺杂的Y3Al5O12。
由于其球形形态意味着可以实现比其它几何形状更高的填充密度,这些粉末可以有利地用作磷光体基体材料。以这种形式,其可以特别有利地用于通过用蓝光发射体和前述磷光体结合制备白光发射照明系统,例如用于无机和有机发光二极管。
为了更好的理解和描述本发明,下面给出了在本发明的保护范围内的实施例。然而,由于上述本发明的原理的一般有效性,将本发明的保护范围减小为仅仅这些实施例是不合适的。
实施例
实施例1
将六水合硝酸镁(分析级,获自Merck KGaA)和九水合硝酸铝(分析级,获自Merck KGaA)各自分别溶解在超纯水中。通过络合滴定法测定溶液中的金属含量。其分别为6.365%Mg和4.70%Al。通过剧烈搅拌制备包含摩尔比为1∶2的元素Mg和Al的Mg/Al混合硝酸盐溶液。用超纯水以1∶1的比例稀释该溶液。
进一步添加基于硝酸盐含量计为30%的硝酸铵(分析级,获自Merck KGaA)和含量为溶液总重量的7.5%的脂肪醇乙氧基化物(Lutensol AO3,获自BASF AG)。
将该混合物通过双组分喷嘴喷雾到长度为1.5m的热壁反应器中。通过烧结金属热气体过滤器从热气流中将颗粒分离出来。
其它反应器参数:
进料通量:1.2kg/h
双组分喷嘴处的空气压力:4.0巴
反应器温度:1050℃
过滤器温度:350℃
粉末性质:
-灼烧损失:2.1%
-颗粒尺寸分布:d50=1.8μm,d95=3.5μm,d99.9=7μm
-颗粒形态:球形颗粒(参见图2)
-比表面积(BET):16m2/g
-相(X射线衍射):尖晶石(MgAl2O4)
实施例2
将0.03kg获自Magnesia-Produkte GmbH的MagnifinHIO型Mg(OH)2分散在0.6kg金属含量为4.5%的硝酸铝溶液中,在添加0.125kg硝酸铵之后,如实施例1中所述将混合物喷雾到热壁反应器中并热解。
粉末性质:
-灼烧损失:2.3%
-颗粒尺寸分布:d50=3.5μm,d95=9.0μm,d99.9=17μm
-颗粒形态:球形颗粒
-比表面积(BET):21m2/g
-相(X射线衍射):尖晶石(MgAl2O4),未检测到残余的单一氧化物。
实施例3
将作为Al组分的AlO(OH)分散到乙酸镁溶液(水溶液)中,原料的重量如下:
-0.8kg AlO(OH),获自Albemarle Corp.的Martoxal BN-2A型
-溶解在2kg水中的1.43kg乙酸镁·4H2O
通过双组分喷嘴将该悬浮液喷雾到具有实施例1中给出的参数的热壁反应器中并热解。
粉末性质:
-灼烧损失:3.1%
-比表面积(BET):40m2/g
-平均颗粒尺寸分布(由BET计算):0.04μm
-颗粒形态:球形颗粒
-相(X射线衍射):尖晶石(MgAl2O4)以及Mg和Al的氧化物的晶体部分。
通过在箱式炉中在空气中在1200℃煅烧4h,完全转化为尖晶石。
实施例4
将六水合硝酸钇(Merck KGaA)和九水合硝酸铝(分析级,获自Merck KGaA)各自分别溶解在超纯水中,使得根据络合滴定法测定,该溶液的金属含量为15.4%Y和4.7%Al。然后通过剧烈搅拌制备包含摩尔比为3∶5的元素Y和Al的Y/Al混合硝酸盐溶液。用超纯水以1∶1的比例稀释该溶液。进一步添加基于硝酸盐含量计为30%的硝酸铵(分析级,获自Merck KGaA)和含量为溶液总重量的7.5%的脂肪醇乙氧基化物(LutensolAO3,获自BASFAG)。
在搅拌2小时后,将该混合物通过双组分喷嘴喷雾到长度为1.5m的热壁反应器中。通过烧结金属热气体过滤器从热气流中将颗粒分离出来。
反应器参数:
进料通量:1.3kg/h
双组分喷嘴处的空气压力:4.0巴
反应器温度:1050℃
过滤器温度:325℃
粉末性质:
-灼烧损失:0.5%
-颗粒尺寸分布:d50=2.1μm,d95=4μm,d99.9=7.5μm
-颗粒形态:球形颗粒(参见图3)
-比表面积(BET):6.9m2/g
-相(X射线衍射):91%的X射线无定形组分;2%Y3Al5O12;约4.5%YAlO3,2%Y2O3。
在空气中在1100℃煅烧4h后:
-比表面积(BET):4.8m2/g
-晶体相(X射线衍射):98%的立方晶系YAG相;
-1.5%的六边形YAl12O19,0.5%的单斜晶系Y4Al2O9。
实施例5
将六水合硝酸钇(Merck KGaA)、九水合硝酸铝(分析级,获自Merck KGaA)和六水合硝酸铈(超纯级,获自Merck KGaA)各自分别溶解在超纯水中,使得该溶液中的金属含量为15.4重量%Y、4.7重量%Al和25.2重量%Ce。然后通过剧烈搅拌2小时制备包含摩尔比为2.91∶5∶0.09的元素Y、Al和Ce的Y/Al/Ce混合硝酸盐溶液。用超纯水以1∶1的比例稀释该溶液,然后进一步添加基于硝酸盐含量计为30%的硝酸铵(分析级,获自Merck KGaA)。
将该混合物通过双组分喷嘴喷雾到长度为1.5m的热壁反应器中。通过烧结金属热气体过滤器从热气流中将颗粒分离出来。
反应器参数:
进料通量:1.2kg/h
双组分喷嘴处的空气压力:4.0巴
反应器温度:1050℃
过滤器温度:330℃
粉末性质:
-灼烧损失:0.5%
-颗粒尺寸分布:d50=1.7μm,d95=3.9μm,d99.9=6.5μm
-颗粒形态:球形颗粒
-比表面积(BET):6.5m2/g
-相(X射线衍射):以Y3Al5O12、YAlO3和Y2O3形式的晶体部分,以及大概以氧化物形式的无定形部分。
在空气中在1130℃煅烧4h后:
-比表面积(BET):4.8m2/g
-晶体相(X射线衍射):95%的立方混合晶体相
-颗粒形态:球形颗粒(参见图4)。
实施例6
根据实施例5制备混合硝酸盐溶液并进行喷雾热解。
在箱式炉中在空气中将该粉末在1100℃煅烧10h后,其具有以下性质:
-颗粒尺寸分布:d50=2.3μm,d95=4.5μm,d99.9=8.5μm
-颗粒形态:球形颗粒
-比表面积(BET):3.4m2/g
-相(X射线衍射):98%的立方晶系混合晶体相
附图:
图1:热壁反应器的原理示图
图2:Mg/Al氧化物粉末(根据实施例1)的SEM照片
图3:Y/Al氧化物粉末(根据实施例4)的SEM照片
图4:添加铈的Y/Al氧化物粉末(根据实施例5)的SEM照片
Claims (17)
1.通过喷雾热解制备平均颗粒尺寸<10μm的球形的、二元或多元混合氧化物粉末的方法,其特征在于:
a)将至少两种以盐、氢氧化物或其混合物形式的原料溶解或分散在水、碱或酸中,或将一种或多种原料分散在盐溶液中,和
b)添加表面活性剂和/或以放热反应分解的无机盐,和
c)将该混合物喷雾到电热热解反应器中、热分解并转变为混合氧化物。
2.根据权利要求1的方法,其特征在于所用的原料是溶解或分散在有机溶剂中的有机金属化合物。
3.根据权利要求1或2的方法,其中使用IIA(IUPAC:2)、IIIA(13)、IIIB(3)和VIB(6)族元素的盐、氢氧化物或有机金属化合物。
4.根据权利要求1~3的方法,其特征在于所用的原料是硝酸盐、氯酸盐、氢氧化物、乙酸盐、乙醇盐、丁醇盐或异丙醇盐或其混合物。
5.根据权利要求1~4中一项或多项的方法,其特征在于所用的原料是IIA和IIIB族元素的铝酸盐。
6.根据权利要求1~5中一项或多项的方法,其特征在于所用的以放热反应分解的无机盐选自硝酸盐、氯酸盐、高氯酸盐和硝酸铵,单独或者以混合物形式使用,添加量是所用原料量的10~80%,20~50%。
7.根据权利要求1~6中一项或多项的方法,其特征在于使用的表面活性剂选自脂肪醇乙氧基化物、脱水山梨醇油酸酯和两亲聚合物,其用量为溶液总重量的3~15%,优选为6~10%。
8.由根据权利要求1~7的方法制备的混合氧化物粉末,其特征在于平均颗粒尺寸在0.005~<10μm范围内,通过BET方法测定的比表面积在3~30m2/g,优选5~15m2/g范围内,且其具有致密的球形形态。
9.根据权利要求8的混合氧化物粉末,其特征在于平均颗粒尺寸在0.005~2μm范围内。
10.根据权利要求8的混合氧化物粉末,其特征在于平均颗粒尺寸在1~5μm范围内。
11.由根据权利要求1~7的方法制备的混合氧化物粉末,其特征在于其平均颗粒尺寸在0.1~1μm范围内,通过BET方法测定的比表面积在10~60m2/g,优选20~40m2/g范围内,且其具有球形形态。
12.根据权利要求8~11之一的混合氧化物粉末在制备高密度、高强度和任选透明的陶瓷中的应用。
13.由根据权利要求1~7的方法制备的混合氧化物粉末,其特征在于其平均颗粒尺寸在0.005~0.1μm范围内,通过BET法测定的比表面积在40~350m2/g,优选50~100m2/g范围内,且其具有球形形态。
14.根据权利要求8~11、13之一的混合氧化物粉末在利用热压技术制备高密度、高强度和任选透明的块状材料中的应用。
15.根据权利要求8~11、13之一的混合氧化物粉末作为磷光体的基体材料或作为磷光体的应用。
16.根据权利要求8、9~11、13之一的混合氧化物粉末作为聚合物或橡胶中的填料的应用。
17.根据权利要求8~11、13之一的混合氧化物粉末作为抛光剂的应用。
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US (1) | US20080145306A1 (zh) |
EP (1) | EP1848663A2 (zh) |
JP (1) | JP2008535750A (zh) |
KR (1) | KR20070103029A (zh) |
CN (1) | CN101119929A (zh) |
AU (1) | AU2006215886A1 (zh) |
DE (1) | DE102005007036A1 (zh) |
WO (1) | WO2006087061A2 (zh) |
Cited By (5)
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CN107074542A (zh) * | 2014-05-07 | 2017-08-18 | 派洛特公司 | 个体化无机粒子 |
CN107406330A (zh) * | 2015-03-18 | 2017-11-28 | 阿纳多卢大学雷克多卢库 | 通过火焰热解法生产芯/壳结构的复合尖晶石粉 |
CN107482162A (zh) * | 2017-08-28 | 2017-12-15 | 中南大学 | 高振实密度金属氧化物、制备方法及锂离子电池 |
CN107645968A (zh) * | 2014-12-15 | 2018-01-30 | 佩洛特公司 | 气溶胶获得的负载有防腐剂的介观结构颗粒 |
CN109607616A (zh) * | 2018-12-19 | 2019-04-12 | 大连理工大学 | 一种喷雾合成金属氧化物空心球粉体及其前驱体的方法 |
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DE102005002659A1 (de) * | 2005-01-19 | 2006-07-27 | Merck Patent Gmbh | Verfahren zur Herstellung von Mischoxiden mittels Sprühpyrolyse |
DE102006059216A1 (de) * | 2006-12-13 | 2008-06-19 | Institut für Oberflächenmodifizierung e.V. | Anorganische Metalloxid-Nanopartikel und Metalloxid-Nanopartikel enthaltende Komposite |
US20090029064A1 (en) * | 2007-07-25 | 2009-01-29 | Carlton Maurice Truesdale | Apparatus and method for making nanoparticles using a hot wall reactor |
WO2009151489A2 (en) * | 2008-02-25 | 2009-12-17 | Corning Incorporated | Nanomaterial and method for generating nanomaterial |
US20100012478A1 (en) * | 2008-07-17 | 2010-01-21 | Nitto Denko Corporation | Thermal treatment for inorganic materials |
JP5743693B2 (ja) * | 2011-04-28 | 2015-07-01 | 第一稀元素化学工業株式会社 | スピネル粉末およびその製造方法、溶射膜の製造方法、ならびにガスセンサ素子の製造方法 |
JP5771161B2 (ja) * | 2012-02-29 | 2015-08-26 | 花王株式会社 | 球状セラミックス粒子の製造方法 |
GB201901061D0 (en) * | 2019-01-25 | 2019-03-13 | Ceramic Powder Tech As | Process |
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GB2210605B (en) * | 1987-10-05 | 1991-06-26 | Merck Patent Gmbh | Process for the preparation of metal oxide powders |
JPH02137709A (ja) * | 1988-11-18 | 1990-05-28 | Furukawa Electric Co Ltd:The | 酸化物超電導体粉末の製造方法 |
DE3916643C1 (zh) * | 1989-05-22 | 1991-01-03 | Merck Patent Gmbh, 6100 Darmstadt, De | |
GB9409660D0 (en) * | 1994-05-13 | 1994-07-06 | Merck Patent Gmbh | Process for the preparation of multi-element metaloxide powders |
JP2000007309A (ja) * | 1998-06-19 | 2000-01-11 | Toyota Central Res & Dev Lab Inc | 多孔質酸化物粉末の製造方法 |
JP2000087033A (ja) * | 1998-09-11 | 2000-03-28 | Kasei Optonix Co Ltd | 蛍光体の製造方法 |
JP2000103616A (ja) * | 1998-09-30 | 2000-04-11 | Toyota Central Res & Dev Lab Inc | スピネル製造用混合溶液および該混合溶液を用いてスピネルを製造する方法 |
US20050119132A1 (en) * | 2001-11-30 | 2005-06-02 | Chao-Nan Xu | Method and apparatus for preparing spherical crystalline fine particles |
JP2003336045A (ja) * | 2002-05-20 | 2003-11-28 | Konica Minolta Holdings Inc | 蛍光体及び蛍光体の製造方法 |
JP4928273B2 (ja) * | 2004-01-23 | 2012-05-09 | ベリー スモール パーティクル コンパニー リミテッド | 多孔質複合酸化物の製造方法 |
-
2005
- 2005-02-15 DE DE102005007036A patent/DE102005007036A1/de not_active Withdrawn
-
2006
- 2006-01-14 CN CNA2006800048894A patent/CN101119929A/zh active Pending
- 2006-01-14 KR KR1020077018611A patent/KR20070103029A/ko not_active Application Discontinuation
- 2006-01-14 JP JP2007554452A patent/JP2008535750A/ja active Pending
- 2006-01-14 EP EP06700835A patent/EP1848663A2/de not_active Withdrawn
- 2006-01-14 WO PCT/EP2006/000298 patent/WO2006087061A2/de active Application Filing
- 2006-01-14 US US11/816,220 patent/US20080145306A1/en not_active Abandoned
- 2006-01-14 AU AU2006215886A patent/AU2006215886A1/en not_active Abandoned
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CN107074542A (zh) * | 2014-05-07 | 2017-08-18 | 派洛特公司 | 个体化无机粒子 |
CN107074542B (zh) * | 2014-05-07 | 2020-10-16 | 派洛特公司 | 个体化无机粒子 |
CN107645968A (zh) * | 2014-12-15 | 2018-01-30 | 佩洛特公司 | 气溶胶获得的负载有防腐剂的介观结构颗粒 |
CN107406330A (zh) * | 2015-03-18 | 2017-11-28 | 阿纳多卢大学雷克多卢库 | 通过火焰热解法生产芯/壳结构的复合尖晶石粉 |
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CN107482162B (zh) * | 2017-08-28 | 2020-12-08 | 中南大学 | 高振实密度金属氧化物、制备方法及锂离子电池 |
CN109607616A (zh) * | 2018-12-19 | 2019-04-12 | 大连理工大学 | 一种喷雾合成金属氧化物空心球粉体及其前驱体的方法 |
CN109607616B (zh) * | 2018-12-19 | 2021-02-19 | 大连理工大学 | 一种喷雾合成金属氧化物空心球粉体及其前驱体的方法 |
Also Published As
Publication number | Publication date |
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KR20070103029A (ko) | 2007-10-22 |
WO2006087061A3 (de) | 2007-03-15 |
JP2008535750A (ja) | 2008-09-04 |
US20080145306A1 (en) | 2008-06-19 |
DE102005007036A1 (de) | 2006-08-17 |
WO2006087061A2 (de) | 2006-08-24 |
AU2006215886A1 (en) | 2006-08-24 |
EP1848663A2 (de) | 2007-10-31 |
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