一种纳米金属氧化物材料的制备方法 专利CN100491256CC类

浙江师范大学  2017-1-6 14:01
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本发明涉及纳米材料的制备技术领域,特别是一种纳米金属氧化物材料的制备方法。本发明的目的是针对现有纳米氧化物材料的制备工艺条件复杂、纳米尺寸可控制性差、制备成本高等不足之处,提供了一种工艺简单、对纳米材料尺寸大小易控制的纳米金属氧化物材料的制备方法。本发明采用的技术方案是:用一定比例组成的金属化合物和有机络合剂制备氧化物前驱体,在氮气等惰性气体保护下在高温焙烧,得到黑色含碳的氧化物,然后将氧化物在较低温度下置于空气中除去碳,得到高比表面积的纳米材料。其中通过调节焙烧温度,可以有效地控制纳米材料的颗粒大小。 说明

一种纳米金属氧化物材料的制备方法

技术领域

本发明涉及纳米材料的制备技术领域,特别是一种纳米金属氧化物材料的制备方法。 背景技术

纳米材料由于量子尺寸效应、小尺寸效应、表面效应和宏观隧道效应等特性,使其在 众多领域有着广泛应用,为此人们进行了大量纳米材料,特别是纳米金属氧化物材料的制 备技术的研究与开发,目前由中国专利文献公开的纳米金属氧化物材料的制备技术数量众 多,例如:

专利号为200310117453.4的制备金属氧化物纳米材料的高温高压超临界流体法。该 制备金属氧化物纳米材料的高温高压超临界流体法,需要特殊的设备,实验条件比较苛刻。

专利号为03154261. 1和专利号为02115326. 4的制备金属氧化物纳米材料的无机盐沉 淀法。该制备金属氧化物纳米材料的无机盐沉淀法,对纳米尺寸的可控制性差,其纳米材 料的晶粒50〜100nm,比表面积〈10m2 • g—、

专利号为03150836.7的制备金属氧化物纳米材料的有机络合物法。该制备金属氧化 物纳米材料的有机络合物法,通常是在空气中直接在高温下把有机络合物燃烧掉,这样制 得的纳米材料颗粒相对较大,比表面积相对较小,其纳米材料的晶粒30〜90nm,比表面积 <20m2 • g—1。

发明内容

本发明的目的是针对现有纳米氧化物材料的制备工艺条件复杂、纳米尺寸可控制性 差、制备成本高等不足之处,提供了一种工艺简单、对纳米材料尺寸大小易控制的纳米金 属氧化物材料的制备方法。

本发明采用的技术方案是通过如下方式完成的:在一定摩尔比金属化合物混合溶液 中,加入一定量的有机络合剂,在搅拌的条件下加热蒸发至粘稠状溶胶,低温烘干,得到 松散粉末状的凝胶(即氧化物前驱体),之后使氧化物前驱体在氮气等保护气体中高温焙 烧一定时间,得到黑色含碳的氧化物,最后将氧化物中的碳在空气中较低温度焙烧去除, 得到高比表面积的纳米材料。其中通过调节焙烧温度,可以有效地控制纳米材料的颗粒大

本发明的纳米氧化物材料制备方法具有步骤如下:(1) 制备氧化物前驱体。在单一组分金属化合物溶液或一种以上组分不同比例的金属 化合物混合溶液中,加入一定量的有机络合剂,有机络合剂的总的物质的量是所有金属总 的物质的量的0.5〜4倍。加入少量的水后搅拌加热,蒸发至粘稠状溶胶;之后控制温度 为80〜12(TC烘干5〜15小时,得到松散粉末状的凝胶即氧化物前驱体。

(2) 制备氧化物中间体。在氮气等惰性保护气体保护下,使氧化物前驱体经高温焙烧, 得到黑色含碳氧化物中间体,焙烧温度控制范围为500〜120(TC,焙烧时间控制范围为l〜 5小时。

(3) 制备纳米氧化物。把含碳氧化物中间体在空气中于300〜70(TC焙烧1〜5小时,即 得到高比表面积的纳米材料。

(4) 根据所制备金属氧化物中各个金属元素的不同含量,相应调解焙烧温度和焙烧时 间,可以控制纳米材料的颗粒大小。

本发明的纳米氧化物材料制备方法与现有的制备纳米材料相比,具有操作方法简易、 快捷和价格低廉等优点,尤其是可以有效的控制不同金属氧化物纳米尺寸和提高比表面 积;用本发明的纳米氧化物材料制备方法能够得到的晶粒小于5rim,比表面积大于100m2 «g—1 的金属氧化物纳米材料。

附图说明

图1为实施例1和对比例1的铈锆氧化物的XRD图谱。 图2为实施例1样品的铈锆氧化物的TEM图谱。 图3为对比例1样品的铈锆氧化物的TEM图谱。 图4为实施例1样品的钸锆氧化物的BET图谱。 图5为对比例1样品的铈锆氧化物的BET图谱。

具体实施方式

下面通过实施例对本发明的纳米氧化物材料制备方法作进一步说明,但本发明并不限 于这些实施例。 实施例1

按照实施例3制备松散粉末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流 速为30〜50ml/min,使氧化物前驱体在80(TC下焙烧3小时,得到黑色含碳氧化物中间体。 最后把黑色含碳氧化物中间体在空气中40(TC焙烧3小时,得到锆铈氧化物,通过XRD、 TEM和BET表征,所制得的铈锆氧化物是具有高比表面积的纳米材料,见附表1和附图1、 附图2、附图4。

对比例1

作为对比实施例。在相同条件下,取一部分实施例3中的松散粉末状的凝胶即氧化物前驱体,直接置于马沸炉中空气气氛常压800'C下焙烧3小时,得到锆铈复合氧化物,通 过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例5中制备的氧化物,见附表1 和附图l、附图3、附图5。 实施例2

称取32. 37g Ce (N03) 3 • 6H20、 8, OOg Zr (N03) 4 • 5H20和16. 16g苹果酸,混合后加 入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用控制电流的电炉加热,小 心蒸发至粘稠状溶胶,于IOO'C左右经10〜14小时烘干,得到松散粉末状的凝胶即氧化 物前驱体。之后在常压下用氮气保护,流速为30〜50 ml /min,使氧化物前驱体在60CTC 下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在空气中400 。C焙烧3小时,得到铈锆氧化物,通过XRD、 TEM和BET表征,所制得的铈锆氧化物是具 有高比表面积的纳米材料,见附表1和附图1〜3。

对比例2

作为对比实施例。在相同条件下,取一部分实施例2中的松散粉末状的凝胶即氧化物 前驱体,直接置于马沸炉中空气气氛常压60(TC下焙烧3小时,得到铈锆复合氧化物,通 过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例2中制备的氧化物,见附表1。

实施例3

称取7. 30g Ce (N03) 2 • 6H20、 28. 87g Zr (N03) 2 • 6H20和17. 66g柠檬酸,混合后加 入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用水浴加热,小心蒸发至粘 稠状溶液,于IO(TC左右经10〜14小时烘干,得到松散粉末状的凝胶即氧化物前驱体。 之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物前驱体在60CTC下焙烧3小 时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在空气中40(TC焙烧3小 时,得到锆铈氧化物,通过XRD、 TEM和BET表征,所制得的锆铈氧化物是具有高比表面 积的纳米材料,见附表l。

对比例3

作为对比实施例。在相同条件下,取一部分实施例3中的松散粉末状的凝胶即氧化物 前驱体,直接置于马沸炉中空气气氛常压60(TC下焙烧3小时,得到锆铈复合氧化物,通 过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例3中制备的氧化物,见附表1。

实施例4

按照实施例2制备松散粉末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流 速为30〜50ml/min,使氧化物前驱体在80CTC下焙烧3小时,得到黑色含碳氧化物中间 体。最后把黑色含碳氧化物中间体在空气中40CTC焙烧3小时,得到铈锆氧化物,通过 XRD、 TEM和BET表征,所制得的铈锆氧化物是具有高比表面积的纳米材料,见附表l。

对比例4 '

作为对比实施例。在相同条件下,取一部分实施例2中的松散粉末状的凝胶即氧化物前驱体,直接置于马沸炉中空气气氛常压80(TC下焙烧3小时,得到铈锆复合氧化物,通 过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例4中制备的氧化物,见附表1。 实施例5

称取3.00g PreOu用适量的浓硝酸溶解,再称取30. 61g Ce (N03) 2 • 6H20和18. 52g 拧檬酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用控制电 流的电炉加热,小心蒸发至粘稠状溶胶,于10(TC左右经10〜14小时烘干,得到松散粉 末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物 前驱体在80(TC下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间 体在马沸炉中空气气氛40(TC焙烧3小时,得到锆铈氧化物,通过XRD、 TEM和BET表征,

所制得的铈镨氧化物是具有高比表面积的纳米材料,见附表1。 对比例5

作为对比实施例。在相同条件下,取一部分实施例l中的松散粉末状的凝胶即氧化物 前驱体,直接置于马沸炉中空气气氛常压80(TC下焙烧3小时,得到铈镨复合氧化物,通 过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例1中制备的氧化物纳米材料, 见附表l。

实施例6

称取6. OOg Gd203用适量的浓硝酸溶解,再称取9. 30g Ce (N03) 2 • 6H20和6. 86g柠檬 酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用控制电流的 电炉加热,小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时烘干,得到松散粉末状 的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物前驱 体在80(TC下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在 空气中700'C焙烧3小时,得到钆氧化物,通过XRD、 TEM和BET表征,所制得的钆氧化

物是具有高比表面积的纳米材料,见附表l。 对比例6

作为对比实施例。在相同条件下,取一部分实施例6中的松散粉末状的凝胶即氧化物 前驱体,直接置于马沸炉中空气气氛常压80(TC下焙烧3小时,得到钆氧化物,通过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例6中制备的氧化物,见附表l。

实施例7

称取6.00g GdA用适量的浓硝酸溶解,再称取6. 16g Ce (N03) 3 • 6H20、 5. 30g柠檬 酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用水浴加热, 小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时烘干,得到松散粉末状的凝胶即氧 化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/rain,使氧化物前驱体在80(TC 下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在空气中500 °C焙烧3小时,得到钆铈氧化物,通过XRD、 TEM和BET表征,所制得钆铈氧化物是具有

6高比表面积的纳米材料,见附表l。 对比例7

作为对比实施例。在相同条件下,取一部分实施例7中的松散粉末状的凝胶即氧化物 前驱体,直接置于马沸炉中空气气氛常压80(TC下焙烧3小时,得到钆铈复合氧化物,通 过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例7中制备的氧化物,见附表1。

实施例8

称取6. OOg GdA用适量的浓硝酸溶解,再称取14. 38g Ce (N03) 3 • 6H20、 4. 10g柠檬 酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用水浴加热, 小心蒸发至粘稠状溶胶,于IOO'C左右经10〜14小时烘干,得到松散粉末状的凝胶即氧 化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物前驱体在60CTC 下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在空气中500 °C焙烧3小时,得到钆铈氧化物,通过XRD、 TEM和BET表征,所制得钆铈氧化物是具有 高比表面积的纳米材料,见附表l。

对比例8

作为对比实施例。在相同条件下,取一部分实施例8中的松散粉末状的凝胶即氧化物 前驱体,直接置于马沸炉中空气气氛常压60(TC下焙烧3小时,得到钆铈复合氧化物,通 过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例8中制备的氧化物,见附表1。

实施例9

称取4. OOg GdA用适量的浓硝酸溶解,再称取14. 38g Ce (N03) 3 • 6H20和18. 10g柠 檬酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用水浴加热, 小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时烘干,得到松散粉末状的凝胶即氧 化物前驱体。之后在常压下用氮气保护保护,流速为30〜50ml/min,使氧化物前驱体在 120CTC下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在空 气中50(TC焙烧3小时,得到铈钆氧化物,通过XRD、 TEM和BET表征,所制得铈钆氧化 物是具有高比表面积的纳米材料,见附表l。

对比例9

作为对比实施例。在相同条件下,取一部分实施例9中的松散粉末状的凝胶即氧化物 前驱体,直接置于马沸炉中空气气氛常压120(TC下焙烧3小时,得到铈钆复合氧化物, 通过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例9中制备的氧化物,见附 表l。

实施例10

称取2. 50g Gd203用适量的浓硝酸溶解,再称取23. 96g Ce歸3 • 6H20和26.10g柠 檬酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用水浴加热, 小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时烘干,得到松散粉末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物前驱体在1000 。C下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在空气中 500°C焙烧3小时,得到铈钆氧化物,通过XRD、 TEM和BET表征,所制得铈钆氧化物是 具有高比表面积的纳米材料,见附表l。 对比例10

作为对比实施例。在相同条件下,取一部分实施例10中的松散粉末状的凝胶即氧化 物前驱体,直接置于马沸炉中空气气氛常压IOO(TC下焙烧3小时,得到钆铈复合氧化物, 通过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例10中制备的氧化物,见附 表l。

实施例11

称取23. 96gCe (N03) 3 • 6H20和33. 10g柠檬酸,混合后加入适量的去离子水溶解,得 前驱物溶液。然后在搅拌的条件下用水浴加热,小心蒸发至粘稠状溶胶,于IO(TC左右经 10〜14小时烘干,得到松散粉末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流 速为30〜50ml/min,使氧化物前驱体在90CTC下焙烧3小时,得到黑色含碳氧化物中间 体。最后把黑色含碳氧化物中间体在空气中50CTC焙烧3小时,得到铈氧化物,通过XRD、 TEM和BET表征,所制得的铈氧化物是具有高比表面积的纳米材料,见附表l。

对比例11

作为对比实施例。在相同条件下,取一部分实施例11中的松散粉末状的凝胶即氧化 物前驱体,直接置于马沸炉中空气气氛常压90(TC下焙烧3小时,得到铈复合氧化物,通 过XRD、 TEM和BET表征,其晶粒和比表面积明显大于实施例11中制备的氧化物,见附表 1。

通过实验对比发现,本发明的纳米氧化物材料的制备技术与现有纳米材料的制备技术 相比,具有操作方法简易、快捷和价格低廉等优点,尤其是可以有效的控制不同金属氧化 物或复合金属氧化物的纳米尺寸和比表面积方面,具有很大的优势。

实施例12

称取3. OOgPreOu用适量的浓硝酸溶解,再称取11. 35gZr (N03) 4 • 5H20和41. 52g苹果 酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用控制电流的 电炉加热,小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时烘干,得到松散粉末状 的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物前驱 体在80(TC下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在 马沸炉中空气气氛中65CTC焙烧3小时,得到锆镨氧化物,见附表2。

实施例13

称取2. OOgPrA,'用适量的浓硝酸溶解,再称取26. 48gZr (N03) 4 • 5H20和17. 32g苹果 酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用控制电流的电炉加热,小心蒸发至粘稠状溶胶,于IO(TC左右经10~14小时烘干,得到松散粉末状 的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物前驱 体在80CTC下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在 马沸炉中空气气氛65(TC焙烧3小时,得到锆镨氧化物,见附表2。 实施例14

按照实施例13步骤,制备黑色含碳氧化物中间体,将其在马沸炉中空气气氛95(TC焙 烧3小时,得到锆镨氧化物,见附表2。 实施例15

称取2. OOgPreOn用适量的浓硝酸溶解,再称取15. 98gZr (N03) 4 • 5H20和12. 03g苹果 酸,混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件下用控制电流的 电炉加热,小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时烘干,得到松散粉末状 的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物前驱 体在80(TC下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间体在 马沸炉中空气气氛95(TC焙烧3小时,得到锆镨氧化物,见附表2。

实施例16

称取0. 38gErA、 1. 2(^^03用适量的浓硝酸溶解,再称取30. 42gZr (N03) 4 • 5H20和 40.72g聚乙二醇(1000),混合后加入适量的去离子水溶解,得前驱物溶液。然后在搅拌 的条件下用控制电流的电炉加热,小心蒸发至粘稠状溶胶,于10CTC左右经10〜14小时 烘干,得到松散粉末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜 50ml/min,使氧化物前驱体在800°C下焙烧3小时,得到黑色含碳氧化物中间体。最后把 黑色含碳氧化物中间体在马沸炉中空气气氛65(TC焙烧3小时,得到锆钇铒氧化物,见附 表2。

实施例17

按照实施例16步骤,制备黑色含碳氧化物中间体,将其在马沸炉中空气气氛95(TC焙 烧3小时,得到锆钇铒氧化物,见附表2。 实施例18

称取1. 200g La203用适量的浓硝酸溶解,再称取1. 78 g Cu (N03) 2 • 3H20、 25. 60 g Ce (N03) 3*6&0和30.20g聚乙二醇(1000),混合后加入适量的去离子水溶解,得前驱 物溶液。然后在搅拌的条件下用水浴加热,小心蒸发至粘稠状溶胶,于IO(TC左右经10〜 14小时烘干,得到松散粉末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为 30〜50ml/min,使氧化物前驱体在90(TC下焙烧3小时,得到黑色含碳氧化物中间体。最 后把黑色含碳氧化物中间体在马沸炉中空气气氛700。C焙烧3小时,得到铈镧铜氧化物, 见附表2。 '

实施例19称取1. 200gSm203用适量的浓硝酸溶解,再称取23. 64gZr (N03) 4 • 5H20、 14. 10g柠檬 酸,和5.51g5(m的Mn (N03) 2溶液混合后,加入适量的去离子水溶解,得前驱物溶液。然 后在搅拌的条件下用水浴加热,小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时烘 干,得到松散粉末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜 50ml/min,使氧化物前驱体在80(TC下焙烧3小时,得到黑色含碳氧化物中间体。最后把 黑色含碳氧化物中间体在马沸炉中空气气氛650'C焙烧3小时,得到锆钐锰氧化物,见附 表2。

实施例20

称取1.50gMg (OH) 2用适量的浓硝酸溶解,再称取29.44gZr (N03) 4 • 5H20、 17. 10g 柠檬酸,和6.86g50W的Mn (N03) 2溶液混合后,加入适量的去离子水溶解,得前驱物溶液。 然后在搅拌的条件下用水浴加热,小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时 烘干,得到松散粉末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜 50ml/min,使氧化物前驱体在800°C下焙烧3小时,得到黑色含碳氧化物中间体。最后把 黑色含碳氧化物中间体在马沸炉中空气气氛65(TC焙烧3小时,得到锆锰镁氧化物,见附 表2。

实施例21

称取1. 78gCu (N03) 2 • 3H20、 25, 60gCe (N03) 3 • 6H20和16. 20g拧檬酸,及6. 86g50% 的Mn (N03) 2溶液混合后,加入适量的去离子水溶解,得前驱物溶液。然后在搅拌的条件 下用水浴加热,小心蒸发至粘稠状溶胶,于IO(TC左右经10〜14小时烘干,得到松散粉 末状的凝胶即氧化物前驱体。之后在常压下用氮气保护,流速为30〜50ml/min,使氧化物 前驱体在80(TC下焙烧3小时,得到黑色含碳氧化物中间体。最后把黑色含碳氧化物中间 体在马沸炉中空气气氛95(TC焙烧3小时,得到铈锰铜氧化物,见附表2。

从以上实施例可以得出本发明的制备纳米氧化物材料技术,具有操作方法简易、快捷 和价格低廉等优点,尤其是可以有效的控制不同金属氧化物或复合金属氧化物的纳米尺 寸。表l实施树1~11的两种方法对比数欏

*气保护

空气直饞烧

为鹏 例 «化物 □ Air/ □ 晶斷 Dm 比表面粉 m2 • g" 例 Air/ □ 飾 比表面粉 m2 • g"

1 Ceo.2Zfo.gOy 800 400 4.4 130,6 1 800 26.4 3.8

2 Ceo.gZro.20y 歸 400 4.7 70.1 2 600 19.0 16.0

3 CeiuZro.gOy 600 400 4.2 128.2 600 15.0 20.1

4 Ceo.gZrajOy 800 400 5.4 85.0 4 800 31.3 6.4

800 柳 4.2 112.0 5 800 21.2 12.8

6 G*203 800 700 26.0 38.2 6 &00 211.0 8.0

7-1 Ceo.3Cdo.7Oy 800 500 8.1 86.7 7 800 58.1 14.9

8 Ceo.5CMro.5Oy 600 500 5.4 110.3 8 600 21.3 19.4

9 1200 500 31.5 36.1 9 12加 725.0 6.3

10 Ce0.gGdr0.2Oy ■ 500 25.5 48.5 10 騰 2H.0 7.6

11 Ce02 900 500 11.2 39.9 11 900 36.3 3.9

表2 $||例12~21的实睡黻裙

实據例 氣化物 氣气保护

PV口 Air/O 晶粒Mm

12 Pr。4Zro,60y 800 6邻 4.9

13 Proi6Zr。.84 Oy 800 650 5.6

14 Pro,24Zr0.76 Oy 800 950 18.3

15 PT(U6Zro.84 Oy 800 950 20.5

16 ZrYo.15Ero.wOy 800 650 4.9

17 ZrY(usErooooiOy 800 950 5.6

18 Ceo.8Lao.iCU(uOy 邻0 700 12.3

19 Zro.8SmojM1^).!Oy 800 650 U.5

20 Zr。.8Mn(uMgo.宜Oy 800 650 12.8

21 Ceo'gMnojCuo.iOy 800 950 20.5

11

专利公开号:CN100491256C 专利状态/类型:授权 专利申请号:CN 200510050420 专利公开日:2009年5月27日 专利申请日:2005年6月21日 发明者:应跃芳, 萍 方, 罗孟飞, 谢云龙, 谢冠群 申请人:浙江师范大学
专利引用
引用的专利 申请日期公开日 申请人专利名
CN1347958A2001年11月16日2002年5月8日清华大学一种纳米级钼酸盐基质上转换荧光材料及其制备方法
CN1523077A2003年9月5日2004年8月25日中国科学院上海硅酸盐研究所稀土氧化物基纳米发光粉体的制备方法
CN1622283A2004年12月15日2005年6月1日贺平复合氧化物半导体纳米材料的制备方法
非专利引用
参考文献
1LaMgAl11O19:R(R=Tb,Mn)的真空紫外光谱特性. 尤洪鹏等.中国稀土学报,第20卷第6期. 2002
2稀土复合氧化物纳米微晶RE2Sn2-xB'xO7的制备、结构和红外光谱(RE=Sm,Ce,B'=Fe,Co,Ni,x=0-1.0). 巩雄等.无机材料学报,第12卷第2期. 1997
分类
国际分类号C04B35/622, C01G1/02
法律事件
日期代码事件说明
2006年12月27日C06Publication
2007年2月14日C10Request of examination as to substance
2009年5月27日C14Granted
2013年8月7日C17Cessation of patent right
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