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CN1032260A - 超导材料制备方法及所得产品 - Google Patents

超导材料制备方法及所得产品 Download PDF

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CN1032260A
CN1032260A CN88106732A CN88106732A CN1032260A CN 1032260 A CN1032260 A CN 1032260A CN 88106732 A CN88106732 A CN 88106732A CN 88106732 A CN88106732 A CN 88106732A CN 1032260 A CN1032260 A CN 1032260A
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nitrate
aforesaid right
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玛丽-欧迪尔·莱芬
克劳德·玛格尼尔
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Rhodia Chimie SAS
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Abstract

本发明涉及基本上以稀土，至少一种碱土，至少 一种过渡金属和氧为基础制成超导细粉的方法，其特 征是其中包括以下步骤：a)将稀土溶胶与至少一种碱 土硝酸盐和至少一种过渡金属硝酸盐的溶液混合，所 得混合物的pH应调为能使硝酸盐均溶于混合物的 值；b)然后干燥所得的混合物；c)焙烧该干燥产品； d)必要时研磨焙烧粉。本发明还涉及该法制得的产 品。

Description

本发明涉及超导材料。
人们已知，超导性的特点是极低温度下导体内电阻全部消失。
直到不久前，某些材料的超导状态还只在极限温度以下出现，极限温度即“临界温度”，一般接近于绝对零度。这一限制显然严重阻碍了超导性各种潜在实际用途的大规模发展。
但是，此后不久，研究表明已能够找出在更高温度即在70～90°K，甚至高达100°K下表现出超导性的新材料。
这些材料大部分是以稀土，碱土，过渡金属和氧为基础制成的。更具体地讲，已发现最有前途的体系似乎是以钇和/或镧，钡和/或锶和/或钙，铜和/或镍和/或钴和/或锰，和氧为基础的体系。
文献中制备这些材料的一般合成方法是让相应元素的氧化物和/或含阴离子盐（如碳酸盐）之间于高温（1000℃）下进行固相反应，后者化合物呈粉态。
不过，该法不利于精确控制并且制成的粉的烧结能力似显不够。
但是，在某些实际应用中，单独使用超导烧结产品才具有现实意义。
因此，要求既要获得致密和均匀的烧结材料，同时又要保存初始粉的内在超导本性。这就要求首先制得具有良好烧结能力的均匀超导粉。
因此，本发明的目的是解决上述问题，其中提出简单而有效的方法，该法易于用来以再现方式制得具有优良烧结能力的均匀超导粉以及高密度超导烧结材料。
作为本发明的第一目的，现已发现，用本发明方法可制得可烧结超导细粉，该法特征是其中包括以下步骤：
a）将稀土溶胶与至少一种碱土硝酸盐和至少一种过渡金属硝酸盐的溶液混合，所得混合物的pH应调为能使硝酸盐均溶于混合物的值;
b）然后干燥所得混合物;
c）焙烧该干燥产品;
d）必要时研磨焙烧粉。
在本发明以下的说明中，所谓稀土一方面包括元素周期表中原子序数从57～71（包括57和71）的所有元素，另一方面包括钇，按习惯钇在这里类似于稀土。
另一方面，所谓“钇族稀土”指的是原子序数从钐到镥并包括钇的最重稀土元素。
最后，所谓“溶胶”包括各种由固体胶态细颗粒在水相中以分散液构成的体系。
一般来说，本发明所用稀土溶胶可按各种已知方法制得，如按US-A-3024199所述方法，即通过相应水合稀土氧化物的热胶溶制得。
更具体地讲，在制备钇族稀土溶胶时，可按法国专利申请n°8712669所述方法操作。
按此方法，先于室温和搅拌条件下将稀土氧化物与可溶于水并且pKa为2.5～5.0的可控量一元酸如乙酸反应，然后将所得反应介质加热到70～100℃，之后保温1～4h，优选为3～4h。
该文献所述方法还优选包括以下特点：
稀土氧化物（如Y2O3）呈高纯度（高于99%）细粉态，其粒径为几微米左右，该氧化物已预先于850～1050℃，优选为约950℃焙烧2～4h;
采用浓度为1～4°N的乙酸溶液，其量应使其不足化学计量，也就是说酸和以金属阳离子计的稀土氧化物之mol比小于2.5，优先为约1.5;
有时未反应的稀土氧化物过滤，倾析或离心分离除去。
按本发明的优选实施方式，用钇或镧溶胶操作，更优选的是用钇溶胶操作。
按本发明方法，向溶胶中混入可溶于水的至少一种碱土硝酸盐和至少一种过渡金属硝酸盐的溶液。
可用于本发明的碱土硝酸盐主要为钙，钡和锶的硝酸盐。
过渡金属硝酸盐选自铜，镍，锰，钴和铁等的硝酸盐。
上述范围内的溶胶和硝酸盐的选择当然要考虑到要求制得的超导粉的性质和组成。
同样，初始溶液中各元素的比例一般也要根据最终产品所要求的化学计量来加以调节，当然应使其适于获得超导性。
本发明方法还特别适于制得Y-Ba-Cu-O型超导体系。该体系已在Journal    of    Ameriean    Chemical    Society，1987，109，2528-2530的文章中作了说明。
按本发明方法的基本特征，将所得混合物的pH调为能使硝酸盐均处于溶解态，即不出现沉淀的值。该调节主要是通过加酸，优选为硝酸或乙酸来完成的。
按本发明的特别实施方式，先用硝酸或乙酸使初始硝酸盐溶液酸化，然后向其中加稀土溶胶，引入硝酸盐溶液的酸量应使加溶胶后的最终pH低于硝酸在混合物中沉淀的pH。
作为例子，在钇溶胶-硝酸钡-硝酸铜体系的情况下，该临界的pH值为约4.1。
所得混合物含约10～30%（重）的干物质，然后应使其干燥。
干燥可用各种已知方法，如喷雾，即在热气中将混合物喷成雾滴来完成。
优选的是在“flash”反应器中进行干燥，如申请人提出并特别记述于法国专利n°2257326，2419754和2431321中。在这种情况下，使处理气作螺旋运动并在油井式涡流中流动。溶液沿着具有气体螺旋轨迹对称轴的混乱轨迹注入，这可极好地将气体的动量传递给溶液。气体还起双重作用：一方面是进行喷雾，即将溶液转化成细微雾滴，另一方面干燥所得雾滴。此外，颗粒在反应器中的停留时间极短，不足1/10秒左右，这排除了与气体接触时间过长而带来的所有过热危险。
根据气体和液体各自的流量不同，气体入口温度为600～900℃，优选为700～900℃，干固体出口温度为100～300℃，优选为150～250℃。
所得干产品粒径为几微米左右，如1～10μm。
产品然后进行焙烧。
焙烧在700～1000℃，优选在800～900℃下进行，历时30mm-24h，优选为5-15h。
焙烧在空气或各种空气/氧气混合物，但优选在空气中进行。
另一方面，按本发明特别实施方式，将焙烧产品极快速地冷至室温，相当于淬火操作，例如可用冷空气清扫。
冷却时间一般为几秒钟左右。
焙烧结束后得到超导粉，肉眼可见的粒径为1-10μ左右，这些1-10μ的颗粒是由粒径100-600
Figure 881067326_IMG1
左右的雏晶构成的。
所得粉一般还应加以研磨，优选是进行干性研磨，以进行良好的烧结。粉的平均粒径分布为0.5-2μ左右，优选为1-2μ。
这些超导粉的显著特征是烧结后可制成极均匀的超导烧结材料，其密度大于该材料理论密度的96%。
粉的烧结温度为900～1000℃，烧结时间一般为2-10h。优选的是，烧结在氧气中进行。
更具体地讲，本发明超导粉的烧结特性是按以下方法确定的：
粉首先在1.5T/cm2的单嵫沽ο录踊虿患诱辰峒炼瞥善缓笥? 950℃下烧结2h并于7h内冷至室温;并测定所得产品密度。各种情况下测得的最终密度均大于所说材料理论密度的95%。
另一方面，还观察到所得产品的超导性极好。
从以下实施例中可清楚地看出本发明的其它优点和实施方案。
实施例
该实施例说明按本发明制备式Y-Ba2-Cu3-Ox（6.5≤x≤7）的超导材料的方法。
A-制粉
向800ml    70℃的水中溶入76.8g硝酸钡和106.6g硝酸铜。
用27ml浓乙酸酸化此溶液。
然后于搅拌条件下向此混合物中加100ml    166g/l的氧化钇浓钇溶胶。该溶胶根据例如法国专利申请n°8712669所述方法制得。
混合均匀后将所得溶液进行喷雾干燥。
干燥在“flash”反应器，如法国专利n°2257326，2419754和2431321所述反应器中进行。
气体入口温度为800℃，其出口温度为200℃。
干燥后所得粉然后于850℃在空气中焙烧10-15h，之后极迅速地冷却至室温。
这以后，进行干式研磨以制成平均粒径小于2μm的粉。
所得粉的特点如下：
比表面积（BET） 3m2/g
总孔容 0.38cm3/g
其真实孔容 0.28cm3/g
和粒间容积 0.10cm3/g
孔隙范围    0.02-10μm
平均孔径    0.6μm
平均粒径    1.3μm
晶体的平均尺寸 约400
Figure 881067326_IMG2
颗粒粒径分布如下（φ＝直径）
φ＞4μm    20%
0.7μm＜φ＜4μm    60%
φ＜0.7μm    20%
B-粉的烧结
粉在干性单轴压力下制成片，压力为1.5T/cm2，然后于950°在氧气中烧结2h并于7h内冷至室温。
所得材料密度等于理论密度的96%。
该材料具有超导性，开始转变的“onset”温度从92°K开始，其平均式为Y-Ba2-Cu3-O6.9。

Claims (20)

1、基本上以稀土，至少一种碱土，至少一种过渡金属和氧为基础制成超导细粉的方法，其特征是其中包括以下步骤：
a)将稀土溶胶与至少一种碱土硝酸盐和至少一种过渡金属硝酸盐的溶液混合。所得混合物的pH应调为能使硝酸盐均溶于混合物的值；
b)然后干燥所得混合物；
c)焙烧酶稍锊罚?
d)必要时研磨焙烧粉。
2、权利要求1的方法，其特征是加硝酸或乙酸调节pH。
3、权利要求2的方法，其特征是加料在硝酸盐溶液中进行。
4、上述权利要求中任一项的方法，其特征是进行喷雾干燥。
5、权利要求4的方法，其特征是喷雾是将溶液沿着具有螺旋轨迹对称轴的混乱轨迹注入来进行的并且热气的油井式涡流可确保喷雾后进行干燥，颗粒在反应器中的停留时间少于1/10秒左右。
6、权利要求5的方法，其特征是热气入口温度为600～900℃。
7、权利要求6的方法，其特征是入口温度为700～900℃。
8、上述权利要求中任一项的方法，其特征是干固体出口温度为100～300℃。
9、权利要求8的方法，其特征是出口温度为150～250℃。
10、上述权利要求中任一项的方法，其特征是焙烧在700～1000℃，优选为800～900℃下进行。
11、上述权利要求中任一项的方法，其特征是焙烧在空气中进行。
12、上述权利要求中任一项的方法，其特征是焙烧产品极迅速地冷至室温。
13、上述权利要求中任一项的方法，其特征是进行干式研磨。
14、权利要求10的方法，其特征是研磨使焙烧产品平均粒径小于2μm。
15、上述权利要求中任一项的方法，其特征是碱土硝酸盐选自钙，锶和钡的硝酸盐。
16、上述权利要求中任一项的方法，其特征是过渡金属硝酸盐选自铜，镍，锰，钴和铁的硝酸盐。
17、上述权利要求中任一项的方法，其特征是采用稀土溶胶和硝酸钡和硝酸铜的溶液。
18、上述权利要求中任圆柱的方法，其特征是采钇溶液。
19、基本上以稀土，至少一种碱土，至少一种过渡金属和氧的基础并易于用权利要求1～18中任一项所述方法制得的超导陶瓷粉。
20、基本上以稀土，至少一种碱土，至少一种过渡金属和氧为基础并易于用权利要求19的粉烧结而成的超导烧结陶瓷材料。
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