CN113862672B - 用于熔盐电解法的钨电极的制备方法 - Google Patents

用于熔盐电解法的钨电极的制备方法 Download PDF

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CN113862672B
CN113862672B CN202111153293.3A CN202111153293A CN113862672B CN 113862672 B CN113862672 B CN 113862672B CN 202111153293 A CN202111153293 A CN 202111153293A CN 113862672 B CN113862672 B CN 113862672B
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张鸣一
高平
王昊
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Inner Mongolia Metal Material Research Institute
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Abstract

本发明公开了一种用于熔盐电解法的钨电极的制备方法。该制备方法包括如下步骤：(1)将铜粉采用等离子喷涂工艺喷涂在待处理的钨电极的待喷涂部位，形成第一复合层；(2)将复合粉末采用超高速激光熔覆工艺覆盖在第一复合层上，形成第二复合层；(3)将氧化锆粉末采用等离子喷涂工艺覆盖在第二复合层上，形成第三复合层。该方法能够提高钨电极的使用寿命。

Description

用于熔盐电解法的钨电极的制备方法
技术领域
本发明涉及一种用于熔盐电解法的钨电极的制备方法，特别涉及一种用于熔盐电解法制备稀土的钨电极的制备方法。
背景技术
稀土元素具有广泛的用途，已被应用于航空、航天及军工材料中。稀土元素易于与氧等元素结合，所以单质稀土无法稳定存在。目前主要采用熔盐电解法制备稀土单质。在熔盐电解过程中通常采用氟化物及氧化物作为熔盐电解液，电解电流可以达到5000A以上，电解质工作温度为1000～1400℃，电解液挥发会产生浓度较高的氢氟酸气体，具有较强的腐蚀性。实际生产过程中通常采用钨棒作为阴极，石墨作为阳极。钨棒暴露在熔盐电解液液面以上，特别是靠近熔盐电解液液面的部位，除了要经受高温外，还要受到挥发性气体的氧化，导致钨棒电极的寿命仅能达到200天左右，增加了生产成本，影响了生产效率。提升钨电极的使用寿命成为亟待解决的问题。
发明内容
本发明的目的在于提供一种用于熔盐电解法的钨电极的制备方法，该方法能够提高钨电极的使用寿命。
本发明提供了一种用于熔盐电解法的钨电极的制备方法，包括如下步骤：
(1)将铜粉采用等离子喷涂工艺喷涂在待处理的钨电极的待喷涂部位，形成第一复合层；
其中，所述铜粉的粒度≤200目；所述钨电极的待喷涂部位为自钨电极与导电电极片相连的一端起，钨电极长度的1/15～1/7处至钨电极长度的1/5～2/5处之间区域的钨电极表面；
(2)将复合粉末采用超高速激光熔覆工艺覆盖在第一复合层上，形成第二复合层；
其中，所述复合粉末的粒度≤200目；所述复合粉末包括C 0.01～0.08wt％，Si1.0～3.5wt％，W 2.0～5.0wt％，Fe 3.0～7.0wt％，Ni 40.00～60.00wt％，Mo 10～17wt％，Cr 20～30wt％和B 0.3～0.9wt％；
(3)将氧化锆粉末采用等离子喷涂工艺喷涂在第二复合层上，形成第三复合层；
其中，所述氧化锆粉末的粒度≤200目。
根据本发明的制备方法，优选地，铜粉为气化球形铜粉。
铜粉的粒度≤200目；优选为≤300目；更优选≤500目。铜粉可以为气化球形铜粉。这样有助于形成高质量的第一复合层，这样的第一复合层与钨电极之间的结合力强，增强钨电极的抗腐蚀性；且能够提高与第二复合层之间的附着力，防止第二复合层在使用的过程中脱落。
钨电极可以为圆棒状。钨电极的直径可以为50～120mm；优选为60～100mm；更优选为70～90mm。钨电极的长度可以为700～1300mm；优选为800～1200mm；更优选为900～1100mm。
根据本发明的制备方法，优选地，还包括如下步骤：
采用喷砂工艺对钨电极的表面进行净化及毛化处理，得到待处理的钨电极。
钨电极经过净化及毛化处理能够增加钨电极的粗糙度，增加复合层和基体的附着面积和结合力。
优选地，钨电极的待喷涂部位为自钨电极与导电电极片相连的一端起，钨电极长度的1/12～1/9处至钨电极长度的1/5～1/3处之间区域的钨电极表面。导电电极片可以为铜板。
根据本发明的制备方法，优选地，步骤(1)中，等离子喷涂工艺的参数为：电流400～800A；电压40～80V；送粉速率：10～25g/min；送气速率25～45L/min。
本发明采用等离子喷涂工艺形成第一复合层。等离子喷涂工艺的参数如下：电流为400～800A，优选为500～700A；电压为40～80V，优选为60～70V；送粉速率为10～25g/min，优选为12～20g/min；送气速率为25～45L/min，优选为28～36L/min。这样对钨电极的热影响小，且提高了第一复合层的均匀性，从而有助于提高钨电极的使用寿命。
第一复合层的厚度可以为0.1～0.8mm；优选为0.2～0.7mm；更优选为0.5～0.6mm。这样既能够延长钨电极的使用寿命，又能够节约成本。
复合粉末中包括C、Si、W、Fe、Ni、Mo、Cr和B。在某些实施方式中，复合粉末由C、Si、W、Fe、Ni、Mo、Cr和B组成。复合粉末中，C的含量为0.01～0.08wt％；优选为0.02～0.07wt％；更优选为0.04～0.06wt％。Si的含量为1.0～3.5wt％；优选为1.5～3.0wt％；更优选为2.3～2.7wt％。W的含量为2.0～5.0wt％；优选为2.5～4.5wt％；更优选为3.4～4.0wt％。Fe的含量为3.0～7.0wt％；优选为4.0～6.0wt％；更优选为4.0～4.6wt％。Ni的含量为40.00～60.00wt％；优选为45.00～55.00wt％；更优选为45.00～50.00wt％。Mo的含量为10～17wt％；优选为12～15wt％。Cr的含量为20～30wt％；优选为25～28wt％。B的含量为0.3～0.9wt％；优选为0.5～0.7wt％。这样能够得到耐高温且耐腐蚀性能良好的第二复合层，从而有助于提高钨电极的使用寿命。
复合粉末的粒度≤200目；优选为≤300目；更优选≤500目。复合粉末可以由原料混粉采用行星式球磨机细化混匀得到。这样能够提高第二复合层的腐蚀性能和耐高温性能，且有助于提高与第一复合层的结合力。
根据本发明的制备方法，优选地，步骤(2)中，超高速激光熔覆工艺的参数为：功率2～5kW；送粉速度10～25g/min；保护气量10～30L/min，送粉气速率0.5～2.5L/min。
本发明采用超高速激光熔覆工艺在第一复合层上，形成第二复合层。超高速激光熔覆工艺的参数如下：功率为2～5kW；优选为3～4kW。送粉速度为10～25g/min；优选为15～20g/min。保护气量为10～30L/min；优选为15～20L/min。送粉气流速为0.5～2.5L/min；优选为1.0～1.8L/min。这样能够提高效率，保证第二复合层的质量。
第二复合层的厚度可以为1.0～2.5mm；优选为1.5～2.0mm。这样既能够延长钨电极的使用寿命，又能够节约成本。
氧化锆粉末的粒度≤200目；优选为≤300目；更优选≤500目。这样能够得到与第二复合层附着力强，且耐高温性能好的第三复合层。
根据本发明的制备方法，优选地，步骤(3)中，等离子喷涂工艺的参数为：电流400～800A；电压40～80V；送粉速率：10～25g/min；送气速率25～45L/min。
本发明采用等离子喷涂工艺形成第三复合层。离子喷涂工艺的参数如下：电流为400～800A，优选为500～650A；电压为40～80V，优选为55～68V；送粉速率为10～25g/min；优选为12～20g/min；送气速率为25～45L/min；优选为28～36L/min。这样能够提高第三复合层的均匀性。
第三复合层的厚度可以为0.2～1.0mm；优选为0.3～0.8mm；更优选为0.6～0.8mm。这样既能够延长钨电极的使用寿命，又能够节约成本。
根据本发明的制备方法，优选地，所述第一复合层的厚度为0.1～0.8mm，所述第二复合层的厚度为1.0～2.5mm，所述第三复合层的厚度为0.2～1.0mm。
根据本发明的制备方法，优选地，还包括如下步骤：
将第三复合层抛光擦亮，得到复合钨电极；将复合钨电极退火，得到用于熔盐电解法的钨电极。
根据本发明的制备方法，优选地，将第三复合层用百叶轮将表面打平，然后用麻轮进行中抛，再用棉轮配合抛光膏进行细抛；将细抛后的第三复合层表面擦亮，得到复合钨电极。这样能够提高钨电极的抗腐蚀效果，提高钨电极的使用寿命。
根据本发明的制备方法，优选地，退火温度为150～250℃，保温时间为6～10h。
在本发明中，退火温度为150～250℃；优选为180～220℃。保温时间为6～10h；优选为7～9h。退火可以在高温电阻炉内进行。这样能够防止内部或表面产生应力裂纹，提高钨电极的使用寿命。
本发明的用于熔盐电解法的钨电极的使用寿命为300天以上；优选为310～360天；更优选为320～340天。
本发明在钨电极的特定部位依次形成由铜形成的第一复合层，由复合粉末形成的第二复合层，由氧化锆粉末形成的第三复合层，三层复合层共同作用，提高了钨电极的耐腐蚀性和耐高温性。这些复合层形成在钨电极的特定部位，既节约了成本又提高了钨电极的使用寿命。
具体实施方式
下面介绍测试方法：
钨电极的使用寿命的测试工况：电解质为质量比为85:15的氟化镧与氟化锂的混合熔盐，电解温度为1100℃，电解电流为8000A，电解电压为8V。
下面介绍原料：
气化球形铜粉：购买自南宫市鑫盾合金焊材喷涂有限公司。
实施例1～3
将钨电极棒(Φ80mm×1000mm)采用喷砂工艺进行表面净化及毛化处理，得到待处理的钨电极。
将气化球形铜粉采用等离子喷涂工艺喷涂在待处理的钨电极的待喷涂部位，形成第一复合层。钨电极的待喷涂部位为自钨电极与导电电极片相连的一端起，钨电极长度的1/10处至钨电极长度的1/4处之间区域的钨电极表面。气化球形铜粉的粒度，形成第一复合层的工艺参数，第一复合层的厚度如表1所示。
将原料混粉采用行星式球磨机细化混匀，得到复合粉末。将复合粉末采用超高速激光熔覆工艺覆盖在第一复合层上，形成第二复合层。超高速激光熔覆工艺使用的设备为6kW超高速激光熔覆设备。复合粉末的成分及粒度，形成第二复合层的工艺参数，第二复合层的厚度如表1所示。
将氧化锆粉末采用等离子喷涂工艺喷涂在第二复合层上，形成第三复合层。氧化锆粉末的粒度，形成第三复合层的工艺参数，第三复合层的厚度如表1所示。
将第三复合层用百叶轮将表面打平，然后用麻轮进行中抛，再用棉轮配合抛光膏进行细抛；将细抛后的第三复合层表面擦亮，得到复合钨电极。
将复合电极在高温电阻炉内退火，退火温度为200℃，保温时间为8h，得到用于熔盐电解法的钨电极。
表1
比较例
将与实施例1相同的钨电极棒直接使用。使用寿命为201天。
本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员可以想到的任何变形、改进、替换均落入本发明的范围。

Claims (8)

1.一种用于熔盐电解法的钨电极的制备方法，特征在于，包括如下步骤：
(1)将铜粉采用等离子喷涂工艺喷涂在待处理的钨电极的待喷涂部位，形成第一复合层；
其中，所述铜粉的粒度≤200目；所述钨电极的待喷涂部位为自钨电极与导电电极片相连的一端起，钨电极长度的1/15～1/7处至钨电极长度的1/5～2/5处之间区域的钨电极表面；
(2)将复合粉末采用超高速激光熔覆工艺覆盖在第一复合层上，形成第二复合层；
其中，所述复合粉末的粒度≤200目；所述复合粉末包括C0.01～0.08wt％，Si 1.0～3.5wt％，W 2.0～5.0wt％，Fe 3.0～7.0wt％，Ni 40.00～60.00wt％，Mo 10～17wt％，Cr20～30wt％和B 0.3～0.9wt％；
(3)将氧化锆粉末采用等离子喷涂工艺喷涂在第二复合层上，形成第三复合层；
其中，所述氧化锆粉末的粒度≤200目；
(4)将第三复合层抛光擦亮，得到复合钨电极；将复合钨电极退火，得到用于熔盐电解法的钨电极；
其中，退火温度为150～250℃，保温时间为6～10h。
2.根据权利要求1所述的制备方法，其特征在于，所述第一复合层的厚度为0.1～0.8mm，所述第二复合层的厚度为1.0～2.5mm，所述第三复合层的厚度为0.2～1.0mm。
3.根据权利要求1所述的制备方法，其特征在于，铜粉为气化球形铜粉。
4.根据权利要求1所述的制备方法，其特征在于，步骤(1)中，等离子喷涂工艺的参数为：电流400～800A；电压40～80V；送粉速率10～25g/min；送气速率25～45L/min。
5.根据权利要求1所述的制备方法，其特征在于，步骤(2)中，超高速激光熔覆工艺的参数为：功率2～5kW；送粉速度10～25g/min；保护气量10～30L/min，送气速率0.5～2.5L/min。
6.根据权利要求1所述的制备方法，其特征在于，步骤(3)中，等离子喷涂工艺的参数为：电流400～800A；电压40～80V；送粉速率：10～25g/min；送气速率25～45L/min。
7.根据权利要求1所述的制备方法，其特征在于，还包括如下步骤：
采用喷砂工艺对钨电极的表面进行净化及毛化处理，得到待处理的钨电极。
8.根据权利要求1所述的制备方法，其特征在于，步骤(4)中，将第三复合层用百叶轮将表面打平，然后用麻轮进行中抛，再用棉轮配合抛光膏进行细抛；将细抛后的第三复合层表面擦亮，得到复合钨电极。
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