CN106747406A - 无铅高绝缘陶瓷涂层氧化锌避雷器阀片及其制备方法 - Google Patents

无铅高绝缘陶瓷涂层氧化锌避雷器阀片及其制备方法 Download PDF

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Publication number
CN106747406A
CN106747406A CN201710078786.2A CN201710078786A CN106747406A CN 106747406 A CN106747406 A CN 106747406A CN 201710078786 A CN201710078786 A CN 201710078786A CN 106747406 A CN106747406 A CN 106747406A
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China
Prior art keywords
unleaded
arrester valve
ceramic coatings
valve block
ball
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Pending
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CN201710078786.2A
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English (en)
Inventor
裴广强
顾涛
姚政
时雯
施利毅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDK Electronics AG
University of Shanghai for Science and Technology
Original Assignee
AIPUKESI ELECTRONIC ELEMENT (ZHUHAI BONDED AREA) Co Ltd
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Application filed by AIPUKESI ELECTRONIC ELEMENT (ZHUHAI BONDED AREA) Co Ltd filed Critical AIPUKESI ELECTRONIC ELEMENT (ZHUHAI BONDED AREA) Co Ltd
Priority to CN201710078786.2A priority Critical patent/CN106747406A/zh
Publication of CN106747406A publication Critical patent/CN106747406A/zh
Priority to EP18720355.9A priority patent/EP3584073A2/en
Priority to JP2019543336A priority patent/JP6880425B2/ja
Priority to US16/486,148 priority patent/US10774011B2/en
Priority to PCT/IB2018/050880 priority patent/WO2018150325A2/zh
Pending legal-status Critical Current

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Abstract

本发明公开了无铅高绝缘陶瓷涂层氧化锌避雷器阀片及其制备方法，无铅高绝缘陶瓷涂层氧化锌避雷器阀片包括避雷器阀片本体1，所述避雷器阀片本体侧面覆有无铅高绝缘陶瓷涂层2，上下面覆有铝层3，其中所述高绝缘陶瓷涂层由质量配比范围为ZnO:86‑95%，Bi2O3:1.0‑3.0%，Co3O4:0.5‑1.5%，Mn3O4:0.2‑1.0%，Sb2O3:3.0‑9.0%，NiO:0.2‑1.0%，SiO2:1.0‑3.0%和PVA溶液及玛瑙磨球制成。本发明配方中不含有铅成分，在其制备过程中将不会产生有害物质，无铅对人类社会和环境友好，有利于环保，符合当今世界走可持续发展的趋势。

Description

无铅高绝缘陶瓷涂层氧化锌避雷器阀片及其制备方法
技术领域
本发明涉及电工陶瓷技术领域，尤其是涉及无铅高绝缘陶瓷涂层氧化锌避雷器阀片及其制备方法。
背景技术
氧化锌避雷器是一种过电压保护装置，氧化锌避雷器阀片作为氧化锌避雷器的核心部件，它的性能直接影响着避雷器的使用，而侧面绝缘涂层的好坏会直接决定避雷器耐受大电流冲击水平的高低。目前，氧化锌避雷器阀片侧面涂层材料包括含铅侧面釉、以环氧涂层和有机硅涂层为主的有机涂层和传统的无机涂层。
含铅侧面釉的由于其主要成分为PbO，而PbO是一种有毒的物质，当坯体处于高温烧结或加工时易挥发，将对人类社会和自然界造成长期无法逆转的危害，不符合当今世界环境友好的发展趋势。
对于有机涂层由于其与电阻片坯体存在结合性不好，因此，表面容易吸附水或者有气泡产生，使得它的耐受过电压变差，此外，环氧涂料的热膨胀系数与电阻片坯体差别会较大，当受到冲击时环氧树脂可能会产生裂纹而导致侧面绝缘涂层的闪络。有机涂层的使用温度不高，在一定程度上也限制了此类氧化锌电阻片的使用范围。
传统的无机涂层需要把电阻片坯体预烧过，才能进行施涂，这样就带来了一个二次烧结的问题，与其他工艺相比，多出了一道工序，导致工艺繁琐，烧结次数增加，烧结时间延长，对于电阻片各项电性能的稳定性控制变差，且极大浪费电能，不利于环保，也不利于工业生产的节能减排要求。
发明内容
基于现有技术的不足，本发明的目的是提供一种烧结无铅高绝缘陶瓷涂层氧化锌避雷器阀片及其制备方法，采用与坯体组分相容性好的无机材料组成，经过科学的配比与筛选，制备出与坯体的膨胀系数相适应且致密度高的陶瓷涂层，并通过一系列工艺将该陶瓷涂层覆与氧化锌避雷器阀片本体上，实现在电阻片侧面形成绝缘强度高的无机保护层，简化工艺，避免二次烧结的工艺繁琐，降低成本。
为实现上述目的，本发明的技术方案为：
无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，包括以下步骤：
步骤一：按以下质量百分比的原料配置初始粉料：ZnO:86-95%；Bi2O3:1.0-3.0%；Co3O4:0.5-1.5%；Mn3O4:0.2-1.0%；Sb2O3:3.0-9.0%；NiO:0.2-1.0%；SiO2:1.0-3.0%；
步骤二：配置陶瓷涂层粉料，其中初始粉料总质量、去离子水质量、玛瑙磨球质量的比例为3:2:4；装入聚氨酯球磨罐中球磨，将球磨后的浆料烘干、粉碎，制得陶瓷涂层粉料；
步骤三：先配置PVA溶液，再取步骤二制得的陶瓷涂层粉料，其中陶瓷涂层粉料、PVA溶液、玛瑙磨球质量的比例为1:0.6:3，装入聚氨酯球磨罐中球磨，制得陶瓷涂层浆料；
步骤四：将陶瓷涂层浆料均匀涂布于压制成型的ZnO压敏电阻片的侧面，待浆体干燥后，随坯体放入加热炉进行整体排胶，将排胶后的电阻片烧成，对烧成后的坯体进行磨片处理和热处理，对热处理后的电阻片端面进行喷铝电极，即可制得一次烧结无铅高绝缘陶瓷涂层氧化锌避雷器阀片产品。
优选的，步骤二中球磨时间12-48h，转速为450r/min。
优选的，步骤三中球磨12-48h，转速为400r/min。
优选的，步骤四中按照施涂质量范围为8-12 mg/cm2将陶瓷涂层浆料均匀涂布于压制成型的ZnO压敏电阻片的侧面。
优选的，步骤四中排胶温度为500℃～650℃，保温2-3h。
优选的，步骤四中烧成工艺为在980℃～1080℃温度条件下进行烧成，保温3-4h。
优选的，步骤四中热处理工艺中热处理温度：480℃～515℃，保温时间1～2h。
优选的，步骤二中在球磨前添加初始粉料总、去离子水和玛瑙磨球总质量的0.5%-1.0%的聚丙烯酸铵分散剂一起球磨。
优选的，步骤三中球磨前添加陶瓷涂层粉料、PVA溶液和玛瑙磨球总质量的1%-2%聚丙烯酸铵分散剂一起球磨。
无铅高绝缘陶瓷涂层氧化锌避雷器阀片，包括避雷器阀片本体，所述避雷器阀片本体侧面覆有无铅高绝缘陶瓷涂层，上下面覆有铝层，其中所述高绝缘陶瓷涂层由质量配比范围为ZnO:86-95%，Bi2O3:1.0-3.0%，Co3O4:0.5-1.5%，Mn3O4:0.2-1.0%，Sb2O3:3.0-9.0%，NiO:0.2-1.0%，SiO2:1.0-3.0%和PVA溶液及玛瑙磨球制成。
所述PVA溶液的质量百分比浓度为5-10%。
本发明的有益效果为：
本发明的一次烧结无铅高绝缘陶瓷涂层氧化锌避雷器阀片产品配方中不含有铅成分，在其制备过程中将不会产生有害物质，无铅对人类社会和环境友好，有利于环保，符合当今世界走可持续发展的趋势；
本发明采用与坯体组分匹配性好的无机材料组成，涂层和坯体的热膨胀系数接近，烧结后，涂层和坯体结合良好，且无机涂层使用温度较有机涂层高，扩大了施涂此种电阻片的使用范围；
本发明只需经过一次烧结，就能够在电阻片侧面形成绝缘强度高的无机保护层，简化了工艺，避免了二次烧结的工艺繁琐，降低了成本。
附图说明
图1为本发明具体实施例的结构示意图；
图2为本发明具体实施例的剖面示意图。
具体实施方式
以下将结合实施例和附图对本发明的构思、具体结构及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法的实施例一：
1、按以下重量百分比的原料配置：ZnO：88.4%；Bi2O3:2.5%；Co3O4:0.6%；Mn3O4:0.4%；Sb2O3:7%；NiO:0.3%；SiO2:0.8%。
2、按上述配比配制陶瓷涂层粉料，粉料总质量、去离子水质量、玛瑙磨球质量的比例为3:2:4，加入聚丙烯酸铵型分散剂，其用量为粉料总质量的0.5%，装入10L规格聚氨酯球磨罐中，用罐式球磨机球磨48h，转速设置为450r/min。将球磨后的浆料取出，过筛后放入烘箱中烘干，然后用粉碎机进行粉碎并过筛；由此制得ZnO陶瓷涂层粉料。
3、取质量百分比浓度为10%PVA溶液和用量为粉料总质量的1%聚丙烯酸铵型分散剂，得到混合溶液并过筛。取上述陶瓷涂层粉料，粉料总重量为0.5kg，粉料总质量、混合溶液、玛瑙磨球质量的比例为1:0.6:3，装入5L规格聚氨酯球磨罐中，用罐式球磨机球磨16h，转速设置为400r/min。将球磨后的浆料取出，过筛，浆料含固率为70%左右。
4、将上述制备的陶瓷涂层浆料采取辊涂方式均匀涂布于压制成型的ZnO压敏电阻片的侧面，施涂质量约为8 mg/cm2，待浆体干燥后，随坯体放入加热炉进行整体排胶，温度控制为405℃，保温3h。将排胶后的电阻片在980℃温度条件下进行烧成，保温4h。对烧成后的坯体进行磨片处理。将研磨后的电阻片放在高温电炉中进行热处理，热处理温度495℃，热处理保温时间2h。对热处理后的电阻片端面进行喷铝电极处理即可制得一次烧结无铅高绝缘陶瓷涂层氧化锌避雷器阀片产品。
实施例二：
1、按以下重量百分比的原料配置：ZnO：89.2%；Bi2O3:2.0%；Co3O4:1.0%；Mn3O4:0.8%；Sb2O3:5.0%；NiO:0.5%；SiO2:1.5%。
2、按上述配比配制陶瓷涂层粉料，粉料总质量、去离子水质量、玛瑙磨球质量的比例为3:2:4，加入聚丙烯酸铵型分散剂，其用量为粉料总质量的1.0%，装入10L规格聚氨酯球磨罐中，用罐式球磨机球磨48h，转速设置为450r/min。将球磨后的浆料取出，过筛后放入烘箱中烘干，然后用粉碎机进行粉碎并过筛；由此制得ZnO陶瓷涂层粉料。
3、取质量百分比浓度为6.5%PVA溶液和用量为粉料总质量的1%聚丙烯酸铵型分散剂，得到混合溶液并过筛。取上述陶瓷涂层粉料，粉料总重量为0.5kg，粉料总质量、混合溶液、玛瑙磨球质量的比例为1:0.6:3，装入5L规格聚氨酯球磨罐中，用罐式球磨机球磨16h，转速设置为400r/min。将球磨后的浆料取出，过筛，浆料含固率约为55%。
4、将上述制备的陶瓷涂层浆料采取辊涂方式均匀涂布于压制成型的ZnO压敏电阻片的侧面，施涂质量约为9 mg/cm2，待浆体干燥后，随坯体放入加热炉进行整体排胶，温度控制为415℃，保温3h。将排胶后的电阻片在1010℃温度条件下进行烧成，保温4h。对烧成后的坯体进行磨片处理。将研磨后的电阻片放在高温电炉中进行热处理，热处理温度：510℃，热处理保温时间2h。对热处理后的电阻片端面进行喷铝电极处理即可制得一次烧结无铅高绝缘陶瓷涂层氧化锌避雷器阀片产品。
实施例三：
1、按以下重量百分比的原料配置：ZnO：86%；Bi2O3:1.0%；Co3O4:0.5%；Mn3O4:0.2%；Sb2O3:3%；NiO:0.2%；SiO2:1%。
2、按上述配比配制陶瓷涂层粉料，粉料总质量、去离子水质量、玛瑙磨球质量的比例为3:2:4，加入聚丙烯酸铵型分散剂，其用量为粉料总质量的0.5%，装入10L规格聚氨酯球磨罐中，用罐式球磨机球磨48h，转速设置为450r/min。将球磨后的浆料取出，过筛后放入烘箱中烘干，然后用粉碎机进行粉碎并过筛；由此制得ZnO陶瓷涂层粉料。
3、取质量百分比浓度为5%PVA溶液和用量为粉料总质量的1%聚丙烯酸铵型分散剂，得到混合溶液并过筛。取上述陶瓷涂层粉料，粉料总重量为0.5kg，粉料总质量、混合溶液、玛瑙磨球质量的比例为1:0.6:3，装入5L规格聚氨酯球磨罐中，用罐式球磨机球磨16h，转速设置为400r/min。将球磨后的浆料取出，过筛，浆料含固率为65%左右。
4、将上述制备的陶瓷涂层浆料采取辊涂方式均匀涂布于压制成型的ZnO压敏电阻片的侧面，施涂质量约为8 mg/cm2，待浆体干燥后，随坯体放入加热炉进行整体排胶，温度控制为405℃，保温3h。将排胶后的电阻片在980℃温度条件下进行烧成，保温4h。对烧成后的坯体进行磨片处理。将研磨后的电阻片放在高温电炉中进行热处理，热处理温度495℃，热处理保温时间2h。对热处理后的电阻片端面进行喷铝电极处理即可制得一次烧结无铅高绝缘陶瓷涂层氧化锌避雷器阀片产品。
实施例四：
1、按以下重量百分比的原料配置：ZnO：95%；Bi2O3:3%；Co3O4:1.5%；Mn3O4:1.0%；Sb2O3:9%；NiO:1.0%；SiO2:3.0%。
2、按上述配比配制陶瓷涂层粉料，粉料总质量、去离子水质量、玛瑙磨球质量的比例为3:2:4，加入聚丙烯酸铵型分散剂，其用量为粉料总质量的1.0%，装入10L规格聚氨酯球磨罐中，用罐式球磨机球磨48h，转速设置为450r/min。将球磨后的浆料取出，过筛后放入烘箱中烘干，然后用粉碎机进行粉碎并过筛；由此制得ZnO陶瓷涂层粉料。
3、取质量百分比浓度为6%PVA溶液和用量为粉料总质量的1%聚丙烯酸铵型分散剂，得到混合溶液并过筛。取上述陶瓷涂层粉料，粉料总重量为0.5kg，粉料总质量、混合溶液、玛瑙磨球质量的比例为1:0.6:3，装入5L规格聚氨酯球磨罐中，用罐式球磨机球磨16h，转速设置为400r/min。将球磨后的浆料取出，过筛，浆料含固率为80%。
4、将上述制备的陶瓷涂层浆料采取辊涂方式均匀涂布于压制成型的ZnO压敏电阻片的侧面，施涂质量约为8 mg/cm2，待浆体干燥后，随坯体放入加热炉进行整体排胶，温度控制为405℃，保温3h。将排胶后的电阻片在980℃温度条件下进行烧成，保温4h。对烧成后的坯体进行磨片处理。将研磨后的电阻片放在高温电炉中进行热处理，热处理温度495℃，热处理保温时间2h。对热处理后的电阻片端面进行喷铝电极处理即可制得一次烧结无铅高绝缘陶瓷涂层氧化锌避雷器阀片产品。
上述四个实施例的测试结果为，避雷器阀片在500A、通电时间2ms的通电电流下都可以安全通过，在100KA、4/10μs下也可安全通过。
如图1和图2所示，由上述方法制成的无铅高绝缘陶瓷涂层氧化锌避雷器阀片，包括避雷器阀片本体1，所述避雷器阀片本体侧面覆有无铅高绝缘陶瓷涂层2，上下面覆有铝层3，其中所述高绝缘陶瓷涂层由质量配比范围为ZnO:86-95%，Bi2O3:1.0-3.0%，Co3O4:0.5-1.5%，Mn3O4:0.2-1.0%，Sb2O3:3.0-9.0%，NiO:0.2-1.0%，SiO2:1.0-3.0%和PVA溶液及玛瑙磨球制成。
本发明PVA溶液质量百分比浓度为5-10%。
需要说明的是，以上所述只是本发明的较佳实施例而已，本发明并不局限于上述实施方式，只要其以相同的手段达到本发明的技术效果，都应属于本发明的保护范围。

Claims (10)

1.无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于包括以下步骤：
步骤一：按以下质量百分比的原料配置初始粉料：ZnO:86-95％；Bi2O3:1.0-3.0％；Co3O4:0.5-1.5％；Mn3O4:0.2-1.0％；Sb2O3:3.0-9.0％；NiO:0.2-1.0％；SiO2:1.0-3.0％；
步骤二：配置陶瓷涂层粉料，其中初始粉料总质量、去离子水质量、玛瑙磨球质量的比例为3:2:4；装入聚氨酯球磨罐中球磨，将球磨后的浆料烘干、粉碎，制得陶瓷涂层粉料；
步骤三：先配置PVA溶液，再取步骤二制得的陶瓷涂层粉料，其中陶瓷涂层粉料、PVA溶液、玛瑙磨球质量的比例为1:0.6:3，装入聚氨酯球磨罐中球磨，制得陶瓷涂层浆料；
步骤四：将陶瓷涂层浆料均匀涂布于压制成型的ZnO压敏电阻片的侧面，待浆体干燥后，随坯体放入加热炉进行整体排胶，将排胶后的电阻片烧成，对烧成后的坯体进行磨片处理和热处理，对热处理后的电阻片端面进行喷铝电极，即可制得无铅高绝缘陶瓷涂层氧化锌避雷器阀片产品。
2.如权利要求1所述的无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于：步骤二中球磨时间12-48h，转速为450r/min。
3.如权利要求1所述的无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于：步骤三中球磨12-48h，转速为400r/min。
4.如权利要求1所述的无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于：步骤四中按照施涂质量范围为8-12mg/cm2将陶瓷涂层浆料均匀涂布于压制成型的ZnO压敏电阻片的侧面。
5.如权利要求1所述的无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于：步骤四中排胶温度为500℃～650℃，保温2-3h。
6.如权利要求1所述的无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于：步骤四中烧成工艺为在980℃～1080℃温度条件下进行烧成，保温3-4h。
7.如权利要求1所述的无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于：步骤四中热处理工艺中热处理温度：480℃～515℃，保温时间1～2h。
8.如权利要求1所述的无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于：步骤二中在球磨前添加初始粉料总、去离子水和玛瑙磨球总质量的0.5％-1.0％的聚丙烯酸铵分散剂一起球磨。
9.如权利要求1所述的无铅高绝缘陶瓷涂层氧化锌避雷器阀片制备方法，其特征在于：步骤三中球磨前添加陶瓷涂层粉料、PVA溶液和玛瑙磨球总质量的1％-2％聚丙烯酸铵分散剂一起球磨。
10.无铅高绝缘陶瓷涂层氧化锌避雷器阀片，其特征在于：包括避雷器阀片本体，所述避雷器阀片本体侧面覆有无铅高绝缘陶瓷涂层，上下面覆有铝层，其中所述高绝缘陶瓷涂层由质量配比范围为ZnO:86-95％，Bi2O3:1.0-3.0％，Co3O4:0.5-1.5％，Mn3O4:0.2-1.0％，Sb2O3:3.0-9.0％，NiO:0.2-1.0％，SiO2:1.0-3.0％和PVA溶液及玛瑙磨球制成。
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