CN108238791A - 一种高性能高梯度避雷器阀片的配方及工艺 - Google Patents

一种高性能高梯度避雷器阀片的配方及工艺 Download PDF

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CN108238791A
CN108238791A CN201611227915.1A CN201611227915A CN108238791A CN 108238791 A CN108238791 A CN 108238791A CN 201611227915 A CN201611227915 A CN 201611227915A CN 108238791 A CN108238791 A CN 108238791A
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葛平安
伍建新
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XI'AN TIANGONG ELECTRIC CO Ltd
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Abstract

本发明公开了一种高性能高梯度避雷器阀片的配方及工艺，该阀片采用常规的铋系氧化锌组分系统，常规的原材料和熟料工艺，通过优化Bi2O3和Sb2O3、Cr2O3及SiO2的重量比例，引进烧结后的热处理工艺和低温烧玻璃釉工艺，及控制铝电极的留边大小，达到了低漏流、低压比、高2ms方波通流容量，高温下低功耗和加速老化下低Kct等一系列高性能。本发明采用常规的原材料和熟料工艺，降低高梯度阀片的压比、漏流、高温下功耗和加速老化下的Kct，提高2ms方波通流容量，给小型化的GIS避雷器提供高性能的高梯度阀片，大幅提高GIS避雷器的各项性能，从而提高GIS避雷器的运行可靠性和保护水平。

Description

一种高性能高梯度避雷器阀片的配方及工艺
技术领域
本发明属于电力系统避雷器技术领域，是一种高性能高梯度避雷器阀片的配方及工艺。
背景技术
为了实现避雷器的小型化，三菱公司的Imataki等人于1984年就提出了高梯度氧化锌避雷器阀片的构想。日本的三菱、日立和东芝公司于1997年开发出梯度达400V/mm的高梯度氧化锌避雷器阀片并成功应用于GIS避雷器，大大缩小了GIS避雷器的体积，使GIS避雷器的设计和安装更容易且成本更低。东芝等公司经不断改进，大幅提高了高梯度避雷器阀片的性能，目前的2ms方波通流的能量密度可达300J/cm3，直径100毫米的阀片的10kA压比为1.54左右。国内生产高梯度氧化锌避雷器阀片的公司主要有西电避雷器公司和西安天工。西电避雷器公司从2000年就开始生产高梯度氧化锌避雷器阀片，梯度达320V/mm；西安天工从2012年开始生产高梯度氧化锌避雷器阀片，梯度达360V/mm。近些年国内有很多公司、大学和研究所对高梯度氧化锌避雷器阀片做了大量研究，发表了许多论文，申请了很多高梯度氧化锌避雷器阀片方面的专利，如CN103951415A，CN103021608A，CN102515742A，CN101383208A，CN104671771A。这些专利实现高梯度的技术路线，有的是添加稀土金属氧化物，有的是降低烧成温度，有的是采用高能球磨或纳米原材料，有的是采用化学共沉法制备复合添加剂，因工艺难控制、成本高及综合性能欠佳等不同原因，都较难应用于实际生产；另外这些专利中都没有在高温下功耗的数据。
发明内容
本发明的目的是针对现有技术的不足，采用常规的原材料和熟料工艺，降低高梯度阀片的压比、漏流、高温下功耗和加速老化下的Kct，提高2ms方波通流容量，给小型化的GIS避雷器提供高性能的高梯度阀片，大幅提高GIS避雷器的各项性能，从而提高GIS避雷器的运行可靠性和保护水平。
本发明的高性能高梯度避雷器阀片由圆柱形的氧化锌压敏陶瓷、氧化锌压敏陶瓷侧面的玻璃釉和氧化锌压敏陶瓷上下端面的铝电极三部分构成。
本发明采用常规的铋系氧化锌压敏陶瓷且只用普通梯度氧化锌压敏陶瓷所用的常规添加剂，通过优化Bi2O3和Sb2O3、Cr2O3及SiO2的重量比例及煅烧料的细化来实现高梯度，主要是降低氧化铋的添加量和提高氧化锑的添加量，而不引入稀土金属氧化物。氧化铋的熔点约850度，在烧成时会熔化形成液相而促进氧化锌晶粒长大，从而降低梯度。氧化锑的熔点虽为620度，在烧成升温过程中也会熔化，但其后跟氧化锌反应生成锑锌尖晶石相；锑锌尖晶石相在烧成过程中不会熔化，会在晶界处对氧化锌晶粒的生长起钉扎作用而阻碍其生长，从而提高梯度。
本发明喷铝时使用硅橡胶套做掩模，控制铝电极的留边在0.5毫米以内，主要以此提高2ms方波通流容量。
为了实现上述目的，本发明采取的技术方案是：
一种高性能高梯度避雷器阀片，由下列重量百分比的原材料组成：
1.5-3％的Bi2O3,4-7％的Sb2O3,1-2％的NiO,0.5-2.0％的Co3O4,0.5-2.0％的MnCO3,0.05-0.5％的Cr2O3,0.05-0.5％的SiO2,0.05-0.3％的银玻璃粉，0.01-0.06％的Al(NO3)3*9H2O，其余为ZnO。
如上所述的一种高梯度避雷器阀片，其中，Bi2O3和Sb2O3、Cr2O3及SiO2的重量比例，4x Bi2O3≈Sb2O3+10x(Cr2O3+SiO2)。
如上所述的一种高梯度避雷器阀片，其中，不含稀土金属氧化物。
一种高梯度避雷器阀片的制备工艺，具体步骤如下：
煅烧料制备——浆料制备——喷雾造粒——压制成型——排胶、预烧——烧成——喷玻璃胶——烧釉、热处理——研磨、清洗、烘干——喷铝电极。
如上所述的一种高梯度避雷器阀片的制备工艺，其中，排胶和预烧合为一道工序，排胶的温度为350-450℃，预烧的温度为750-900℃。
如上所述的一种高梯度避雷器阀片的制备工艺，其中，将烧成后的热处理工艺和烧玻璃釉工艺合为一道工序；热处理温度为450-600℃。
如上所述的一种高梯度避雷器阀片的制备工艺，其中，喷铝时使用硅橡胶套做掩模，控制铝电极的留边在0.5毫米以内。
与现有技术相比，本发明产生的有益效果主要体现在：
本发明通过优化Bi2O3和Sb2O3、Cr2O3及SiO2的重量比例，细化煅烧过的添加剂，引进烧结后的热处理工艺和低温烧玻璃釉工艺，及控制铝电极的留边大小，达到了高梯度、低漏流、低压比、低高温下功耗、高2ms方波通流容量及加速老化下的低Kct等一系列高性能。具体的技术效果如下：
1)对D78及D99的阀片，电压梯度都大于360V/mm。
2)漏流低，对D78及D99的阀片，漏流小于5μA。
3)雷电压比低，对D78及D99的阀片，10kA雷电压比分别为1.50和1.46。
4)2ms方波通流容量高，对D78及D99的阀片，通流分别为1200A和1800A，18个脉冲，能量密度达300J/cm3以上。
5)115℃下交流加速老化的Kct小，对D78及D99的阀片，都为0.6左右。
6)高温下功耗低，对D78及D99的阀片，200℃下的功耗都为～100mW/cm3。
具体实施方式
为了便于理解本发明的目的、技术方案及其效果，现将结合实施例对本发明做进一步详细阐述。
本发明的高性能高梯度避雷器阀片，是通过大量的配方和工艺实验并结合理论指导，优化配方和工艺所得，且经多次重复实验验证。对一些术语的说明如下：U1mA指流过阀片的直流电流为1mA时，阀片两端的电压；漏流，指在阀片两端施加0.75*U1mA的直流电压时流过阀片的泄漏电流；电压梯度，指阀片单位厚度的U1mA电压；雷电压比，指8/20μs雷电冲击电流下的残压与U1mA的比值；2ms方波通流容量，需承受18个脉冲，每个脉冲的电流；交流加速老化，在115℃下施加交流电压1000小时，Kct为施加电压1000小时后的功耗和起始功耗的比值；200℃高温下功耗，施加连续工作电压在200℃下测得的功耗；漏流、雷电压比、Kct和200℃下功耗，值越小代表性能越好；2ms方波通流容量，值越大代表性能越好。
本发明的高性能高梯度避雷器阀片，氧化锌压敏陶瓷的主成分为氧化锌，添加剂的重量百分比为：1.5-3％的Bi2O3,4-7％的Sb2O3,1-2％的NiO,0.5-2.0％的Co3O4,0.5-2.0％的MnCO3,0.05-0.5％的Cr2O3,0.05-0.5％的SiO2,0.05-0.3％的银玻璃粉，0.01-0.06％的Al(NO3)3*9H2O，其余为ZnO。
如上所述的一种高梯度避雷器阀片，其中，Bi2O3和Sb2O3、Cr2O3及SiO2的重量比例，4x Bi2O3≈Sb2O3+10x(Cr2O3+SiO2)。
如上所述的一种高梯度避雷器阀片，其中，不含稀土金属氧化物。
一种高梯度避雷器阀片的制备工艺，具体步骤如下：
煅烧料制备——浆料制备——喷雾造粒——压制成型——排胶、预烧——烧成——喷玻璃胶——烧釉、热处理——研磨、清洗、烘干——喷铝电极。
下面结合具体实施例对本发明做进一步说明。
实施例1
本实施例的高性能高梯度避雷器阀片，氧化锌压敏陶瓷各成分的重量百分比如下：90.52％的ZnO，1.8％的Bi2O3,4.2％的Sb2O3,1.0％的NiO,1.0％的Co3O4,1.0％的MnCO3,0.1％的Cr2O3,0.2％的SiO2,0.15％的银玻璃粉，0.03％的Al(NO3)3*9H2O。其生产工艺是按照以下步骤进行的。
1)煅烧料制备
按配方用电子天平分别称取Bi2O3,Sb2O3,NiO,Co3O4,MnCO3,Cr2O3,SiO2,银玻璃粉和Al(NO3)3*9H2O。先用搅拌球磨机将Bi2O3,Sb2O3,NiO,Co3O4,MnCO3,Cr2O3,SiO2和银玻璃粉磨细到1.5微米，再将球磨好的浆料烘干并干混均匀，然后装入刚玉匣钵在推板窑中于800℃下煅烧，最后将煅烧料用搅拌球磨机磨细到0.5微米左右。
2)浆料制备
将氧化锌分散到去离子水中，然后加入磨细的煅烧料、溶解好的硝酸铝、分散剂、消泡剂和溶解好的粘合剂，搅拌2小时以使浆料混合均匀，控制浆料的固含量在65％。
3)造粒
用喷雾干燥机将浆料烘干并造粒，以制备具有一定流动性和堆积密度的粉料，制成的造粒料的平均粒径为100微米左右。
4)压制成型
先用V形含水混料机，以喷雾的形式在造粒料中加入1.2％的去离子水并混料1小时以上，然后将含水的造粒料陈腐36小时，最后按照设定的成型高度和坯体重量干压制成圆柱形坯体。
5)排胶、预烧
将压制的坯体装入有开口的莫来石匣钵中于推板窑中排胶、预烧。排胶的温度为350～450℃，预烧的温度为800℃。
6)烧成
将预烧好的坯体装入无开口的莫来石匣钵中，在1100℃下于推板窑中烧成。
7)喷玻璃浆料
先制备粘合剂溶液，再将玻璃粉和粘合剂溶液搅拌混合均匀，最后将一定重量的玻璃浆料喷涂在陶瓷片的侧面。
8)烧釉、热处理
热处理和烧釉合并在一起，热处理温度为550度。
9)研磨、清洗、烘干
先研磨烧好釉的陶瓷片的上下端面，磨到设定的高度，并满足两端面平行度和端面平整度的要求，再清洗干净，最后烘干。
10)喷铝电极
在研磨好的陶瓷片的上下端面喷上铝电极，使用硅橡胶套做掩模，控制留边在0.4毫米以内。
本实施例的高性能高梯度避雷器阀片，性能处于国际先进水平，能满足各种GIS避雷器的使用要求，测得的性能指标如下表所示。
上面结合实施例对本发明做了进一步的叙述，但本发明并不限于上述实施方式，在本领域的普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下做出各种变化。

Claims (7)

1.一种高梯度避雷器阀片，其特征在于：由下列重量百分比的原材料组成：
1.5-3％的Bi2O3,4-7％的Sb2O3,1-2％的NiO,0.5-2.0％的Co3O4,0.5-2.0％的MnCO3,0.05-0.5％的Cr2O3,0.05-0.5％的SiO2,0.05-0.3％的银玻璃粉，0.01-0.06％的Al(NO3)3*9H2O，其余为ZnO。
2.根据权利要求1所述的高梯度避雷器阀片，其特征在于
其中，Bi2O3和Sb2O3、Cr2O3及SiO2的重量比例，4x Bi2O3≈Sb2O3+10x(Cr2O3+SiO2)。
3.根据权利要求1所述的高梯度避雷器阀片，其特征在于：不含稀土金属氧化物。
4.一种高梯度避雷器阀片的制备工艺，具体步骤如下：
煅烧料制备——浆料制备——喷雾造粒——压制成型——排胶、预烧——烧成——喷玻璃胶——烧釉、热处理——研磨、清洗、烘干——喷铝电极。
5.根据权利要求4所述的一种高梯度避雷器阀片的制备工艺，其特征在于：
排胶和预烧合为一道工序，排胶的温度为350-450℃，预烧的温度为750-900℃。
6.根据权利要求4所述的一种高梯度避雷器阀片的制备工艺，其特征在于：
将烧成后的热处理工艺和烧玻璃釉工艺合为一道工序；热处理温度为450-600℃。
7.根据权利要求4所述的一种高梯度避雷器阀片的制备工艺，其特征在于：喷铝时使用硅橡胶套做掩模，控制铝电极的留边在0.5毫米以内。
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