CN106946561B - Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷及制备方法 - Google Patents
Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷及制备方法 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000013078 crystal Substances 0.000 claims abstract description 91
- 239000000463 material Substances 0.000 claims abstract description 63
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 32
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 26
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 25
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 24
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 11
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 22
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 238000009417 prefabrication Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 description 25
- 238000000034 method Methods 0.000 description 12
- 239000011701 zinc Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910009253 Y(NO3)3 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷及其制备方法，包括有基料和掺杂料，所述基料按重量份计包括有ZnO：87‑95份、Bi2O3：2.0‑4.0份、MnO2：0.4‑0.7份、Sb2O3：1.5‑3.5份、Co2O3：0.5‑1.5份、Cr2O3：0.2‑1.0份、籽晶掺杂料：1‑5份；所述籽晶掺杂料为ZnO、Nb2O5和Y2O3，其质量分数比为ZnO：Nb2O5：Y2O3＝90‑95：0.1‑5：0.1‑5。本发明Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷具有既能降低ZnO晶粒电阻率，又能控制ZnO晶格畸变的特点，最终达到ZnO压敏电阻残压低、老化寿命长、脉冲电流耐受强的特点。
Description
技术领域
本发明涉及一种ZnO压敏陶瓷及其制备方法，特别是一种无Al3+掺杂的 Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷及其制备方法。
背景技术
ZnO压敏电阻是以ZnO为主要原料，添加少量Bi2O3、Co3O4、MnO2、Sb2O3、 Cr2O3等原料，采用陶瓷烧结工艺制备而成。压敏电阻具有良好的非线性和大通流能力等优点，它作为雷电浪涌保护元件在电子电路和电力系统中得到了广泛的应用。随着微电子信息技术的迅猛发展，对元器件的小型化、集成化以至模块化要求愈来愈迫切。小型化的电子元件灵敏度高、抗过电压水平低，这提升了电子设备对雷电防护的需求，需要ZnO压敏电阻能有更低的残压保护水平。
在雷电流侵入设备时，ZnO压敏电阻的ZnO晶界导通，其性能主要有ZnO 晶粒电阻决定。要降低ZnO压敏电阻的残压，必须降低ZnO压敏电阻的电阻率。
现有方法一：在工业生产中大多采用Al离子作为施主离子添加到ZnO压敏电阻原材料中。一般仅添加了0.005mol％Al离子作为施主离子，因此导致 ZnO压敏电阻率降低并不明显。但是如果添加大量的Al离子作为施主离子，又会由于添加Al离子进入尖晶石相和富Bi相中，引起界面态密度下降和势垒高度的降低。使得ZnO压敏电阻的泄漏电流急剧增大，非线性系数下降。
现有方法二：为了能够将施主离子Al有效掺杂到ZnO晶粒中，一些企业改进生产工艺，先将ZnO与Al(NO3)3·9H2O混合，在1200℃～1300℃温度下煅烧，制成籽晶，然后再将籽晶添加到ZnO压敏电阻的配料中，采用陶瓷烧结工艺制备压敏电阻，这样做可以避免Al离子进入尖晶石相和富Bi相中，引起界面态密度下降和势垒高度的降低。上面的方法能达到降低残压的目的，同时也取得一定的效果。为了能降低ZnO晶粒电阻，除了采用上面的籽晶二步法生产工艺外，往往掺杂大量的施主离子Al。但由于Al离子半径仅为0.0535nm，而Zn离子半径为0.074nm，两者的离子半径相差比较大，形成施主掺杂后导致ZnO晶格畸变严重，这必然导致ZnO压敏电阻老化寿命、脉冲电流耐受等性能指标大幅下降，已不能满足工业应用的需求。
发明内容
本发明的目的在于，开发一种无Al3+掺杂的ZnO压敏陶瓷配方及制备方法，本发明Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷具有既能降低ZnO晶粒电阻率，又能控制ZnO晶格畸变的特点，最终达到ZnO压敏电阻残压低、老化寿命长、脉冲电流耐受强的特点。
本发明的技术方案：一种Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷，包括有基料和掺杂料，所述基料按重量份计包括有ZnO：87-95份、Bi2O3：2.0-4.0 份、MnO2：0.4-0.7份、Sb2O3：1.5-3.5份、Co2O3：0.5-1.5份、Cr2O3：0.2-1.0 份、籽晶掺杂料：1-5份；所述籽晶掺杂料为ZnO、Nb2O5和Y2O3，其质量分数比为ZnO：Nb2O5：Y2O3＝90-95：0.1-5：0.1-5。
前述的Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷，所述基料按重量份计包括有ZnO：89-92份、Bi2O3：2.5-3.5份、MnO2：0.5-0.6份、Sb2O3：2-3 份、Co2O3：0.8-1.2份、Cr2O3：0.3-0.8份、籽晶掺杂料：2-4份；所述籽晶掺杂料为ZnO、Nb2O5和Y2O3，其质量分数比为ZnO：Nb2O5：Y2O3＝92-94： 1-4：1-3。
前述的Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷，所述基料按重量份计包括有ZnO：90.5份、Bi2O3：3.0份、MnO2：0.5份、Sb2O3：2.5份、Co2O3：1 份、Cr2O3：0.5份、籽晶掺杂料2份，所述籽晶掺杂料质量分数比为ZnO：Nb2O5： Y2O3＝94：3.5：2.5。
一种前述的Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，包括如下步骤：
(1)籽晶预制：将ZnO：Nb2O5：Y2O3按所述比例混合，Nb2O5和Y2O3可采用硝酸盐的形式加入，同时加入酒精或去离子水，球磨8-24小时，形成籽晶悬浊液，将籽晶悬浊液烘干，得籽晶配合料；
(2)籽晶烧结：将步骤(1)制得的籽晶配合料放入1200-1350℃下烧结3-6小时，烧结后随炉缓慢降至常温，制成籽晶烧结料；
(3)籽晶球磨：将步骤(2)制得的籽晶烧结料球磨处理，籽晶平均粒径小于5μm，制得籽晶备用；
(4)配料、造粒、制坯：向步骤(3)制得的籽晶中按比例加入ZnO、 Bi2O3、MnO2、Sb2O3、Co2O3和Cr2O3混合，向混合物中加入去离子水、聚乙烯醇溶液、分散剂，球磨8-12小时，得到悬浮液，喷雾造粒，压成坯体；
(5)陶瓷烧结：将步骤(4)制得的坯体放入电炉中升温至400℃进行保温排胶，排胶时间4-6小时，排胶后升温至1200-1350℃进行烧结，烧结时间18-23小时，烧结完成后保温3-6小时，使其致密成瓷，然后随炉降温至常温即可。
前述的Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，所述步骤(1) 中，球磨时间为15-17小时。
前述的Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，所述步骤(2) 中，是将步骤(1)制得的籽晶原料放入1270-1280℃下烧结4-5小时。
前述的Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，所述步骤(4) 中，加入聚乙烯醇溶液的质量百分比为5％wt，加入聚乙烯醇溶液的比例为每千克混合物中加入50g聚乙烯醇溶液。
本发明的有益效果：本发明通过复合施主掺杂Nb离子和Y离子，由于Nb 离子半径为0.064nm，Y离子半径为0.09nm，而Zn离子半径为0.074nm。Nb、Y、 Zn的离子半径相差不大，易于形成替位式掺杂，并且Nb离子、Y离子替代了铅锌矿结构中Zn离子格点位置，Nb离子替位掺杂导致晶格收缩、Y离子替位掺杂导致晶格膨胀，可以通过控制Nb离子、Y离子的掺杂比例来精确控制ZnO 晶格畸变，施主掺杂降低了晶粒电阻率和降低ZnO压敏电阻残压、抑制了泄漏电流的增长、抑制非线性系数的下降的同时，又增强了ZnO压敏电阻老化寿命、脉冲电流耐受能力，从而使该材料具有更高的性能和更适于工业应用。
本实验例共以3种不同的制作工艺制作实验样品，第一种为传统工艺，传统工艺不加籽晶掺杂料；第二种为添加籽晶的工艺，如背景技术中所述现有方法二所示；第三种按照本发明所述方法制备；测试样品的压敏电压、漏电流、标称放电电流、残压、加速老化寿命，结果如表1所示。
表1对比数据
通过表1可知：采用本发明专利技术制备的样品漏电流更小、残压更低、脉冲电流耐受能力更强、老化寿命更长，其电性能全面优于传统工艺和现有方法二制备的样品。
具体实施方式
下面结合实施例对本发明作进一步的说明，但并不作为对本发明限制的依据。
本发明的实施例
实施例1：一种Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷，包括有基料和掺杂料，所述基料按重量份计包括有ZnO：90.5份、Bi2O3：3.0份、MnO2： 0.5份、Sb2O3：2.5份、Co2O3：1份、Cr2O3：0.5份、籽晶掺杂料2份，所述籽晶掺杂料质量分数比为ZnO：Nb(NO3)5:Y(NO3)3＝94：3.5：2.5。
实施例2：一种Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷，包括有基料和掺杂料，所述基料按重量份计包括有ZnO：87份、Bi2O3：2.0份、MnO2： 0.4份、Sb2O3：1.5份、Co2O3：0.5份、Cr2O3：0.2份、籽晶掺杂料：1份；所述籽晶掺杂料为ZnO、Nb2O5和Y2O3，其质量分数比为ZnO：Nb2O5：Y2O3＝90： 0.1：0.1。
实施例3：一种Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷，包括有基料和掺杂料，所述基料按重量份计包括有ZnO：95份、Bi2O3：4.0份、MnO2： 0.7份、Sb2O3：3.5份、Co2O3：1.5份、Cr2O3：1.0份、籽晶掺杂料：5 份；所述籽晶掺杂料为ZnO、Nb2O5和Y2O3，其质量分数比为ZnO：Nb2O5：Y2O3＝95：5：5。
实施例4：上述的Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷的制备方法，步骤如下：
(1)籽晶预制：将ZnO、Nb2O5和Y2O3按所述比例混合，加入去离子水和酒精，球磨16小时，形成籽晶悬浊液，将籽晶悬浊液烘干，得籽晶配合料；
(2)籽晶烧结：将步骤(1)制得的籽晶配合料放入1270℃下烧结4 小时，烧结后随炉缓慢降至常温，制成籽晶烧结料；
(3)籽晶球磨：将步骤(2)制得的籽晶烧结料球磨处理，籽晶平均粒径小于5μm，制得籽晶备用；
(4)配料、造粒、制坯：向步骤(3)制得的籽晶烧结料中按比例加入 ZnO、Bi2O3、MnO2、Sb2O3、Co2O3和Cr2O3混合，向混合物中加入去离子水、聚乙烯醇溶液、分散剂，球磨10小时，得悬浮液，喷雾造粒，压成坯体；
(5)陶瓷烧结：将步骤(4)制得的坯体放入电炉中升温至400℃进行保温排胶，排胶时间5小时，排胶后升温至1270℃进行烧结，烧结时间20 小时，烧结完成后保温4小时，使其致密成瓷，然后随炉降温至常温即可。
上述步骤(4)中，加入聚乙烯醇溶液的质量百分比为5％wt，加入聚乙烯醇溶液的比例为每千克混合物中加入50g聚乙烯醇溶液。
实施例5：上述的Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷的制备方法，步骤如下：
(1)籽晶预制：将ZnO、Nb(NO3)3和Y(NO3)3按所述比例混合，加入去离子水和酒精，球磨8小时，形成籽晶悬浊液，将籽晶悬浊液烘干，得籽晶配合料；
(2)籽晶烧结：将步骤(1)制得的籽晶配合料放入1200℃下烧结6 小时，烧结后随炉缓慢降至常温，制成籽晶烧结料；
(3)籽晶球磨：将步骤(2)制得的籽晶烧结料球磨处理，籽晶平均粒径小于5μm，制得籽晶备用；
(4)配料、造粒、制坯：向步骤(3)制得的籽晶烧结料中按比例加入 ZnO、Bi2O3、MnO2、Sb2O3、Co2O3和Cr2O3混合，向混合物中加入去离子水、聚乙烯醇溶液、分散剂，球磨12小时，得悬浮液，喷雾造粒，压成坯体；
(5)陶瓷烧结：将步骤(4)制得的坯体放入电炉中升温至400℃进行保温排胶，排胶时间4小时，排胶后升温至1200℃进行烧结，烧结时间23 小时，烧结完成后保温3小时，使其致密成瓷，然后随炉降温至常温即可。
上述步骤(4)中，加入聚乙烯醇溶液的质量百分比为5％wt，加入聚乙烯醇溶液的比例为每千克混合物中加入50g聚乙烯醇溶液。
实施例6：上述的Y3+、Nb5+复合施主掺杂制备的ZnO压敏陶瓷的制备方法，步骤如下：
(1)籽晶预制：将ZnO、Nb2O5和Y2O3按所述比例混合，加入去离子水和酒精，球磨24小时，形成籽晶悬浊液，将籽晶悬浊液烘干，得籽晶配合料；
(2)籽晶烧结：将步骤(1)制得的籽晶配合料放入1350℃下烧结3 小时，烧结后随炉缓慢降至常温，制成籽晶烧结料；
(3)籽晶球磨：将步骤(2)制得的籽晶烧结料球磨处理，籽晶平均粒径小于5μm，制得籽晶备用；
(4)配料、造粒、制坯：向步骤(3)制得的籽晶烧结料中按比例加入 ZnO、Bi2O3、MnO2、Sb2O3、Co2O3和Cr2O3混合，向混合物中加入去离子水、聚乙烯醇溶液、分散剂，球磨12小时，得悬浮液，喷雾造粒，压成坯体；
(5)陶瓷烧结：将步骤(4)制得的坯体放入电炉中升温至400℃进行保温排胶，排胶时间6小时，排胶后升温至1350℃进行烧结，烧结时间18 小时，烧结完成后保温6小时，使其致密成瓷，然后随炉降温至常温即可。
上述步骤(4)中，加入聚乙烯醇溶液的质量百分比为5％wt，加入聚乙烯醇溶液的比例为每千克混合物中加入50g聚乙烯醇溶液。
Claims (5)
1.一种Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，其特征在于，包括如下步骤：
（1）籽晶预制：将ZnO：Nb2O5：Y2O3按比例混合，Nb2O5和Y2O3采用硝酸盐的形式加入，同时加入酒精或去离子水，球磨8-24小时，形成籽晶悬浊液，将籽晶悬浊液烘干，得籽晶配合料；
（2）籽晶烧结：将步骤（1）制得的籽晶配合料放入1200-1350℃下烧结3-6小时，烧结后随炉缓慢降至常温，制成籽晶烧结料；
（3）籽晶球磨：将步骤（2）制得的籽晶烧结料球磨处理，籽晶平均粒径小于5μm，制得籽晶备用；
（4）配料、造粒、制坯：向步骤（3）制得的籽晶中按比例加入ZnO、Bi2O3、MnO2、Sb2O3、Co2O3和Cr2O3混合，向混合物中加入去离子水、聚乙烯醇溶液、分散剂，球磨8-12小时，得到悬浮液，喷雾造粒，压成坯体；
（5）陶瓷烧结：将步骤（4）制得的坯体放入电炉中升温至400℃进行保温排胶，排胶时间4-6小时，排胶后升温至1200-1350℃进行烧结，烧结时间18-23小时，烧结完成后保温3-6小时，使其致密成瓷，然后随炉降温至常温即可；
所述ZnO压敏陶瓷包括有基料和掺杂料，所述基料按重量份计包括有ZnO：87-95份、Bi2O3：2.0-4.0份、MnO2：0.4-0.7份、Sb2O3：1.5-3.5份、Co2O3：0.5-1.5份、Cr2O3：0.2-1.0份、籽晶掺杂料：1-5份；所述籽晶掺杂料为ZnO、Nb2O5和Y2O3，其质量分数比为ZnO：Nb2O5：Y2O3＝90-95：0.1-5：0.1-5；
所述步骤（4）中，加入聚乙烯醇溶液的质量百分比为5wt％，加入聚乙烯醇溶液的比例为每千克混合物中加入50g聚乙烯醇溶液。
2.根据权利要求1所述的Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，其特征在于：所述基料按重量份计包括有ZnO：89-92份、Bi2O3：2.5-3.5份、MnO2：0.5-0.6份、Sb2O3：2-3份、Co2O3：0.8-1.2份、Cr2O3：0.3-0.8份、籽晶掺杂料：2-4份；所述籽晶掺杂料为ZnO、Nb2O5和Y2O3，其质量分数比为ZnO：Nb2O5：Y2O3＝92-94：1-4：1-3。
3.根据权利要求2所述的Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，其特征在于：所述基料按重量份计包括有ZnO：90.5份、Bi2O3：3.0份、MnO2：0.5份、Sb2O3：2.5份、Co2O3：1份、Cr2O3：0.5份、籽晶掺杂料2份，所述籽晶掺杂料质量分数比为ZnO：Nb2O5：Y2O3＝94：3.5：2.5。
4.根据权利要求1所述的Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，其特征在于：所述步骤（1）中，球磨时间为15-17小时。
5.根据权利要求1所述的Y3+、Nb5+复合施主掺杂ZnO压敏陶瓷的制备方法，其特征在于：所述步骤（2）中，是将步骤（1）制得的籽晶原料放入1270-1280℃下烧结4-5小时。
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