CN116903360A - 一种高梯度氧化锌压敏电阻片的制备方法 - Google Patents
一种高梯度氧化锌压敏电阻片的制备方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 43
- 238000000498 ball milling Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000005416 organic matter Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000011521 glass Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000007873 sieving Methods 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical group CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 abstract description 9
- 239000011029 spinel Substances 0.000 abstract description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000000306 component Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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Abstract
本发明公开了一种高梯度氧化锌压敏电阻片的制备方法，属于电工材料制备技术领域。该方法包括：(1)将Y2O3与表面活性剂水溶液于160‑180℃水热反应得g‑Y2O3；(2)准备第一粉体，包括ZnO、Bi2O3、Sb2O3、Co2O3、MnCO3、NiO、Y2O3和Ag‑glass；(3)将第一粉体和去离子水、有机物水分散液及分散剂混合后球磨，球磨浆料造粒后过100目筛网，得第三粉体；(4)将第三粉体压制成圆柱状样品；(5)圆柱状样品高温煅烧。该方法在高温烧结时稀土氧化物与Zn、Bi等生成新的尖晶石，由于尖晶石的钉扎效应而降低ZnO晶粒的生长速度，导致压敏电阻晶粒尺寸减小，使得电位梯度得以提高。
Description
技术领域
本发明涉及电工材料制备技术领域，具体涉及一种高梯度氧化锌压敏电阻片的制备方法。
背景技术
非线性氧化锌(ZnO)压敏电阻片(以下简称电阻片)是一种高非线性多晶电子陶瓷型电气保护元件，具有优异的非线性电流-电压特性。其优异的非线性特性被广泛应用于过电压保护领域，在金属氧化物避雷器(简称避雷器)领域，电阻片是一个不可或缺的核心部件。然而，特高压电力***中应用的电阻片圆柱具有较高的高度，这通常会导致电位分布不均匀和结构复杂。提高电阻片电位梯度是降低避雷器高度的有效途径，但是电阻片电位梯度的提高往往伴随着电阻片大电流通流能力的降低。此外，电阻片制造过程中引入的杂质、气孔也严重限制了电阻片性能的提升。
目前，通过降低压敏电阻烧成温度和缩短保温时间来减小ZnO晶粒生长速度并减少晶粒生长时间从而提高ZnO压敏电阻的梯度，然而这种方法使ZnO压敏电阻的通流能量、非线性及老化性能等变差；另外的方法是添加适量的Al2O3、SiO2等来抑制ZnO晶粒的生长以提高电位梯度。
发明内容
为了解决现有技术中存在的上述不足之处，本发明的目的在于提供一种高梯度氧化锌压敏电阻片的制备方法，该方法在电阻片配方中添加稀土氧化物并优化各组分配比，高温烧结时稀土氧化物与Zn、Bi，Sb等生成新的尖晶石，由于尖晶石的钉扎效应而降低ZnO晶粒的生长速度，导致压敏电阻晶粒尺寸减小，使得电位梯度得以提高。
为实现上述目的，本发明所采用的技术方案如下：
一种高梯度氧化锌压敏电阻片的制备方法，该方法包括如下步骤：
(1)将Y2O3与表面活性剂的水溶液于160-180℃水热反应10-12h，得到改性后的Y2O3(g-Y2O3)；
(2)准备第一粉体，所述第一粉体包括ZnO、Bi2O3、Sb2O3、Co2O3、MnCO3、NiO、Y2O3和Ag-glass；所述Ag-glass为银玻璃粉；
(3)将第一粉体放入球磨桶内，加入适量去离子水、有机物水分散液及分散剂球磨一定时间，球磨后所得浆料于喷雾造粒塔中造粒，得到第二粉体；将第二粉体过100目筛网，得到第三粉体；
(4)将第三粉体于油压机中压制成圆柱状样品；
(5)将圆柱状样品于高温煅烧炉中在一定温度下煅烧一定时间，即得到所述高梯度氧化锌压敏电阻片。
上述步骤(1)中，所述表面活性剂的水溶液是将表面活性剂分散于水中后得到，所述表面活性剂为聚乙二醇和/或葡萄糖，所述Y2O3与表面活性剂的重量比例为100：(1～5)。
上述步骤(1)中，所述表面活性剂的含固率为3-10wt％。
上述步骤(2)中，所述第一粉体按重量百分比计的组成如下：
上述步骤(3)中，所述第一粉体、去离子水、有机物水分散液和分散剂的质量比例为(45-55)：(45-50)：(20-30)：1。
所述有机物水分散液是将有机物分散到水中后获得，所述有机物为聚乙烯醇、乙烯共聚物和羧甲基纤维素钠中的一种；所述有机物水分散液中有机物的质量浓度为5-10％；所述分散剂为甲基戊醇或聚丙烯酰胺。
上述步骤(3)中，所述球磨的方式为滚桶球磨或搅拌球磨，球磨转速为300-500rpm，球磨时间为5-10h；所述第二粉体的粒度为50-80μm。
上述步骤(4)中，所述圆柱状样品的高度为10-50mm，直径为30-80mm。
上述步骤(5)中，所述煅烧温度为1100-1250℃，煅烧时间为2-4h。
本发明的优点和有益效果如下：
1、ZnO压敏电阻器单位厚度上的晶粒和晶界数量越多，其电位梯度就越高，因此，电阻片晶粒细小化是提高电位梯度的重要途径。本发明通过配方的改进，在配方中添加稀土氧化物，高温烧结时稀土氧化物与Zn、Bi，Sb等生成新的尖晶石，由于尖晶石的钉扎效应而降低ZnO晶粒的生长速度，导致压敏电阻晶粒尺寸减小，电位梯度得以提高。该方法不破坏原有的工艺过程，适应性强，有利于工业化应用。
2、本发明电阻片配方中的稀土氧化物Y2O3使用表面接枝改性工艺，在Y2O3表面包覆一层亲水性的有机物，从而使Y2O3在体系中分布更加均匀，从而使Y2O3与Zn、Bi、Sb等生成的尖晶石分布更加均匀。此外，该工艺可以减少电阻片制造过程中引入的气孔从而保障产品的质量稳定和可控。
3、本旭有在体系中引入表面接枝改性后的稀土氧化物g-Y2O3，高温烧结时该g-Y2O3与Zn、Bi、Sb等生成新的尖晶石，由于尖晶石的钉扎效应而降低ZnO晶粒的生长速度，导致压敏电阻晶粒尺寸减小，使ZnO压敏电阻单位厚度上的晶粒和晶界数量增多，电位梯度得以提高。
具体实施方式
为了便于理解本发明，下文将结合实施例对本发明作更全面、细致地描述，但本发明的保护范围并不限于以下具体的实施例。
除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解的含义相同。本文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。
除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等，均可通过市场购买得到或者可通过现有方法制备得到。
实施例1：
本实施例高梯度氧化锌压敏电阻片的制备方法如下：
S1：将Y2O3与3wt％含固率的聚乙二醇水溶液于170℃水热反应12h，得到改性后的Y2O3(g-Y2O3)。所述Y2O3与聚乙二醇的重量比例为100：2。
S2：准备第一粉体，所述第一粉体为ZnO、Bi2O3、Sb2O3、Co2O3、MnCO3、NiO、Y2O3和Ag-glass(银玻璃粉)；所述第一粉体组分按质量含量为：ZnO为90％，Bi2O3为2％，Sb2O3为3％，Co2O3为1％，MnCO3为1％，NiO为1.5％，g-Y2O3为0.5％，Ag-glass为1％。
S3：将第一粉体放入球磨桶内加适量去离子水、有机物水分散液及分散剂球磨6h，其中：第一粉体、去离子水、有机物水分散液和分散剂的质量比例为50:50:20:1。球磨后的浆料于喷雾造粒塔中造粒，得到粒度为50-80μm的第二粉体，将第二粉体过100目筛网，得到第三粉体。其中：所述有机物水分散液是将聚乙烯醇分散到水中后获得，浓度为8％；所述分散剂为聚丙烯酰胺。所述球磨方式为搅拌球磨，球磨转速为450rpm。
S4：将第三粉体于油压机压制成直径50mm、高度为15mm的圆柱形状样品。
S5：将圆柱形状样品于高温煅烧炉中在1200℃煅烧2h。陶瓷样品在高温煅烧后，样品尺寸在径向和轴向上会有收缩。实际烧成后的样品为直径40.12mm、高度为12.32mm的圆柱形状氧化锌压敏电阻片。
实施例2：
本实施例高梯度氧化锌压敏电阻片的制备方法如下：
S1：将Y2O3与5wt％含固率的葡萄糖水溶液于175℃水热反应10h，得到改性后的Y2O3(g-Y2O3)。所述Y2O3与葡萄糖的重量比例为100：2。
S2：准备第一粉体，所述第一粉体为ZnO、Bi2O3、Sb2O3、Co2O3、MnCO3、NiO、Y2O3和Ag-glass(银玻璃粉)；所述第一粉体组分按质量含量为：ZnO为90％，Bi2O3为2％，Sb2O3为3％，Co2O3为1％，MnCO3为1％，NiO为1％，g-Y2O3为1％，Ag-glass为1％。
S3：将第一粉体放入球磨桶内加适量去离子水、有机物水分散液及分散剂球磨6h；其中：第一粉体、去离子水、有机物水分散液和分散剂的质量比例为50:50:20:1。球磨后的浆料于喷雾造粒塔中造粒，得到粒度为50-80μm的第二粉体，将第二粉体过100目筛网，得到第三粉体。其中：所述有机物水分散液是将羧甲基纤维素钠分散到水中后获得，浓度为8％；所述分散剂为聚丙烯酰胺。所述球磨方式为滚桶球磨，球磨转速为400rpm。
S4：将第三粉体于油压机压制成直径50mm、高度为15mm的圆柱形状样品。
S5：将圆柱样品于高温煅烧炉中在1220℃煅烧2h。陶瓷样品在高温煅烧后，样品尺寸在径向和轴向上会有收缩。实际烧成后的样品为直径40.15mm、高度为12.30mm的圆柱形状氧化锌压敏电阻片。
性能检测：用金属氧化物直流参数测试仪对实施例的ZnO压敏电阻片的U1mA进行检测，检测结果如表1。
表1：实施例的电学性能测试结果：
尽管已描述了本发明的优选实施例，但本领域内的技术人员一旦得知了基本创造性概念，则可对这些实施例作出另外的变更和修改。所以，所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内，则本发明也意图包含这些改动和变型在内。
Claims (9)
1.一种高梯度氧化锌压敏电阻片的制备方法，其特征在于：该方法包括以下步骤：
(1)将Y2O3与表面活性剂的水溶液于160-180℃水热反应10-12h，得到改性后的Y2O3(g-Y2O3)；
(2)准备第一粉体，所述第一粉体包括ZnO、Bi2O3、Sb2O3、Co2O3、MnCO3、NiO、Y2O3和Ag-glass；所述Ag-glass为银玻璃粉；
(3)将第一粉体放入球磨桶内，加入适量去离子水、有机物水分散液及分散剂球磨一定时间，球磨后所得浆料于喷雾造粒塔中造粒，得到第二粉体；将第二粉体过100目筛网，得到第三粉体；
(4)将第三粉体于油压机中压制成圆柱状样品；
(5)将圆柱状样品于高温煅烧炉中在一定温度下煅烧一定时间，即得到所述高梯度氧化锌压敏电阻片。
2.根据权利要求1所述的高梯度氧化锌压敏电阻片的制备方法，其特征在于：步骤(1)中，所述表面活性剂的水溶液是将表面活性剂分散于水中后得到，所述表面活性剂为聚乙二醇和/或葡萄糖，所述Y2O3与表面活性剂的重量比例为100：(1～5)。
3.根据权利要求1或2所述的高梯度氧化锌压敏电阻片的制备方法，其特征在于：步骤(1)中，所述表面活性剂的含固率为3-10wt％。
4.根据权利要求1所述的高梯度氧化锌压敏电阻片的制备方法，其特征在于：步骤(2)中，所述第一粉体按重量百分比计的组成如下：
5.根据权利要求1所述的高梯度氧化锌压敏电阻片的制备方法，其特征在于：步骤(3)中，所述第一粉体、去离子水、有机物水分散液和分散剂的质量比例为(45-55)：(45-50)：(20-30)：1。
6.根据权利要求1或5所述的高梯度氧化锌压敏电阻片的制备方法，其特征在于：所述有机物水分散液是将有机物分散到水中后获得，所述有机物为聚乙烯醇、乙烯共聚物和羧甲基纤维素钠中的一种；所述有机物水分散液中有机物的质量浓度为5-10％；所述分散剂为甲基戊醇或聚丙烯酰胺。
7.根据权利要求1所述的高梯度氧化锌压敏电阻片的制备方法，其特征在于：步骤(3)中，所述球磨的方式为滚桶球磨或搅拌球磨，球磨转速为300-500rpm，球磨时间为5-10h；所述第二粉体的粒度为50-80μm。
8.根据权利要求1所述的高梯度氧化锌压敏电阻片的制备方法，其特征在于：步骤(4)中，所述圆柱状样品的高度为10-50mm，直径为30-80mm。
9.根据权利要求1所述的高梯度氧化锌压敏电阻片的制备方法，其特征在于：步骤(5)中，所述煅烧温度为1100-1250℃，煅烧时间为2-4h。
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