CN109574653A - 一种高非线性、低漏电流压敏电阻片及其制备方法 - Google Patents
一种高非线性、低漏电流压敏电阻片及其制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 25
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 22
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 22
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 22
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 22
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 20
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 20
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 abstract description 10
- 238000010304 firing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 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 9
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 3
- 239000004615 ingredient Substances 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 37
- 239000011787 zinc oxide Substances 0.000 claims description 33
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000003595 mist Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
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- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000005245 sintering Methods 0.000 abstract description 8
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- 239000011701 zinc Substances 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 67
- 229910000416 bismuth oxide Inorganic materials 0.000 description 14
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 14
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 8
- 229910000423 chromium oxide Inorganic materials 0.000 description 8
- 229910000428 cobalt oxide Inorganic materials 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
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- 239000006096 absorbing agent Substances 0.000 description 1
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- 230000003679 aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KAGOZRSGIYZEKW-UHFFFAOYSA-N cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Co+3].[Co+3] KAGOZRSGIYZEKW-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
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Abstract
本发明提供了一种高非线性、低漏电流压敏电阻片，组成成分包括：ZnO、Bi2O3、Co2O3、MnO2、Sb2O3、Cr2O3、NiO、SiO2和Al2O3，且各成分之间的摩尔比为ZnO:Bi2O3:Co2O3:MnO2:Sb2O3:Cr2O3:NiO:SiO2:Al2O3＝1520‑1540:7‑12:15‑17:8‑10:13‑16:4‑6:7‑9:23‑25:0.8‑1.5。进一步的，本发明还提供了上述高非线性、低漏电流压敏电阻片的制备方法。本发明通过氧化物原料的特定配比影响烧结机制和势垒高度，降低了烧成温度并提高了ZnO压敏电阻的非线性，降低ZnO电阻片漏电流，具有更高的性能且制备过程工艺简单，生产成本低，利于规模化生产。
Description
技术领域
本发明属于电工材料制备技术领域，具体涉及一种高非线性、低漏电流压敏电阻片及其制备方法。
背景技术
氧化锌(ZnO)压敏陶瓷是一种多晶的电子陶瓷烧结体，是在氧化锌(ZnO)粉末中加入微量的氧化铋(Bi2O3)、氧化钴(Co2O3)，二氧化锰(MnO2)、氧化锑(Sb2O3)、氧化铬(Cr2O3)等添加物，经过混合成型后在高温下烧结而成的瓷体。它可以作为浪涌吸收器、电压保护器、变阻器和避雷器等，已成为电子陶瓷领域的重要材料。随着集成电路和输电电压等级的不断提高，设备的绝缘问题也日益严峻，采用高梯度的ZnO压敏电阻可以降低设备的绝缘水平，从而减少在提高设备绝缘方面的高昂投入。高的非线性系数会带来更快速的响应和对设备更高效的保护。
ZnO压敏陶瓷配方大多都要在超高的温度(1000～1300℃)下才能实现烧结，颗粒在高温下容易长大和烧结出现硬团聚现象，所以在制备高非线性ZnO压敏陶瓷领域里最大的挑战是限制ZnO晶粒的长大。此外，现在对电子产品安全等级的要求越来越高，也就要求ZnO压敏电阻片的漏电流需要控制在很小的范围之内。
在当前的研究和工业生产中大多通过降低压敏电阻烧成温度，或者缩短保温时间来减小晶粒的生长。然而这种方法使压敏电阻的U-I非线性、老化性能和通流能量变差。此外，当前普遍采用Al离子作为施主离子添加到ZnO压敏电阻中来提高ZnO晶粒的电阻率，从而起到降低残压的目的。但是Al离子的添加会造成电阻片的漏电流增大，非线性系数降低和老化特性变差。
发明内容
有鉴于此，本发明提供了一种高非线性、低漏电流压敏电阻片及其制备方法，能够有效解决添加Al离子造成的电阻片漏电流增大、非线性系数降低的问题。
本发明第一方面提供了一种高非线性、低漏电流压敏电阻片，组成成分包括：ZnO、Bi2O3、Co2O3、MnO2、Sb2O3、Cr2O3、NiO、SiO2和Al2O3，且各成分之间的摩尔比为ZnO:Bi2O3:Co2O3:MnO2:Sb2O3:Cr2O3:NiO:SiO2:Al2O3＝1520-1540:7-12:15-17:8-10:13-16:4-6:7-9:23-25:0.8-1.5。
本发明提供的压敏电阻片性能与各组分配比直接相关，SiO2的适量添加影响了烧结机制和势垒高度，促进SiO2和ZnO的反应、以及Bi12SiO20玻璃相的形成，有效抑制添加Al2O3带来的漏电流的增加。
本发明第二方面提供了上述高非线性、低漏电流压敏电阻片的制备方法，步骤包括：
S1、将氧化物添加剂和去离子水混合后进行一次球磨；所述氧化物添加剂包括：Bi2O3、Co2O3、MnO2、Sb2O3、Cr2O3、NiO、SiO2和Al2O3；以摩尔比计，Bi2O3:Co2O3:MnO2:Sb2O3:Cr2O3:NiO:SiO2:Al2O3＝7-12:15-17:8-10:13-16:4-6:7-9:23-25:0.8-1.5；
S2、向一次球磨后的浆料中加入ZnO、分散剂、聚乙烯醇溶液和去离子水，并进行二次球磨；
S3、将二次球磨后的浆料喷雾造粒得到的粉料，将粉料压制成坯体；
S4、将坯体高温煅烧，从10-30℃升温至445-455℃进行排胶，升温用时200-250min，然后在445-455℃保温100-120min，排胶结束；
S5、排胶结束后直接升温至1000-1100℃进行烧成，升温用时270-350min，保温时间为120-180min；烧成后，随炉冷却。
本发明提供的压敏电阻片采用特定配比的氧化物配方，影响烧结机制，采用特定煅烧工艺，在较低的烧成温度下即可实现产品高非线性、低漏电流的稳定、良好的电性能，且降低了生产成本。
优选的，步骤S1中，所述一次球磨时间为2400-3000min。
优选的，步骤S2中，所述二次球磨时间为1200-1560min。
优选的，步骤S2中，所加入的ZnO与一次球磨混合浆料中的Bi2O3的摩尔比为1520-1540:7-12。
优选的，步骤S2中，所述分散剂为聚乙二醇，聚丙烯酸铵，十二烷基醋酸胺，脂肪醇聚氧乙烯醚中的一种或几种。
更加优选的，步骤S2中，所述分散剂添加质量为ZnO质量的1.5～2％。分散剂的种类以及添加量以能够实现氧化物的均匀分散为准，分散剂并不局限于一种，也可以是几种分散剂的混合物。上述ZnO质量按ZnO的理论用量计。
优选的，步骤S2中，所述聚乙烯醇溶液的质量浓度为5.1-6％。
更加优选的，步骤S2中，每克氧化物对应聚乙烯醇溶液的添加量为0.4-0.45mL。
优选的，步骤S3所述压制过程中，成型压力为9-11MPa，成型时间为2-4min。压制成型工艺影响粉体颗粒排列、影响致密性及晶粒生长过程，从而影响压敏电阻片电性能。
与现有技术相比，本发明的有益效果是：本发明通过SiO2的适量添加影响了烧结机制和势垒高度，降低了烧成温度并提高了ZnO压敏电阻的非线性。这主要是由于SiO2和ZnO的化学缺陷反应可以产生氧，此外Si替换ZnO结晶里面的Zn形成了作为电荷的中心，增加了束缚电子的能力，从而影响势垒的高度。此外，纳米SiO2的适量添加还可以影响烧结机制，这是由于Si4+具有小的离子半径(0.26埃)，进入连续通路比其他的过渡金属离子要容易，从而影响了ZnO晶胞的体积，影响烧结机制。不但如此，纳米SiO2还可与Bi2O3反应生成Bi12SiO20玻璃相可以抑制晶粒生长，从而影响烧结机制。使用Al2O3并采用微量添加，从而限制了ZnO电阻片漏电流的增加。材料不仅具有更高的性能，而且制备过程工艺简单，氧化物添加量和种类较少，生产成本低，可用于规模化生产。
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
本实施例提供了一种高非线性、低漏电流压敏电阻片，配方成分包括氧化锌ZnO191.25mol、氧化铋Bi2O31mol、三氧化二钴Co2O32mol、二氧化锰MnO21.13mol、三氧化锑Sb2O31.75mol、三氧化二铬Cr2O30.625、氧化镍NiO1mol、二氧化硅SiO23mol、氧化铝Al2O30.18mol。
上述高非线性、低漏电流压敏电阻片的制备方法包括以下步骤：
(a)将氧化物添加剂Bi2O3(1mol)、Co2O3(2mol)、MnO2(1.13mol)、Sb2O3(1.75mol)、Cr2O3(0.625mol)、NiO(1mol)、SiO2(3mol)、Al2O3(0.18mol)加入球磨罐中，并加入去离子水，进行一次球磨，球磨时间为2400min。
(b)向一次球磨的浆料中加入ZnO(191.25mol)，分散剂、聚乙烯醇PVA、去离子水并在球磨罐中进行二次球磨，二次球磨的时间为1200min。
(c)将二次球磨的浆料经过喷雾干燥机喷雾造粒；将喷雾造粒得到的粉料用压片机压制成坯体，成型压力10MPa，成型时间3min。
(d)将压制的坯体至于高温煅烧炉中，从室温用时200min升温至450℃进行排胶，450℃保温时间为100min。
(e)排胶后直接升温，用时270min至1100℃进行烧成，保温时间为120min。烧成后随炉冷却至室温。
实施例2
本实施例提供了一种高非线性、低漏电流压敏电阻片，配方成分包括氧化锌ZnO191.25mol、氧化铋Bi2O31mol、三氧化二钴Co2O32mol、二氧化锰MnO21.13mol、三氧化锑Sb2O31.75mol、三氧化二铬Cr2O30.625mol、氧化镍NiO1mol、二氧化硅SiO22.875mol、氧化铝Al2O30.1mol。
上述高非线性、低漏电流压敏电阻片的制备方法包括以下步骤：
(a)将氧化物添加剂Bi2O3(1mol)、Co2O3(2mol)、MnO2(1.13mol)、Sb2O3(1.75mol)、Cr2O3(0.625mol)、NiO(1mol)、SiO2(2.875mol)、Al2O3(0.1mol)加入球磨罐中，并加入去离子水，进行一次球磨，球磨时间为2400min。
(b)向一次球磨的浆料中加入ZnO(191.25mol)，分散剂、聚乙烯醇PVA、去离子水并在球磨罐中进行二次球磨，二次球磨的时间为1200min。
(c)将二次球磨的浆料经过喷雾干燥机喷雾造粒；将喷雾造粒得到的粉料用压片机压制成坯体，成型压力10MPa，成型时间3min。
(d)将压制的坯体至于高温煅烧炉中，从室温用时200min升温至450℃进行排胶，450℃保温时间为100min。
(e)排胶后直接升温，用时270min至1100℃进行烧成，保温时间为120min。烧成后随炉冷却至室温。
将实施例1和实施例2制备得到的样品进行电性能测试，非线性系数均大于65，漏电流也得到了有效的控制，数值都小于0.5μA，具体结果如表1所示。
表1实施例1和实施例2所得产品的电气性能
实施例3
本实施例提供了一种高非线性、低漏电流压敏电阻片，配方成分包括氧化锌ZnO153.0mol、氧化铋Bi2O31.1mol、三氧化二钴Co2O31.6mol、二氧化锰MnO20.9mol、三氧化锑Sb2O31.5mol、三氧化二铬Cr2O30.5mol、氧化镍NiO0.8mol、二氧化硅SiO22.4mol、氧化铝Al2O30.1mol。
上述高非线性、低漏电流压敏电阻片的制备方法包括以下步骤：
(a)将氧化物添加剂Bi2O3(1.1mol)、Co2O3(1.6mol)、MnO2(0.9mol)、Sb2O3(1.5mol)、Cr2O3(0.5mol)、NiO(0.8mol)、SiO2(2.4mol)、Al2O3(0.1mol)加入球磨罐中，并加入去离子水，进行一次球磨，球磨时间为2800min。
(b)向一次球磨的浆料中加入ZnO(153.0mol)，分散剂脂肪醇聚氧乙烯醚、5.5wt％的聚乙烯醇PVA溶液、去离子水并在球磨罐中进行二次球磨，二次球磨的时间为1400min。所述分散剂用量为ZnO理论用量的2wt％。每克氧化物原料混合物中加入聚乙烯醇溶液的量为0.4mL。
(c)将二次球磨的浆料经过喷雾干燥机喷雾造粒；将喷雾造粒得到的粉料用压片机压制成坯体，成型压力10MPa，成型时间3min。
(d)将压制的坯体至于高温煅烧炉中，从室温用时220min升温至445℃进行排胶，445℃保温时间为120min。
(e)排胶后直接升温，用时300min至1000℃进行烧成，保温时间为150min。烧成后随炉冷却至室温。
将制备得到的样品进行电性能测试，产品电性能与实施例1产品基本一致。
实施例4
本实施例提供了一种高非线性、低漏电流压敏电阻片，配方成分包括氧化锌ZnO152.4mol、氧化铋Bi2O30.9mol、三氧化二钴Co2O31.5mol、二氧化锰MnO21.0mol、三氧化锑Sb2O31.4mol、三氧化二铬Cr2O30.6mol、氧化镍NiO0.7mol、二氧化硅SiO22.5mol、氧化铝Al2O30.13mol。
上述高非线性、低漏电流压敏电阻片的制备方法包括以下步骤：
(a)将氧化物添加剂Bi2O3(0.9mol)、Co2O3(1.5mol)、MnO2(1.0mol)、Sb2O3(1.4mol)、Cr2O3(0.6mol)、NiO(0.7mol)、SiO2(2.5mol)、Al2O3(0.13mol)加入球磨罐中，并加入去离子水，进行一次球磨，球磨时间为2700min。
(b)向一次球磨的浆料中加入ZnO(152.4mol)，分散剂十二烷基醋酸胺、6wt％的聚乙烯醇PVA溶液、去离子水并在球磨罐中进行二次球磨，二次球磨的时间为1500min。所述分散剂用量为ZnO理论用量的1.8wt％。每克氧化物原料混合物中加入聚乙烯醇溶液的量为0.45mL。
(c)将二次球磨的浆料经过喷雾干燥机喷雾造粒；将喷雾造粒得到的粉料用压片机压制成坯体，成型压力10MPa，成型时间3min。
(d)将压制的坯体至于高温煅烧炉中，从室温用时250min升温至455℃进行排胶，455℃保温时间为100min。
(e)排胶后直接升温，用时280min至1020℃进行烧成，保温时间为180min。烧成后随炉冷却至室温。
将制备得到的样品进行电性能测试，产品电性能与实施例1产品基本一致。
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 (10)
1.一种高非线性、低漏电流压敏电阻片，其特征在于：组成成分包括：ZnO、Bi2O3、Co2O3、MnO2、Sb2O3、Cr2O3、NiO、SiO2和Al2O3，且各成分之间的摩尔比为ZnO:Bi2O3:Co2O3:MnO2:Sb2O3:Cr2O3:NiO:SiO2:Al2O3＝1520-1540:7-12:15-17:8-10:13-16:4-6:7-9:23-25:0.8-1.5。
2.权利要求1所述高非线性、低漏电流压敏电阻片的制备方法，步骤包括：
S1、将氧化物添加剂和去离子水混合后进行一次球磨；所述氧化物添加剂包括：Bi2O3、Co2O3、MnO2、Sb2O3、Cr2O3、NiO、SiO2和Al2O3；以摩尔比计，Bi2O3:Co2O3:MnO2:Sb2O3:Cr2O3:NiO:SiO2:Al2O3＝7-12:15-17:8-10:13-16:4-6:7-9:23-25:0.8-1.5；
S2、向一次球磨后的浆料中加入ZnO、分散剂、聚乙烯醇溶液和去离子水，并进行二次球磨；
S3、将二次球磨后的浆料喷雾造粒得到的粉料，将粉料压制成坯体；
S4、将坯体高温煅烧，从10-30℃升温至445-455℃进行排胶，升温用时200-250min，然后在445-455℃保温100-120min，排胶结束；
S5、排胶结束后直接升温至1000-1100℃进行烧成，升温用时270-350min，保温时间为120-180min；烧成后，随炉冷却。
3.如权利要求2所述的高非线性、低漏电流压敏电阻片的制备方法，其特征在于：步骤S1中，所述一次球磨时间为2400-3000min。
4.如权利要求2所述的高非线性、低漏电流压敏电阻片的制备方法，其特征在于：步骤S2中，所述二次球磨时间为1200-1560min。
5.如权利要求2所述的高非线性、低漏电流压敏电阻片的制备方法，其特征在于：步骤S2中，所加入的ZnO与一次球磨混合浆料中的Bi2O3的摩尔比为1520-1540:7-12。
6.如权利要求2所述的高非线性、低漏电流压敏电阻片的制备方法，其特征在于：步骤S2中，所述分散剂为聚乙二醇、聚丙烯酸铵、十二烷基醋酸胺、脂肪醇聚氧乙烯醚中的一种或几种。
7.如权利要求6所述的高非线性、低漏电流压敏电阻片的制备方法，其特征在于：步骤S2中，所述分散剂添加质量为ZnO质量的1.5～2％。
8.如权利要求2所述的高非线性、低漏电流压敏电阻片的制备方法，其特征在于：步骤S2中，所述聚乙烯醇溶液的质量浓度为5.1-6％。
9.如权利要求8所述的高非线性、低漏电流压敏电阻片的制备方法，其特征在于：步骤S2中，每克氧化物对应聚乙烯醇溶液的添加量为0.4-0.45mL。
10.如权利要求2所述的高非线性、低漏电流压敏电阻片的制备方法，其特征在于：步骤S3所述压制过程中，成型压力为9-11MPa，成型时间为2-4min。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285676A (zh) * | 2020-02-24 | 2020-06-16 | 武汉理工大学 | 一种氧化锌压敏陶瓷材料及其制备方法 |
| CN111517778A (zh) * | 2020-05-20 | 2020-08-11 | 华南理工大学 | 一种低温烧结氧化锌压敏陶瓷及其制备方法 |
| CN112608142A (zh) * | 2020-08-07 | 2021-04-06 | 佛山(华南)新材料研究院 | 一种热压烧结工艺制备Zn0电阻片的方法 |
| CN115073163A (zh) * | 2022-07-01 | 2022-09-20 | 深圳振华富电子有限公司 | 片式压敏电阻器及其制备方法和应用 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290176A (zh) * | 2011-06-08 | 2011-12-21 | 上海大学 | 一种直流氧化锌压敏电阻片及其制备方法 |
| CN102476949A (zh) * | 2011-11-10 | 2012-05-30 | 中国科学院过程工程研究所 | 一种低温制备电性能可控的氧化锌压敏电阻材料的方法 |
| CN103396116A (zh) * | 2013-08-13 | 2013-11-20 | 广东风华高新科技股份有限公司 | 氧化锌压敏电阻生料、其制备方法及压敏电阻器 |
| EP2857374A1 (en) * | 2013-10-02 | 2015-04-08 | Razvojni Center eNem Novi Materiali d.o.o. | Method for manufacturing varistor ceramics and varistors having low leakage current |
| CN105272205A (zh) * | 2015-10-12 | 2016-01-27 | 中国科学院上海硅酸盐研究所 | 一种低温烧结氧化锌压敏电阻器材料及其制备方法 |
| CN105924149A (zh) * | 2016-04-23 | 2016-09-07 | 上海大学 | 一种城市轨道交通过电压保护器用电阻片的制备方法 |
-
2018
- 2018-11-19 CN CN201811373514.6A patent/CN109574653A/zh active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290176A (zh) * | 2011-06-08 | 2011-12-21 | 上海大学 | 一种直流氧化锌压敏电阻片及其制备方法 |
| CN102476949A (zh) * | 2011-11-10 | 2012-05-30 | 中国科学院过程工程研究所 | 一种低温制备电性能可控的氧化锌压敏电阻材料的方法 |
| CN103396116A (zh) * | 2013-08-13 | 2013-11-20 | 广东风华高新科技股份有限公司 | 氧化锌压敏电阻生料、其制备方法及压敏电阻器 |
| EP2857374A1 (en) * | 2013-10-02 | 2015-04-08 | Razvojni Center eNem Novi Materiali d.o.o. | Method for manufacturing varistor ceramics and varistors having low leakage current |
| CN105272205A (zh) * | 2015-10-12 | 2016-01-27 | 中国科学院上海硅酸盐研究所 | 一种低温烧结氧化锌压敏电阻器材料及其制备方法 |
| CN105924149A (zh) * | 2016-04-23 | 2016-09-07 | 上海大学 | 一种城市轨道交通过电压保护器用电阻片的制备方法 |
Non-Patent Citations (4)
| Title |
|---|
| BAI HAIRUI 等: "Influence of SiO2 on electrical properties of the highly nonlinear ZnO-Bi2O3-MnO2 varistors", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| WU ZHENHONG 等: "Effect of SiO2 addition on the microstructure and electrical properties of ZnO-based varistors", 《INTERNATIONAL JOURNAL OF MINERALS, METALLURGY AND MATERIALS》 * |
| 程器 等: "添加剂微纳化对ZnO压敏电阻性能的影响", 《电瓷避雷器》 * |
| 陈奕创: "高电位梯度ZnO压敏陶瓷材料的制备", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285676A (zh) * | 2020-02-24 | 2020-06-16 | 武汉理工大学 | 一种氧化锌压敏陶瓷材料及其制备方法 |
| CN111285676B (zh) * | 2020-02-24 | 2021-03-30 | 武汉理工大学 | 一种氧化锌压敏陶瓷材料及其制备方法 |
| CN111517778A (zh) * | 2020-05-20 | 2020-08-11 | 华南理工大学 | 一种低温烧结氧化锌压敏陶瓷及其制备方法 |
| CN111517778B (zh) * | 2020-05-20 | 2021-07-20 | 华南理工大学 | 一种低温烧结氧化锌压敏陶瓷及其制备方法 |
| CN112608142A (zh) * | 2020-08-07 | 2021-04-06 | 佛山(华南)新材料研究院 | 一种热压烧结工艺制备Zn0电阻片的方法 |
| CN115073163A (zh) * | 2022-07-01 | 2022-09-20 | 深圳振华富电子有限公司 | 片式压敏电阻器及其制备方法和应用 |
| CN115073163B (zh) * | 2022-07-01 | 2023-09-01 | 深圳振华富电子有限公司 | 片式压敏电阻器及其制备方法和应用 |
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