CN108751978A - 氧化锌压敏陶瓷电阻片的制备方法 - Google Patents
氧化锌压敏陶瓷电阻片的制备方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000000919 ceramic Substances 0.000 title claims abstract description 22
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000004945 emulsification Methods 0.000 claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 239000007767 bonding agent Substances 0.000 claims abstract description 5
- 238000003801 milling Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000011344 liquid material Substances 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims 1
- 238000010008 shearing Methods 0.000 claims 1
- 230000035939 shock Effects 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 20
- 239000002245 particle Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012071 phase Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000007790 solid phase Substances 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 12
- 229960001296 zinc oxide Drugs 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010316 high energy milling Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052905 tridymite 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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Abstract
本发明涉及电阻片技术领域,具体为氧化锌压敏陶瓷电阻片的制备方法,包括先高能乳化、再超细磨,同时完成自循环和双循环的工作次序,保证了粉料粒度,同时形成了AlNO3与ZnO间稳定的附着结构;主体材料的高能乳化超细磨过程和加入结合剂分开,成为两个单独的过程。本发明提供的氧化锌压敏陶瓷电阻片的制备方法,实现了粒度均匀、分散度小,降低了烧结温度和烧结时间,粉末高度细化,产生塑性变形,引发新的固相相变,达到合成新材料的效果,保证了压敏陶瓷结构的一致性,提高了产品电位梯度。保证了新材料中AlNO3与ZnO形成稳定的附着结构,提高了工作电流密度。通流能力大幅提高。
Description
技术领域
本发明涉及电阻片技术领域,具体为氧化锌压敏陶瓷电阻片的制备方法。
背景技术
氧化锌压敏电阻的特性、应用、生产,是半导体技术应用与研究的重要领域,是国家科技重点扶植发展的专业、产业方向。我国80年代就开始了该领域的生产活动,技术进步、产品升级和科研活动一直持续进行,主要针对如何提高压敏电阻的各项性能指标,如何稳定产品的一致性,提高产品的成品率。该产品的生产过程主要有材料准备、组份混合、制坯成型、烧结生长半导体电阻材料制备和后期的电极、绝缘、封装,以及测试、老化等生产过程。
影响该产品的因素很多,经过多年科研试制,和产品生产,已经认识到影响该产品的几个关键因素有,烧结温度及过程、组份配比、粉料粒度与混合度。三个方向对产品的各项性能都有很大影响,目前相关领域的各大科研院所,仍然在不断摸索各种方案,以提升氧化锌压敏电阻的特性,各个生产厂家也在不断的做实验以期提升产品性能降低成本。
传统的Zn0压敏陶瓷粉体的合成工艺是固相法,它以固体物料在高温下经热分解或高温反应而得。固相法制备Zn0压敏陶瓷粉体是把质t比90%左右的纯Zn0与其它金属氧化物粉体如Bi2O3、Co2O3,MnO2,Sb2O3和Cr203等在球磨机或其它机械混合设备中棍合。由于主原料Zn0粉体的平均粒度在0.6μm左右,而添加剂粉料的平均粒度在5μm左右。通过两次球磨和一次锻烧,添加剂中各元素的分布均匀性得到了一定提高,但其粉料的平均粒度很难降至Zn0粉体平均粒度以下。这种方法不易保证成分准确、均匀,而且还会带来研磨介质的污染,也不可能获得粒度细、活性好的粉体。对形成最终的理想的压敏陶瓷的微观结构非常不利,严重影响压敏电阻性能。
另一方案为化学共沉淀法,通常使用法国PCF公司提供的草酸盐共沉淀法生产的复合压敏肉瓷粉体来制备多层氧化锌压敏电阻,该方法中掺杂元素在压敏陶瓷中的分布更加均匀,因此多层压敏电阻的电性能优于固相法的。利用Zn、Bi、Co、Mn和Cr的硝酸盐及SbO3,以NH3·H2O为沉淀剂,采用化学共沉淀工艺制备出了Zn0复合压敏陶瓷粉体。这种粉体的粒度为0.5μm,活性好,比表面积为7.93m2/g。用这种复合陶瓷粉体所制备的压敏电阻的电位梯度为304.6V/mm,非线性系数a为50,性能远优于固相法粉体所制备的压敏电阻。这些优异性能源于共沉淀粉体混合均匀,因而能够制得微观结构均匀的压敏电阻。目前采用化学共沉淀法制备的Zn0纳米复合压敏陶瓷粉体,研制出的压敏电阻器的电位梯度大于330V/mm,漏电流小于1μA,非线性系数a大于58。该工艺复杂,生产成本较高,另外厂品的参数性能较低。
发明内容
本发明提供了一种新的湿法高能球磨工艺,提高氧化锌压敏陶瓷粉体的颗粒粒度一致性,使得颗粒粒径在0.5μm,且粒度分布很窄,形成的陶瓷具有较好的精细微观结构,压敏电阻的电位梯度比其他传统产品大一个数量级,达到1500V/mm。
具体技术方案为:
制造氧化锌压敏陶瓷电阻片的主要流程是:氧化锌粉末制粒--添加辅助配方材料—添加结合剂—混合制成原料粉—磨具压制成型—烧结—冷却—涂装电极—包绝缘层—老化检验。本发明特别对混合制粒的具体过程做了全新的设计和工艺处理,开发了自动化生产线。由于粒度、配比方式带来粉料全新的微结构,烧结产生的陶瓷结构更加适合压敏电阻的非线性特点,提高了各项电气性能指标。具体步骤和工艺参数如下:
氧化锌压敏陶瓷电阻片的制备方法,包括以下步骤:
(1)、氧化锌及辅料、水加入物料罐,水、料质量比1:1,进行高能乳化,搅拌速率为3000转/分,搅拌45分钟;
所述的高能乳化:物料罐的搅拌器在高速运转时,通过搅拌器上双分散盘的上下方高速旋转,在边缘2.5~5mm处形成湍流区,分散盘上下锯齿对固-液物料进行高速的剪切、撞击、粉碎、分散;
(2)、浆料进行研磨,所述的研磨包括自循环和双循环两个过程,
所述的自循环,设置两个物料罐A和B,物料罐中的物料在压力带动下,送入研磨设备后回到原物料罐;
所述的双循环:即双罐间循环,设置两个物料罐A和B,物料罐中的物料在压力带动下,送入研磨设备后送到另一个物料罐的物流过程;
自循环:双循环时间比例为1.618:1;
一次自循环、一次双循环为一个研磨周期,研磨周期不少于三个周期;
(3)、转移到新的罐体中,添加结合剂聚乙烯醇PVA,依次进行高能乳化、不少于三个周期的研磨,所述的高能乳化和研磨分别同步骤(1)和步骤(2);
(4)、采用悬浮喷雾式脱水干燥造粒,再成型、烧结、后加制成压敏电阻片。
本发明提供的氧化锌压敏陶瓷电阻片的制备方法,具有的有益效果:
1、通过以上工艺,实现了粒度均匀、分散度小,降低了烧结温度和烧结时间,节约了大量能源,降低了成本。
2、粉末高度细化,产生塑性变形,引发新的固相相变,达到合成新材料的效果,保证了压敏陶瓷结构的一致性,提高了产品电位梯度。
3、工艺保证了新材料中AlNO3与ZnO形成稳定的附着结构,提高了工作电流密度。通流能力大幅提高。
4、自动化工艺提高了生产效率,提升了产品质量节约了成本,产品各项的电气性能优异。
具体实施方式
结合实施例说明本发明的具体技术方案。
1、氧化锌及辅料统一加入物料料罐,辅料包括Bi2O3、Co2O3、MnO2、Sb2O3、Cr203、SiO2、NiO、Al(NO3)3·9H2O等;在料罐内主要完成搅拌均匀、和精细研磨过程,在精细磨前先充分搅拌乳化,以提高研磨效率。
具体实现方法为加水搅拌,水、料质量比1:1,利用高速搅拌桨叶,按3000转/分,高速搅拌45分钟。
2、浆料通过研磨设备分为自循环和双循环两个过程,以使研磨充分,均匀。合理设计自循环和双循环比例,本实施例工艺过程的时间比例,自循环:双循环=1.618:1),使Al(NO3)3·9H2O与ZnO形成稳定的附着结构。
所述的自循环:设置两个物料罐A和B,物料罐中的物料在压力带动下,送入研磨设备后回到本物料罐的物流过程,如从A罐流出,研磨后回到A罐,为自循环。
所述的双循环:即双罐间循环,设置两个物料罐A和B,物料罐中的物料在压力带动下,送入研磨设备后送到另一个物料罐的物流过程,如从A罐流出,研磨后送到B罐,为双循环。
双循环,保证了全部浆料通过研磨设备,不留死角。
一次自循环、双循环的研磨工艺过程为一个研磨周期,采用不少于三个周期操作,保证研磨粒度符合要求,达到一致的均匀性。
3、在新的罐体中添加结合剂(聚乙烯醇PVA),此时添加是为了避免与AlNO3与ZnO产生化学反应。影响附着结构。
4、结合剂加入后,继续高能乳化、多周期研磨过程,利用C、D罐体。
5、干燥,采用悬浮喷雾式脱水干燥造粒。悬浮喷雾式脱水干燥为常规干燥造粒工艺,在本专利设备中采用自动化工艺,利用隔膜泵把上述工艺之后的浆料直接注入干燥器,实现了全封闭生产工艺,减少了二次倒装造成的密度不均,和杂质的引入,提高了半成品粉料的粒度一致性。
以上过程自动化完成达到精细控制,严格控制每个过程细节,保证工艺质量。
6、采用传统工艺成型、烧结、生成压敏电阻片及后续工艺。
Claims (3)
1.氧化锌压敏陶瓷电阻片的制备方法,其特征在于,包括以下步骤:
(1)、氧化锌及辅料、水加入物料罐,水、料质量比1:1,进行高能乳化;所述的高能乳化:物料罐的搅拌器在高速运转时,通过搅拌器上双分散盘的上下方高速旋转,在边缘2.5~5mm处形成湍流区,分散盘上下锯齿对固-液物料进行高速的剪切、撞击、粉碎、分散;
(2)、浆料进行研磨,所述的研磨包括自循环和双循环两个过程,
所述的自循环,设置两个物料罐A和B,物料罐中的物料在压力带动下,送入研磨设备后回到原物料罐;
所述的双循环:即双罐间循环,设置两个物料罐A和B,物料罐中的物料在压力带动下,送入研磨设备后送到另一个物料罐的物流过程;
一次自循环、一次双循环为一个研磨周期,研磨周期不少于三个周期;
(3)、转移到新的罐体中,添加结合剂聚乙烯醇PVA,依次进行高能乳化、不少于三个周期的研磨,所述的高能乳化和研磨分别同步骤(1)和步骤(2);
(4)、采用悬浮喷雾式脱水干燥造粒,再成型、烧结、后加工制成压敏电阻片。
2.根据权利要求1所述的氧化锌压敏陶瓷电阻片的制备方法,其特征在于,所述的高能乳化,物料罐的搅拌器的搅拌速率为3000转/分,搅拌45分钟。
3.根据权利要求1所述的氧化锌压敏陶瓷电阻片的制备方法,其特征在于,所述的自循环:双循环时间比例为1.618:1。
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