CN111320472A - 采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法 - Google Patents
采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法 Download PDFInfo
- Publication number
- CN111320472A CN111320472A CN202010193560.9A CN202010193560A CN111320472A CN 111320472 A CN111320472 A CN 111320472A CN 202010193560 A CN202010193560 A CN 202010193560A CN 111320472 A CN111320472 A CN 111320472A
- Authority
- CN
- China
- Prior art keywords
- mol
- zno
- doping
- preparing
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 21
- 229910052779 Neodymium Inorganic materials 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003292 glue Substances 0.000 claims abstract description 13
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 26
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 26
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 13
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims 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 description 9
- 239000008187 granular material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 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 4
- -1 wherein the Bi is2O3 Chemical compound 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims 1
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims 1
- 230000032683 aging Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 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 6
- 239000011268 mixed slurry Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—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
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3241—Chromium oxides, chromates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B2235/3267—MnO2
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3294—Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/443—Nitrates or nitrites
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
一种采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，包括原料配制步骤、添加ZnO步骤、离子添加步骤、成型步骤、排胶步骤、烧结步骤，上述步骤依次进行，其特征在于，所述离子添加步骤中，加入Al离子、Zr离子，所述原料制备步骤中加入Nd2O3，所述Zr离子以Zr(NO3)4·5H2O形式计量和添加。其有益效果是：梯度高、残压低、通流容量大、泄露电流小、老化性能稳定。
Description
技术领域
本发明属于材料领域，特别涉及一种采用Nd、Zr离子复合施主掺杂制备兼具高梯度和低残压特性的ZnO压敏电阻陶瓷的方法。
背景技术
ZnO压敏电阻是以ZnO为主要原料，添加少量的Bi2O3、Sb2O3、MnO2、Cr2O3、Co2O3、和B2O3等作为辅助成份，采用陶瓷烧结工艺制备而成。
由于容易制造，而且对不纯物反应迟钝，容易制造，而且经济，所以使用高电压避雷器成为了主流。一般来说，采用前者电压非直线电阻体的避雷元件制作并使用如下烧结元件。主要成分的zn0铋（bi）、锑(sb)、钴(co)、锰(mn)、镍(ni)、硅(si)等的氧化物粉末混合后,圆盘状等规定的形式整容,烧结炉内的高温烧结,烧结体,该烧结体的两端进行面研磨后,两个研磨面电极设置使用。近年来，从节约能源或减少C02排放量的观点来看，为了降低在输电线中的功率损失，在全世界范围内推进输电线电压的超高压化。因此，要求防雷装置使用的防雷元件也能够承受超高压。如果要使避雷器应对超高压，使用通常制作的避雷元件，需要堆积很多个数，因此，所有的避雷元件要变长，而且收纳的容器也要变大。因此，为了使整个避雷器尺寸减小，需要一种每单位厚度的粒界数大，即，粒径小，每单位厚度电压梯度高的避雷元件。同样，超、特高压电网需要更强的抗老化性能，因此，更大的单位厚度上的电压梯度、更小的泄露电流成为了目前ZnO压敏电阻阀片的所需。
发明内容
本发明的目的是为了解决上述问题，设计了一种采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法。具体设计方案为：
一种采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，包括原料配制步骤、添加ZnO步骤、离子添加步骤、成型步骤、排胶步骤、烧结步骤，上述步骤依次进行，其特征在于，所述离子添加步骤中，加入Al离子、Zr离子，所述原料制备步骤中加入Nd2O3，所述Zr离子以Zr(NO3)4·5H2O 形式计量和添加。
所述原料配制步骤中，各成分的摩尔质量比为：SnO2(87.5~95.8mol%)、Bi2O3(0.5~2.0mol%)、Sb2O3(0.5~1.5mol%)、MnO2(0.5~1.0mol%)、Cr2O3(0.5~1.0mol%)、Co2O3(0.5~1.5mol%)、SiO2(1.0~2.0mol%)，以及Al(NO3)3(0.1~1.0mol%)、Nd2O3（0.03～0.04mol%）、Zr(NO3)4·5H2O (1 mol ~3 mol %)，其中所述Bi2O3、Sb2O3、MnO2、Cr2O3、Co2O3、SiO2、Nd2O3为辅料配方。
所述添加ZnO步骤中，将ZnO与辅料混合，并加入去离子水，去离子水与浆料的质量份数比为1-2:1，混合球磨，球磨2-3小时，使所有混合原料分散均匀为止。
所述离子添加步骤中，Al(NO3)3、Zr(NO3)4·5H2O，继续球磨1～2小时，制成粉料。
所述成型步骤中，对所述粉料进行喷雾、含水后，使用液压压片机以及D5的圆柱形模具，将颗粒料压片成型，成型压力为150MPa，保压时间2分钟，形成胚体。
所述排胶步骤中，坯体在封闭的气氛条件下，采用100~250℃/每小时的升温速度，在400℃左右保温排胶20小时。
所述烧结步骤中，从室温升温至烧结温度1240~1260℃，在烧结温度下保温30~40小时，使陶瓷烧结致密。
通过本发明的上述技术方案得到的采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，其有益效果是：
梯度高、残压低、通流容量大、泄露电流小、老化性能稳定。
具体实施方式
下面对本发明进行具体描述。
采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，包括原料配制步骤、添加ZnO步骤、离子添加步骤、成型步骤、排胶步骤、烧结步骤，上述步骤依次进行，其特征在于，所述离子添加步骤中，加入Al离子、Zr离子，所述原料制备步骤中加入Nd2O3，所述Zr离子以Zr(NO3)4·5H2O 形式计量和添加。
所述原料配制步骤中，各成分的摩尔质量比为：SnO2(87.5~95.8mol%)、Bi2O3(0.5~2.0mol%)、Sb2O3(0.5~1.5mol%)、MnO2(0.5~1.0mol%)、Cr2O3(0.5~1.0mol%)、Co2O3(0.5~1.5mol%)、SiO2(1.0~2.0mol%)，以及Al(NO3)3(0.1~1.0mol%)、Nd2O3（0.03～0.04mol%）、Zr(NO3)4·5H2O (1 mol ~3 mol %)，其中所述Bi2O3、Sb2O3、MnO2、Cr2O3、Co2O3、SiO2、Nd2O3为辅料配方。
所述添加ZnO步骤中，将ZnO与辅料混合，并加入去离子水，去离子水与浆料的质量份数比为1-2:1，混合球磨，球磨2-3小时，使所有混合原料分散均匀为止。
所述离子添加步骤中，Al(NO3)3、Zr(NO3)4·5H2O，继续球磨1～2小时，制成粉料。
所述成型步骤中，对所述粉料进行喷雾、含水后，使用液压压片机以及D5的圆柱形模具，将颗粒料压片成型，成型压力为150MPa，保压时间2分钟，形成胚体。
所述排胶步骤中，坯体在封闭的气氛条件下，采用100~250℃/每小时的升温速度，在400℃左右保温排胶20小时。
所述烧结步骤中，从室温升温至烧结温度1240~1260℃，在烧结温度下保温30~40小时，使陶瓷烧结致密。
实施例一：
1）原料配制
该低残压ZnO压敏电阻陶瓷材料按以下比例ZnO(90 mol%)、Bi2O3(1.5 mol%)、Sb2O3 (1mol %)、MnO2 (1 mol %)、Cr2O3 (1 mol %)、Co2O3 (1 mol %)、 SiO2 (1.5 mol %)、Al(NO3)3(1 mol %)、Ga(NO3)3 (1 mol %)、Nd2O3（0.03mol%）和Zr(NO3)4·5H2O (1 mol ~3 mol %)配制初始原料。
2）制备辅助添加浆料
将Bi2O3(1.5 mol%)、Sb2O3 (1 mol %)、MnO2 (1 mol %)、Cr2O3 (1 mol %)、Co2O3 (1 mol%)和 SiO2 (1.5 mol %)、Nd2O3（0.03mol%）放入行星式球磨机的球磨罐中，加入粉料重量1.5倍的去离子水，球磨2个小时。
3）将辅助添加浆料和半数ZnO主料混合
在球磨后的辅助添加浆料中伴去离子水依序加入PVA（结合剂）、分散剂；加入半数配置好的ZnO；
4）添加铝、镓锆离子及剩余ZnO主料
在混合均匀的浆料中，添加Al(NO3)3 (1mol %)和Zr(NO3)4·5H2O（0.01mol %）；加入剩余ZnO主料继续球磨1小时。
5）成型
将上一步中得到的粉料进行喷雾、含水后，使用液压压片机以及D5的圆柱形模具，将颗粒料压片成型，成型压力为150MPa，保压时间2分钟。
6）排胶
用高温电炉在封闭气氛中烧结坯体，具体温度和控制时间如下：
从室温至400℃，升温时间2小时；
在400℃保温排胶20小时；
7）烧结
从室温至300 ℃，升温时间2小时；
从300℃至700℃，升温时间2小时；
从700℃至1000℃，升温时间2小时；
从1000至1200℃，升温时间2小时；
1200℃，保温30小时；
自然降温。
对按以上工艺制备得到的ZnO压敏电阻样品进行了各项性能测试。泄漏电流均值1mA/cm2, 非线性系数均值80，压敏电压梯度均值520V/mm，残压比均值1.41。
实施例二：
1）原料配制
该低残压ZnO压敏电阻陶瓷材料按以下比例ZnO(95.8 mol%)、Bi2O3(0.5mol%)、Sb2O3 (0.5 mol %)、MnO2 (0.5 mol %)、Cr2O3 (0.5 mol %)、Co2O3 (0.5 mol %)、 SiO2 (1mol %)、Al(NO3)3 (0.1 mol %)、Nd2O3（0.03mol%）和Zr(NO3)4·5H2O (2 mol %)配制初始原料。
2）制备辅助添加浆料
将Bi2O3(0.5mol%)、Sb2O3 (0.5 mol %)、MnO2 (0.5 mol %)、Cr2O3 (0.5 mol %)、Co2O3 (0.5 mol %)、 SiO2 (1mol %)、Nd2O3（0.03mol%）放入行星式球磨机的球磨罐中，加入粉料重量1.5倍的去离子水，球磨2个小时。
3）将辅助添加浆料和半数ZnO主料混合
在球磨后的辅助添加浆料中伴去离子水依序加入PVA（结合剂）、分散剂；加入半数配置好的ZnO；
4）添加铝、镓锆离子及剩余ZnO主料
在混合均匀的浆料中，添加Al(NO3)3 (1mol %)、Ga(NO3)3 (1 mol %) 和Zr(NO3)4·5H2O (2 mol %)；加入剩余ZnO主料继续球磨1小时。
5）成型
将上一步中得到的粉料进行喷雾、含水后，使用液压压片机以及D5的圆柱形模具，将颗粒料压片成型，成型压力为150MPa，保压时间2分钟。
6）排胶
用高温电炉在封闭气氛中烧结坯体，具体温度和控制时间如下：
从室温至400℃，升温时间2小时；
在400℃保温排胶20小时；
7）烧结
从室温至300 ℃，升温时间2小时；
从300℃至700℃，升温时间2小时；
从700℃至1000℃，升温时间2小时；
从1000至1200℃，升温时间2小时；
1200℃，保温30小时；
自然降温。
对按以上工艺制备得到的ZnO压敏电阻样品进行了各项性能测试。其泄漏电流得到抑制，均值0.82mA/cm2, 非线性系数均值82，压敏电压梯度均值522V/mm，残压比均值1.40。
实施例三：
1）原料配制
该低残压ZnO压敏电阻陶瓷材料按以下比例ZnO(87.5 mol%)、Bi2O3(2mol%)、Sb2O3 (1.5 mol %)、MnO2 (1mol %)、Cr2O3 (1 mol %)、Co2O3 (1.5 mol %)、 SiO2 (2mol %)、Al(NO3)3 (1 mol %)、Nd2O3（0.04mol%）和Zr(NO3)4·5H2O (2 mol %)配制初始原料。
2）制备球磨辅助添加料
将Bi2O3 (2 mol %)、Sb2O3 (1.5 mol %)、MnO2 (1 mol %)、Cr2O3 (1 mol %)、Co2O3 (1.5mol %)和SiO2 (2mol %) 、Nd2O3（0.04mol%）放入行星式球磨机的球磨罐中，加入粉料重量1.5倍的去离子水，球磨2个小时。
3）将辅助添加浆料和半数ZnO主料混合
在球磨后的辅助添加浆料中伴去离子水依序加入PVA（结合剂）、分散剂；加入半数配置好的ZnO；
4）添加铝、镓锆离子及剩余ZnO主料
在混合均匀的浆料中，添加Al(NO3)3 (1mol %)、Ga(NO3)3 (1 mol %) 和Zr(NO3)4·5H2O (2mol %)；加入剩余ZnO主料继续球磨1小时。
5）成型
将上一步中得到的粉料进行喷雾、含水后，使用液压压片机以及D5的圆柱形模具，将颗粒料压片成型，成型压力为150MPa，保压时间2分钟。
6）排胶
用高温电炉在封闭气氛中烧结坯体，具体温度和控制时间如下：
从室温至400℃，升温时间2小时；
在400℃保温排胶20小时；
7）烧结
从室温至300 ℃，升温时间2小时；
从300℃至700℃，升温时间2小时；
从700℃至1000℃，升温时间2小时；
从1000至1200℃，升温时间2小时；
1200℃，保温30小时；
自然降温。
对按以上工艺制备得到的ZnO压敏电阻样品进行了各项性能测试。其泄漏电流得到抑制，均值1.2mA/cm2, 非线性系数均值79，压敏电压梯度均值511V/mm，残压比均值1.45。
采用传统原料混合研磨工艺以及烧结工艺，通过调整辅助添加料的成份和比例，在ZnO及混合浆料中同时添加了Al、Nd和Zr元素。Al和Zr离子的共同作用下，在烧结过程中Al和Zr固溶进锌晶格，降低了晶粒电阻，降低了大电流区的残压，Nd离子的存在，使得陶瓷本体致密度上升，提高了ZnO压敏电阻陶瓷的电压梯度，与单纯添加Al离子相比，泄漏电流也得到有效抑制。综上所述，能够将ZnO压敏电阻陶瓷的残压比控制在1.4以下，电压梯度不低于500V/mm，使泄漏电流小于1mA/cm2，非线性系数在80以上，所制备的ZnO压敏电阻陶瓷，具备梯度高、残压低、通流容量大、泄露电流小、老化性能稳定的特点。
上述技术方案仅体现了本发明技术方案的优选技术方案，本技术领域的技术人员对其中某些部分所可能做出的一些变动均体现了本发明的原理，属于本发明的保护范围之内。
Claims (7)
1.一种采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，包括原料配制步骤、添加ZnO步骤、离子添加步骤、成型步骤、排胶步骤、烧结步骤，上述步骤依次进行，其特征在于，所述离子添加步骤中，加入Al离子、Zr离子，所述原料制备步骤中加入Nd2O3，所述Zr离子以Zr(NO3)4·5H2O 形式计量和添加。
2.根据权利要求1中所述的采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，其特征在于，所述原料配制步骤中，各成分的摩尔质量比为SnO2(87.5~95.8mol%)、Bi2O3(0.5~2.0mol%)、Sb2O3(0.5~1.5mol%)、MnO2(0.5~1.0mol%)、Cr2O3(0.5~1.0mol%)、Co2O3(0.5~1.5mol%)、SiO2(1.0~2.0mol%)，以及Al(NO3)3(0.1~1.0mol%)、Nd2O3（0.03～0.04mol%）、Zr(NO3)4·5H2O (1 mol ~3 mol %)，其中所述Bi2O3、Sb2O3、MnO2、Cr2O3、Co2O3、SiO2、Nd2O3为辅料配方。
3.根据权利要求2中所述的采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，其特征在于，所述添加ZnO步骤中，将ZnO与辅料混合，并加入去离子水，去离子水与浆料的质量份数比为1-2:1，混合球磨，球磨2-3小时，使所有混合原料分散均匀为止。
4.根据权利要求1中所述的采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，其特征在于，所述离子添加步骤中，Al(NO3)3、Zr(NO3)4·5H2O，继续球磨1～2小时，制成粉料。
5.根据权利要求4中所述的采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，其特征在于，所述成型步骤中，对所述粉料进行喷雾、含水后，使用液压压片机以及D5的圆柱形模具，将颗粒料压片成型，成型压力为150MPa，保压时间2分钟，形成胚体。
6.根据权利要求5中所述的采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，其特征在于，所述排胶步骤中，坯体在封闭的气氛条件下，采用100~250℃/每小时的升温速度，在400℃左右保温排胶20小时。
7.根据权利要求6中所述的采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法，其特征在于，所述烧结步骤中，从室温升温至烧结温度1240~1260℃，在烧结温度下保温30~40小时，使陶瓷烧结致密。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010193560.9A CN111320472A (zh) | 2020-03-18 | 2020-03-18 | 采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010193560.9A CN111320472A (zh) | 2020-03-18 | 2020-03-18 | 采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111320472A true CN111320472A (zh) | 2020-06-23 |
Family
ID=71163872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010193560.9A Pending CN111320472A (zh) | 2020-03-18 | 2020-03-18 | 采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111320472A (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2529281A1 (de) * | 1974-07-25 | 1976-02-05 | Fuji Electric Co Ltd | Verfahren zur herstellung nichtlinearer widerstaende aus zinkoxid und zusatzstoffen |
| DE2910841A1 (de) * | 1979-03-20 | 1980-09-25 | Licentia Gmbh | Spannungsabhaengiges widerstandsmaterial und verfahren zu dessen herstellung |
| JPH0529107A (ja) * | 1991-07-17 | 1993-02-05 | Nec Corp | 電圧非直線抵抗体 |
| CN101333104A (zh) * | 2008-05-20 | 2008-12-31 | 上海大学 | 超塑性纳米氧化物掺杂的氧化锌压敏陶瓷材料及制备方法 |
| CN105601268A (zh) * | 2015-12-25 | 2016-05-25 | 清华大学 | 一种综合电气性能优良的氧化锌压敏电阻陶瓷的配方 |
-
2020
- 2020-03-18 CN CN202010193560.9A patent/CN111320472A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2529281A1 (de) * | 1974-07-25 | 1976-02-05 | Fuji Electric Co Ltd | Verfahren zur herstellung nichtlinearer widerstaende aus zinkoxid und zusatzstoffen |
| DE2910841A1 (de) * | 1979-03-20 | 1980-09-25 | Licentia Gmbh | Spannungsabhaengiges widerstandsmaterial und verfahren zu dessen herstellung |
| JPH0529107A (ja) * | 1991-07-17 | 1993-02-05 | Nec Corp | 電圧非直線抵抗体 |
| CN101333104A (zh) * | 2008-05-20 | 2008-12-31 | 上海大学 | 超塑性纳米氧化物掺杂的氧化锌压敏陶瓷材料及制备方法 |
| CN105601268A (zh) * | 2015-12-25 | 2016-05-25 | 清华大学 | 一种综合电气性能优良的氧化锌压敏电阻陶瓷的配方 |
Non-Patent Citations (1)
| Title |
|---|
| 严群 等: ""添加Nd2O3对氧化锌压敏阀片电性能与显微组织的影响"", 《硅酸盐学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105016721B (zh) | 采用铝、镓和钇离子共同掺杂制备ZnO压敏电阻陶瓷的方法 | |
| CN102557610B (zh) | 高电位梯度氧化锌压敏电阻片及其制法和应用 | |
| AU2020102274A4 (en) | Ceramic having high voltage gradient, low residual voltage and low leakage current and preparation method thereof | |
| CN101503292B (zh) | 直流氧化锌电阻片 | |
| CN105859279A (zh) | 一种制备性能优良氧化锌压敏电阻陶瓷的新型工艺方法 | |
| EP2599759A1 (en) | Process for producing zinc oxide varistor having high potential gradient and high non-linearity coefficient | |
| CN105645948B (zh) | 一种高电压梯度、低泄露电流压敏电阻陶瓷材料的制备方法 | |
| CN105622086B (zh) | 制备高梯度氧化锌压敏电阻陶瓷的方法 | |
| CN102476949A (zh) | 一种低温制备电性能可控的氧化锌压敏电阻材料的方法 | |
| CN101604566B (zh) | 一种适合低浪涌电压电器使用的氧化锌压敏电阻材料及制备方法 | |
| CN101786874A (zh) | 一种制备低残压ZnO压敏电阻陶瓷的工艺方法 | |
| CN102515742A (zh) | 一种高电位梯度氧化锌压敏电阻材料及其制备方法 | |
| CN101503291B (zh) | 高压交流氧化锌电阻片 | |
| CN109574653A (zh) | 一种高非线性、低漏电流压敏电阻片及其制备方法 | |
| CN101279844A (zh) | 复合稀土氧化物掺杂的氧化锌压敏陶瓷材料 | |
| CN108546111A (zh) | 一种高电压梯度、低残压、低泄露电流的氧化锌压敏电阻陶瓷及其制备方法 | |
| CN105481363B (zh) | 一种大通流容量、低残压、高梯度氧化锌压敏电阻陶瓷 | |
| CN105884345A (zh) | 一种高电压梯度、低残压、低泄露电流的陶瓷及其制备方法 | |
| CN100361238C (zh) | 防雷用多元掺杂改性氧化锌压敏材料 | |
| CN110922182A (zh) | 高梯度、低泄漏电流陶瓷的制备方法 | |
| CN111320472A (zh) | 采用Nd、Zr离子复合施主掺杂制备ZnO压敏电阻陶瓷的方法 | |
| CN110078494B (zh) | 一种氧化锌电阻片及其制备方法 | |
| CN109704752B (zh) | 一种SnO2压敏电阻及其制备方法 | |
| CN105601268A (zh) | 一种综合电气性能优良的氧化锌压敏电阻陶瓷的配方 | |
| CN100415681C (zh) | 一种稀土氧化物掺杂的ZnO－Bi2O3系压敏陶瓷介质 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200623 |