CN106278239B - 一种超高梯度氧化锌压敏电阻及其制备方法 - Google Patents

一种超高梯度氧化锌压敏电阻及其制备方法 Download PDF

Info

Publication number
CN106278239B
CN106278239B CN201610655648.1A CN201610655648A CN106278239B CN 106278239 B CN106278239 B CN 106278239B CN 201610655648 A CN201610655648 A CN 201610655648A CN 106278239 B CN106278239 B CN 106278239B
Authority
CN
China
Prior art keywords
mesh
green body
zinc oxide
millimeters
superelevation
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.)
Active
Application number
CN201610655648.1A
Other languages
English (en)
Other versions
CN106278239A (zh
Inventor
覃远东
廖莘
孟凡志
黄绍芬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUANGXI NEW FUTURE INFORMATION INDUSTRY Co Ltd
Original Assignee
GUANGXI NEW FUTURE INFORMATION INDUSTRY Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by GUANGXI NEW FUTURE INFORMATION INDUSTRY Co Ltd filed Critical GUANGXI NEW FUTURE INFORMATION INDUSTRY Co Ltd
Priority to CN201610655648.1A priority Critical patent/CN106278239B/zh
Publication of CN106278239A publication Critical patent/CN106278239A/zh
Application granted granted Critical
Publication of CN106278239B publication Critical patent/CN106278239B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/453Shaped 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64Burning or sintering processes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-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
    • H01C7/10Non-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 voltage responsive, i.e. varistors
    • H01C7/105Varistor cores
    • H01C7/108Metal oxide
    • H01C7/112ZnO type
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225Yttrium oxide or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279Nickel oxides, nickalates, or oxide-forming salts thereof
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3289Noble metal oxides
    • C04B2235/3291Silver oxides
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3293Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3294Antimony oxides, antimonates, antimonites or oxide forming salts thereof, indium antimonate
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明公开了一种超高梯度氧化锌压敏电阻及其制备方法。该压敏电阻是由下述分析纯原料制造:ZnO、Co3O4、Sb2O3、MnCO3、Bi2O3、Ni2O3、ZrO2、SiO2、Y2O3、SnO2、Ba(CH3COO)2、Al(NO3)3·9H2O、AgNO3、H3BO3经球磨混合、喷雾造粒,选取20%~30%直接用于排胶、烧结,形成焙烧颗粒,其余部分,预干压成型,机械粉碎重新造粒,振动筛过筛,按颗粒大小比例选取粉料颗粒,充分混合,干压成型、排胶,依次叠好,坯体与坯体之间撒上微量焙烧颗粒,最后填埋焙烧颗粒埋烧,得到烧结好的瓷片,然后磨片、烘干、丝网印银、还原、焊接、包封,得到一种超高梯度氧化锌压敏电阻。本发明制造方法工艺简单,所制备的压敏电阻耐通流能力强,待机寿命长,能量密度大。

Description

一种超高梯度氧化锌压敏电阻及其制备方法
技术领域
本发明涉及的是一种超高梯度氧化锌压敏电阻及其制备方法,属于压敏电阻制造技术领域。
背景技术
在当今电子信息技术高速发展时代,ZnO压敏电阻器作为过电压保护器已广泛应用于电器、电子、建筑、通信和军事领域。市场前景十分广阔,经过50多年的开发研究,商用氧化锌压敏电阻梯度已经可以做到5~400V/mm几十个系列,可以应用从低压集成电路到高压/超高压输变电系统,尺寸元件直径也能做到5~136mm不等,通流能力最高能达到7.5kA/cm2,脉冲能量耐受能力平均可达到300J/cm3,最高可达750J/cm3。近年来,微型化、小型化和集成化成为了市场的主流,研究高电位梯度氧化锌压敏电阻材料不仅材料成本大大缩减,更重要的是能促使高度集成化,小型化,因此成了许多科学家探索的焦点,但是目前有很多研究只重视基本三参数性能的研究,忽略了重重要的通流能力、能量耐受能力和安全性能的研究,不具备实用价值,如一种高电位梯度氧化锌压敏电阻材料,专利号为201410673596.1,高电位梯度氧化锌压敏电阻片及其制法和应用,专利号为201110451769.1,一种高电位梯度氧化锌压敏电阻材料及其制备方法,专利号为201110421092.7,一种高电位梯度ZnO基压敏瓷料及其制备方法,专利号为201310262113.4,此外,还有目前研发的高梯度压敏电阻的梯度在500V/mm以下,难以达到如今特殊客户高梯度的需求,如一种高电位梯度氧化锌压敏电阻材料及其制备方法,专利号为201410850360.0,氧化锌基高电位梯度压敏陶瓷材料及其制备方法与应用,专利号为200610123901.5。因此从产品本征结构出发,在材料配方改进和工艺改进方面还有很大的技术突破空间。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷,通过高密度粉料颗粒制造技术和高均匀度胚体成型技术,确保坯体在烧结过程中氧化锌晶粒均匀生长,并通过埋烧技术实现烧结温度的均一化和匣钵内部气氛的控制,确保坯体表面与内部生长一致性,有效地克服产品异常晶粒长大导致的本征缺陷,达到高通流、高能量耐受能力最佳化,研制出了一种超高梯度氧化锌压敏电阻及其制备方法。
为了实现上述目的,本发明采取了如下技术方案:一种超高梯度氧化锌压敏电阻,由下述摩尔百分比的原料制备:ZnO:Co3O4:Sb2O3: MnCO3:Bi2O3:Ni2O3:ZrO2:SiO2:Y2O3:SnO2:Ba(CH3COO)2:Al(NO3)3 ▪9H2O:AgNO3:H3BO3等于94.6%~96.3%:0.85%~0.95%:0.7%~1.75%:0.7%~0.85%:0.45%~0.52%:0.43%~0.52%:0.05%~0.1%:0.1%~0.15%:0.3%~0.35%:0.05%~0.1%:0.015%-0.05%:0.005%-0.05%:0.01%~0.05%:0.02%~0.05%,各组分含量之和为100%。
所述超高梯度氧化锌压敏电阻制备方法是:
(1)首先将纯度≥99%的分析纯原料Co3O4、Sb2O3、MnCO3、Bi2O3、Ni2O3、ZrO2、SiO2、Y2O3、SnO2按摩尔百分比Co3O4:Sb2O3: MnCO3:Bi2O3:Ni2O3:ZrO2:SiO2:Y2O3:SnO2等于0.85%~0.95%:0.7%~1.75%:0.7%~0.85%:0.45%~0.52%:0.43%~0.52%:0.05%~0.1%:0.1%~0.15%:0.3%~0.35%:0.05%~0.1%准确称量,加入锆球、去离子水和分散剂,湿式球磨混合4~8小时,配制成超高梯度压敏电阻添加剂备用;其中,锆球、去离子水、分散剂、超高梯度压敏电阻添加剂原料重量比为3~4 ∶1~2 ∶0.01~0.03 ∶ 1;所述分散剂指的是铵盐类阳离子表面活性剂;
(2)另取Ba(CH3COO)2、Al(NO3)3 ▪9H2O、AgNO3、H3BO3完全溶于100~200克去离子水中,配置成添加液;取ZnO原料、去离子水、分散剂、硬脂酸、无水乙醇、添加液进行湿式乳化混合1~4小时,然后与超高梯度压敏电阻添加剂混合,再添加粘结剂和消泡剂,继续乳化混合3~5小时,制成喷雾浆料备用;其中, ZnO、去离子水、分散剂、硬脂酸、无水乙醇、粘结剂、消泡剂的重量比为1 : 0.3~0.55 : 0.01~0.05 : 0.002~0.01 : 0.002~0.01 : 0.1~0.5 : 0.001~0.004;上述的ZnO、Ba(CH3COO)2、Al(NO3)3 ▪9H2O、AgNO3、H3BO3与步骤(1)中的Co3O4、Sb2O3、MnCO3、Bi2O3、Ni2O3、ZrO2、SiO2、Y2O3、SnO2的摩尔比为94.6%~96.3%:0 %~0.05%:0 %~0.05%:0.01%~0.05%:0.02%~0.05%: 0.85%~0.95%:0.7%~1.75%:0.7%~0.85%:0.45%~0.52%:0.43%~0.52%:0.05%~0.1%:0.1%~0.15%:0.3%~0.35%:0.05%~0.1%,上述粘结剂是质量浓度为5%的聚乙烯醇水溶液,上述分散剂是铵盐类阳离子表面活性剂,上述消泡剂是纯度为99%以上的磷酸三丁酯;
(3)将喷雾浆料喷雾干燥成含水量0.45%~0.95%的造粒粉料;
(4)选取步骤(3)中造粒粉料总重量的20%~30%直接经550℃~650℃排胶、1050℃~1200℃烧结,形成焙烧颗粒,待用;
(5)其余部分预干压成型,压制成直径为25毫米,厚度为4毫米~5毫米,密度为3.0~3.5克/立方厘米的陶瓷生坯体A;
(6)将步骤(5)中的陶瓷生坯体A先置入粉碎机中粉碎成颗粒小块体,然后再通过行星式干磨重新造粒,研磨10分钟~25分钟后,用振动筛过筛,按不同粒径颗粒重量百分比325目~500目: 230目~325目: 180目~230目: 120目~180目: 90目~120目: 63目~90目: 40目~63目等于0.2%~0.6%:1%~2%:4.5%~6.4%:30%~35%:30%~35%:15%~20%:6%~10%,各组分含量之和为100%,选取粉料颗粒,置入拌料机中,充分混合,含水量保持在0.35%~0.95%,待用;
(7)将步骤(6)中的混合造粒粉料按常规方法干压成型,制成直径为23.7毫米,厚度为1.34毫米~1.60毫米,密度为3.0~3.5克/立方厘米的陶瓷生坯体B;
(8)将陶瓷生坯体B经550℃~650℃排胶, 然后将排胶好的坯体在匣钵内依次叠好,坯体与坯体之间撒上微量焙烧颗粒,最后用焙烧颗粒埯埋整个堆叠坯体,实现埋烧烧结,烧结温度为1050℃~1200℃,得到500~600V/mm超高梯度氧化锌压敏电阻瓷片;
(9)将烧结好的瓷片印银、还原、焊接、包封、固化;所述印银采用的工艺是常规丝网印刷工艺,印银所用的银电极浆料含银量为75%,所述的固化温度为140℃~190℃。
采取上述措施的本发明具有以下特点:
1. 本发明采用常规的分析纯原料进行配方组分的重新设计和调整,从而实现该产品500~600V/mm超高梯度、高通流、高能量耐受能力以及超长的待机寿命。
2. 本发明通过高密度粉料颗粒制造技术和高均匀度胚体成型技术,确保坯体在烧结过程中朝着氧化锌晶粒均匀性方向生长;
3. 本发明通过埋烧技术实现烧结温度的均一化和匣钵内部气氛的控制,确保坯体表面与内部生长一致性,有效地克服产品异常晶粒长大导致的本征缺陷,达到高通流、高能量耐受能力最佳化。
4. 本发明所采用的产品配方未添加任何的Pb、Cr元素,满足欧盟立法制定的《关于限制在电子电器设备中使用某些有害成分的指令》标准,绿色环保。
5. 本发明产品压敏电压梯度500~600V/mm,压敏电压离散度小,漏电流小于3μA,非线性系数大于85,通流能力达到6.5kA/cm2,脉冲能量耐受能力达到580J/cm3,而且耐组合波能力强,老化性能好,体积大大缩小。
6. 本发明的制造方法工艺简单,制造成本低,并且能够实现大批量工业化生产。
具体实施方式
下面结合实施例对本发明作进一步描述。需要指出的是,按照本发明的技术方案,下述实施例还可以举出许多,根据申请人大量的实验结果证明,在本发明的权利要求书所提出的范围,均可以达到本发明的目的。
实施例1
一种超高梯度氧化锌压敏电阻及其制备方法按下列步骤进行:
1. 首先称量纯度≥99%的分析纯原料Co3O4 461.2727克、Sb2O3 951.6044克、MnCO3186.3170克、Bi2O3 472.0446克、Ni2O3 193.6075克、ZrO2 17.7816克、SiO2 20.2882克、Y2O3162.6731克、SnO2 33.9285克至球磨罐中,然后加入8千克锆球、2.5千克去离子水和49克分散剂,湿式球磨混合4小时,配置成超高梯度压敏电阻添加剂;
2. 称取22.9996克Ba(CH3COO)2、4.2225克Al(NO3)3·9H2O、5.7363克AgNO3和2.7839克H3BO3,加去离子水200克,使之完全溶解,配置成添加液;称取17464.7399克纯度≥99%的分析纯原料ZnO置入搅拌罐中,加入8千克去离子水、200克分散剂、50克硬脂酸、100毫升无水乙醇,与上述的Ba(CH3COO)2、Al(NO3)3·9H2O、AgNO3和H3BO3的全部添加液湿式乳化混合3个小时,然后再与步骤1中超高梯度压敏电阻添加剂混合,再添加5.5千克质量浓度为5%的聚乙烯醇水溶液和60克纯度为99%以上的磷酸三丁酯,继续乳化混合4个小时,即可制成喷雾浆料;
3. 采用喷雾干燥塔将步骤2中的喷雾浆料喷雾干燥成含水量为0.45%~0.95%的造粒粉料;
4. 选取5千克步骤3中的造粒粉料直接经550℃排胶、1200℃烧结,保温90分钟,形成焙烧颗粒,待用;
5.将步骤3中剩余的造粒粉料干压成型,压制成直径为25毫米,厚度为4毫米~4.1毫米,重量为6.43克~6.49克的陶瓷生坯体A;
6. 将步骤5中的陶瓷生坯体A先置入粉碎机中粉碎成颗粒小块体,然后再通过行星式干磨重新造粒,研磨25分钟后,用振动筛过筛,按不同粒径颗粒重量百分比325目~500目: 230目~325目: 180目~230目: 120目~180目: 90目~120目: 63目~90目: 40目~63目等于0.45%:1.03%:4.85%:32.53%:33.56%:18.06%:9.52%选取粉料颗粒,置入拌料机中,充分混合,含水量保持在0.35%~0.95%,待用;
7.将步骤6中的混合均匀的造粒粉料按常规方法干压成型,压制成直径为23.7毫米,厚度为1.42毫米~1.46毫米,重量为2.16克~2.19克的陶瓷生坯体B;
8. 将步骤7中的陶瓷生坯体B经550℃排胶, 然后将排胶好的坯体在匣钵内依次叠好,坯体与坯体之间撒上微量步骤4中制成的焙烧颗粒,最后用焙烧颗粒埯埋整个堆叠坯体,实现埋烧烧结,烧结温度为1080℃,保温250分钟,得到550V/mm超高梯度氧化锌压敏电阻瓷片;
9. 将烧结好的瓷片采用含银量为75%的银电极浆料丝网印银、还原、焊接、包封,然后在160℃条件下固化140分钟,即可得到一种超高梯度氧化锌压敏电阻。
实施例2
一种超高梯度氧化锌压敏电阻及其制备方法按下列步骤进行:
1. 首先称量纯度≥99%的分析纯原料Co3O4 499.5488克、Sb2O3 1138.0000克、MnCO3 217.9489克、Bi2O3 467.7338克、Ni2O3 184.4610克、ZrO2 13.7436克、SiO2 20.1029克、Y2O3 176.2989克、SnO2 26.8949克至球磨罐中,然后加入9千克锆球、3千克去离子水和50克分散剂,湿式球磨混合6小时,配置成超高梯度压敏电阻添加剂;
2. 称取28.4870克Ba(CH3COO)2、4.1840克Al(NO3)3·9H2O、3.7893克AgNO3和3.4481克H3BO3,加去离子水200克,使之完全溶解,配置成添加液;称取17215.3588克纯度≥99%的分析纯原料ZnO置入搅拌罐中,加入8千克去离子水、200克分散剂、60克硬脂酸、100毫升无水乙醇,与上述的Ba(CH3COO)2、Al(NO3)3·9H2O、AgNO3和H3BO3的全部添加液湿式乳化混合4个小时,然后再与步骤1中超高梯度压敏电阻添加剂混合,再添加5.5千克质量浓度为5%的聚乙烯醇水溶液和60克纯度为99%以上的磷酸三丁酯,继续乳化混合5个小时,即可制成喷雾浆料;
3. 采用喷雾干燥塔将步骤2中的喷雾浆料喷雾干燥成含水量为0.45%~0.95%的造粒粉料;
4. 选取5千克步骤3中的造粒粉料直接经600℃排胶、1150℃烧结,保温90分钟,形成焙烧颗粒,待用;
5.将步骤3中剩余的造粒粉料干压成型,压制成直径为25毫米,厚度为4毫米~4.1毫米,重量为6.43克~6.49克的陶瓷生坯体A;
6. 将步骤5中的陶瓷生坯体A先置入粉碎机中粉碎成颗粒小块体,然后再通过行星式干磨重新造粒,研磨10分钟后,用振动筛过筛,按不同粒径颗粒重量百分比325目~500目: 230目~325目: 180目~230目: 120目~180目: 90目~120目: 63目~90目: 40目~63目等于0.6%:1.35%:4.5%:35%:34%:15.4%:9.15%选取粉料颗粒,置入拌料机中,充分混合,含水量保持在0.35%~0.95%,待用;
7.将步骤6中的混合均匀的造粒粉料按常规方法干压成型,压制成直径为23.7毫米,厚度为1.44毫米~1.48毫米,重量为2.18克~2.21克的陶瓷生坯体B;
8. 将步骤7中的陶瓷生坯体B经600℃排胶, 然后将排胶好的坯体在匣钵内依次叠好,坯体与坯体之间撒上微量步骤4中制成的焙烧颗粒,最后用焙烧颗粒埯埋整个堆叠坯体,实现埋烧烧结,烧结温度为1120℃,保温250分钟,得到500V/mm超高梯度氧化锌压敏电阻瓷片;
9. 将烧结好的瓷片采用含银量为75%的银电极浆料丝网印银、还原、焊接、包封,然后在190℃条件下固化95分钟,即可得到一种超高梯度氧化锌压敏电阻。
实施例3
一种超高梯度氧化锌压敏电阻及其制备方法按下列步骤进行:
1. 首先称量纯度≥99%的分析纯原料Co3O4 509.3723克、Sb2O3 1116.4758克、MnCO3 217.5562克、Bi2O3 539.5184克、Ni2O3 158.3506克、ZrO2 27.4376克、SiO2 16.0534克、Y2O3 150.8410克、SnO2 33.5581克至球磨罐中,然后加入9千克锆球、3千克去离子水和49克分散剂,湿式球磨混合8小时,配置成超高梯度压敏电阻添加剂;
2. 称取8.5307克Ba(CH3COO)2、16.7058克Al(NO3)3·9H2O、18.9122克AgNO3和6.8837克H3BO3,加去离子水200克,使之完全溶解,配置成添加液;称取17179.8043克纯度≥99%的分析纯原料ZnO置入搅拌罐中,加入8千克去离子水、200克分散剂、50克硬脂酸、100毫升无水乙醇,与上述的Ba(CH3COO)2、Al(NO3)3·9H2O、AgNO3和H3BO3的全部添加液湿式乳化混合1个小时,然后再与步骤1中超高梯度压敏电阻添加剂混合,再添加5.5千克质量浓度为5%的聚乙烯醇水溶液和60克纯度为99%以上的磷酸三丁酯,继续乳化混合5个小时,即可制成喷雾浆料;
3. 采用喷雾干燥塔将步骤2中的喷雾浆料喷雾干燥成含水量为0.45%~0.95%的造粒粉料;
4. 选取5千克步骤3中的造粒粉料直接经650℃排胶、1100℃烧结,保温120分钟,形成焙烧颗粒,待用;
5.将步骤3中剩余的造粒粉料干压成型,压制成直径为25毫米,厚度为4.7毫米~5.0毫米,重量为7.79克~7.84克的陶瓷生坯体A;
6. 将步骤5中的陶瓷生坯体A先置入粉碎机中粉碎成颗粒小块体,然后再通过行星式干磨重新造粒,研磨20分钟后,用振动筛过筛,按不同粒径颗粒重量百分比325目~500目: 230目~325目: 180目~230目: 120目~180目: 90目~120目: 63目~90目: 40目~63目等于0.35%:1.58%:5.67%:33.89%:32.64%:17%:8.87%选取粉料颗粒,置入拌料机中,充分混合,含水量保持在0.35%~0.95%,待用;
7.将步骤6中的混合均匀的造粒粉料按常规方法干压成型,压制成直径为23.7毫米,厚度为1.32毫米~1.36毫米,重量为2.01克~2.11克的陶瓷生坯体B;
8. 将步骤7中的陶瓷生坯体B经600℃排胶, 然后将排胶好的坯体在匣钵内依次叠好,坯体与坯体之间撒上微量步骤4中制成的焙烧颗粒,最后用焙烧颗粒埯埋整个堆叠坯体,实现埋烧烧结,烧结温度为1050℃,保温250分钟,得到600V/mm超高梯度氧化锌压敏电阻瓷片;
9. 将烧结好的瓷片采用含银量为75%的银电极浆料丝网印银、还原、焊接、包封,然后在140℃条件下固化160分钟,即可得到一种超高梯度氧化锌压敏电阻。
为了检测本发明的性能,对本发明进行了性能测试,测试结果如下表所示:
注:组合波冲击次数±15次,表示正方向连续冲击15次后,反方向连续冲击15次。
从上述测试结果可知,本发明的电位梯度明显高于现有水平电位梯度,其各项性能指标均与现有低电位梯度产品性能指标相当。

Claims (1)

1.一种超高梯度氧化锌压敏电阻的制备方法,所述超高梯度氧化锌压敏电阻由下述摩尔百分比的原料制备:ZnO:Co3O4:Sb2O3:MnCO3:Bi2O3:Ni2O3:ZrO2:SiO2:Y2O3:SnO2:Ba(CH3COO)2:Al(NO3)3▪9H2O:AgNO3:H3BO3等于94.6%~96.3%:0.85%~0.95%:0.7%~1.75%:0.7%~0.85%:0.45%~0.52%:0.43%~0.52%:0.05%~0.1%:0.1%~0.15%:0.3%~0.35%:0.05%~0.1%:0.015%-0.05%:0.005%-0.05%:0.01%~0.05%:0.02%~0.05%,各组分含量之和为100%;其特征在于所述超高梯度氧化锌压敏电阻制备方法是:
(1)首先将纯度≥99%的分析纯原料Co3O4、Sb2O3、MnCO3、Bi2O3、Ni2O3、ZrO2、SiO2、Y2O3、SnO2按摩尔百分比Co3O4:Sb2O3:MnCO3:Bi2O3:Ni2O3:ZrO2:SiO2:Y2O3:SnO2等于0.85%~0.95%:0.7%~1.75%:0.7%~0.85%:0.45%~0.52%:0.43%~0.52%:0.05%~0.1%:0.1%~0.15%:0.3%~0.35%:0.05%~0.1%准确称量,加入锆球、去离子水和分散剂,湿式球磨混合4~8小时, 配制成超高梯度压敏电阻添加剂备用;其中,锆球、去离子水、分散剂、超高梯度压敏电阻添加剂原料重量比为3~4∶1~2∶0.01~0.03∶1;所述分散剂指的是铵盐类阳离子表面活性剂;
(2)另取Ba(CH3COO)2、Al(NO3)3 ▪9H2O、AgNO3、H3BO3完全溶于100~200克去离子水中,配置成添加液;取ZnO原料、去离子水、分散剂、硬脂酸、无水乙醇、添加液进行湿式乳化混合1~4小时,然后与超高梯度压敏电阻添加剂混合,再添加粘结剂和消泡剂,继续乳化混合3~5小时,制成喷雾浆料备用;其中, ZnO、去离子水、分散剂、硬脂酸、无水乙醇、粘结剂、消泡剂的重量比为1 : 0.3~0.55 : 0.01~0.05 : 0.002~0.01 : 0.002~0.01 : 0.1~0.5: 0.001~0.004;上述的ZnO、Ba(CH3COO)2、Al(NO3)3▪9H2O、AgNO3、H3BO3与步骤(1)中的Co3O4、Sb2O3、MnCO3、Bi2O3、Ni2O3、ZrO2、SiO2、Y2O3、SnO2的摩尔比为94.6%~96.3%:0.015%-0.05%:0.005%-0.05%:0.01%~0.05%:0.02%~0.05%: 0.85%~0.95%:0.7%~1.75%:0.7%~0.85%:0.45%~0.52%:0.43%~0.52%:0.05%~0.1%:0.1%~0.15%:0.3%~0.35%:0.05%~0.1%,上述粘结剂是质量浓度为5%的聚乙烯醇水溶液,上述分散剂是铵盐类阳离子表面活性剂,上述消泡剂是纯度为99%以上的磷酸三丁酯;
(3)将喷雾浆料喷雾干燥成含水量为0.45%~0.95%的造粒粉料;
(4)选取步骤(3)中造粒粉料总重量的20%~30%直接经550℃~650℃排胶、1050℃~1200℃烧结,形成焙烧颗粒,待用;
(5)其余部分预干压成型,压制成直径为25毫米,厚度为4毫米~5毫米,密度为3.0~3.5克/立方厘米的陶瓷生坯体A;
(6)将步骤(5)中的陶瓷生坯体A先置入粉碎机中粉碎成颗粒小块体,然后再通过行星式干磨重新造粒,研磨10分钟~25分钟后,用振动筛过筛,按不同粒径颗粒重量百分比325目~500目:230目~325目:180目~230目:120目~180目:90目~120目:63目~90目:40目~63目等于0.2%~0.6%:1%~2%:4.5%~6.4%:30%~35%:30%~35%:15%~20%:6%~10%,各组分含量之和为100%,选取粉料颗粒,置入拌料机中,充分混合,含水量保持在0.35%~0.95%,待用;
(7)将步骤(6)中的混合造粒粉料按常规方法干压成型,制成直径为23.7毫米,厚度为1.34毫米~1.60毫米,密度为3.0~3.5克/立方厘米的陶瓷生坯体B;
(8)将陶瓷生坯体B经550℃~650℃排胶, 然后将排胶好的坯体在匣钵内依次叠好,坯体与坯体之间撒上微量焙烧颗粒,最后用焙烧颗粒埯埋整个堆叠坯体,实现埋烧烧结,烧结温度为1050℃~1200℃,得到500~600V/mm超高梯度氧化锌压敏电阻瓷片;
(9)将烧结好的瓷片印银、还原、焊接、包封、固化;所述印银采用的工艺是常规丝网印刷工艺,印银所用的银电极浆料含银量为75%,所述的固化温度为140℃~190℃。
CN201610655648.1A 2016-08-11 2016-08-11 一种超高梯度氧化锌压敏电阻及其制备方法 Active CN106278239B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610655648.1A CN106278239B (zh) 2016-08-11 2016-08-11 一种超高梯度氧化锌压敏电阻及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610655648.1A CN106278239B (zh) 2016-08-11 2016-08-11 一种超高梯度氧化锌压敏电阻及其制备方法

Publications (2)

Publication Number Publication Date
CN106278239A CN106278239A (zh) 2017-01-04
CN106278239B true CN106278239B (zh) 2019-05-21

Family

ID=57669392

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610655648.1A Active CN106278239B (zh) 2016-08-11 2016-08-11 一种超高梯度氧化锌压敏电阻及其制备方法

Country Status (1)

Country Link
CN (1) CN106278239B (zh)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106518049A (zh) * 2016-09-23 2017-03-22 清华大学 一种提高氧化锌压敏陶瓷电压梯度的制造工艺
CN107473731B (zh) * 2017-08-24 2020-11-03 广西新未来信息产业股份有限公司 一种高能量型压敏电阻及其制造方法
CN108395241B (zh) * 2018-03-23 2021-02-05 电子科技大学 一种低阻氧化锌陶瓷的制备方法
JP7169776B2 (ja) * 2018-06-06 2022-11-11 Koa株式会社 酸化亜鉛バリスタおよびその製造方法
CN111635225A (zh) * 2020-05-09 2020-09-08 广东风华高新科技股份有限公司 片式压敏电阻陶瓷粉料、片式压敏电阻器制备方法及产品
CN111574218A (zh) * 2020-05-20 2020-08-25 汕头市瑞升电子有限公司 压敏电阻介质共烧方法
CN112010644A (zh) * 2020-09-07 2020-12-01 广西新未来信息产业股份有限公司 一种能量型超高梯度氧化锌压敏电阻制造方法
CN112408996A (zh) * 2020-12-07 2021-02-26 广西新未来信息产业股份有限公司 一种压敏电阻瓷片的烧结方法
CN113105229B (zh) * 2021-03-29 2022-08-19 国网湖南省电力有限公司 一种氧化锌电阻片及其制备方法
CN113651610A (zh) * 2021-08-18 2021-11-16 西安神电(泾阳)电器有限公司 不含氧化铬和氧化硅高性能ZnO压敏电阻的制备方法及ZnO压敏电阻
CN114524670B (zh) * 2022-03-15 2023-05-16 福建省乔光电子科技有限公司 一种陶瓷电阻配方及加工工艺及设备
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
CN116903360A (zh) * 2023-07-24 2023-10-20 嘉兴瑞嘉电气股份有限公司 一种高梯度氧化锌压敏电阻片的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103693953A (zh) * 2013-11-27 2014-04-02 广西新未来信息产业股份有限公司 一种中低压氧化锌压敏电阻及其制备方法
CN104591726A (zh) * 2014-12-29 2015-05-06 广西新未来信息产业股份有限公司 一种高电位梯度氧化锌压敏电阻材料及其制备方法
CN105481363A (zh) * 2015-12-25 2016-04-13 清华大学 一种大通流容量、低残压、高梯度氧化锌压敏电阻陶瓷

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103693953A (zh) * 2013-11-27 2014-04-02 广西新未来信息产业股份有限公司 一种中低压氧化锌压敏电阻及其制备方法
CN104591726A (zh) * 2014-12-29 2015-05-06 广西新未来信息产业股份有限公司 一种高电位梯度氧化锌压敏电阻材料及其制备方法
CN105481363A (zh) * 2015-12-25 2016-04-13 清华大学 一种大通流容量、低残压、高梯度氧化锌压敏电阻陶瓷

Also Published As

Publication number Publication date
CN106278239A (zh) 2017-01-04

Similar Documents

Publication Publication Date Title
CN106278239B (zh) 一种超高梯度氧化锌压敏电阻及其制备方法
CN103011798B (zh) 一种高焦耳型压敏电阻及其制备方法
CN104591726B (zh) 一种高电位梯度氧化锌压敏电阻材料及其制备方法
CN107473731A (zh) 一种高能量型压敏电阻及其制造方法
KR101464688B1 (ko) 높은 전위 구배 및 높은 비-선형 계수를 가지는 산화아연 바리스터의 제조 공정
CN103693953B (zh) 一种中低压氧化锌压敏电阻及其制备方法
CN104086170B (zh) 低压压敏电阻陶瓷片及其制备方法、低压压敏电阻器的制备方法
CN104944936A (zh) 一种采用复合添加剂的氧化锌压敏陶瓷变阻器的制备方法
CN104671772B (zh) 改性纳米掺杂制备氧化锌压敏电阻复合粉体及制备方法
CN102390993A (zh) 一种无铬无铅中高压氧化锌压敏电阻材料及其制备方法
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
CN105272205B (zh) 一种低温烧结氧化锌压敏电阻器材料及其制备方法
CN102584206A (zh) 一种氧化锌压敏电阻生料
CN106373685A (zh) 一种低压压敏排阻及其制造方法
CN115536367A (zh) 高阻值低b值热敏电阻陶瓷体、制备方法及热敏电阻
CN106229026B (zh) 合金银粉及其制备方法及由其制备的太阳能导电浆料
JP5485275B2 (ja) セラミックス材料、このセラミックス材料の製造方法、およびこのセラミックス材料からなる電子セラミックス素子
CN103073267A (zh) 一种低电阻率、高b值负温度系数热敏材料及其制备方法
CN108975912A (zh) 三元系铌酸钾钠基无铅压电陶瓷及其制备方法
CN103058634A (zh) 一种用于烧结压敏电阻的承烧板的制备方法
CN101830694B (zh) 高纯二氧化锡电极陶瓷材料及其制备方法
CN104177082B (zh) 一种安全型电涌保护器阀片材料及其制备方法
CN104681223B (zh) 一种防雷浪涌复合型压敏电阻器及其制备方法
CN108863344B (zh) 一种高性能ZnO压敏陶瓷的制备工艺
CN110655400A (zh) 大通流容量氧化锌压敏电阻陶瓷材料、其制备方法及其电阻器的制备方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant