CN107117959A - 一种高居里温度ptc热敏陶瓷材料及其制备方法 - Google Patents
一种高居里温度ptc热敏陶瓷材料及其制备方法 Download PDFInfo
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- CN107117959A CN107117959A CN201710487850.2A CN201710487850A CN107117959A CN 107117959 A CN107117959 A CN 107117959A CN 201710487850 A CN201710487850 A CN 201710487850A CN 107117959 A CN107117959 A CN 107117959A
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 41
- 229910052883 rhodonite Inorganic materials 0.000 claims abstract description 37
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910008572 Li2O—B2O3-SiO2 Inorganic materials 0.000 claims abstract description 34
- 229910008585 Li2O—B2O3—SiO2 Inorganic materials 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 239000000428 dust Substances 0.000 claims abstract description 28
- 239000011521 glass Substances 0.000 claims abstract description 28
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 229910052681 coesite Inorganic materials 0.000 claims description 31
- 229910052906 cristobalite Inorganic materials 0.000 claims description 31
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 229910052682 stishovite Inorganic materials 0.000 claims description 31
- 229910052905 tridymite Inorganic materials 0.000 claims description 31
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 25
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 15
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 239000010431 corundum Substances 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 15
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 15
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 15
- 239000011656 manganese carbonate Substances 0.000 claims description 15
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- 238000003701 mechanical milling Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- 229910052571 earthenware Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000010532 solid phase synthesis reaction Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000036142 Viral infection Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005347 demagnetization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
一种高居里温度PTC热敏陶瓷材料，其特征在于由下述重量配比的原料制成：Ba0.4Pb0.6TiO3 86‑95%，La2O3 0.01‑2.8%，Si3N4 0.1‑4.0%，CaNb2O6 0.01‑1.5%，MnSiO3 0.5‑2%，Li2O‑B2O3‑SiO2玻璃粉 0.01‑2.5%，LaCrZrO5 0.02‑1.5%。本发明还提供上述高居里温度PTC热敏陶瓷材料的一种制备方法。本发明的PTC热敏陶瓷材料居里温度高、室温电阻率低、升阻比高、电阻温度系数（α）大，综合热敏性能好，制备时烧结温度低，可降低成本，并抑制铅的挥发，不污染环境。
Description
技术领域
本发明涉及无机非金属材料技术领域，具体涉及一种高居里温度PTC热敏陶瓷材料及其制备方法。
背景技术
PTC陶瓷是一种半导体化的具有正的温度系数（Positive TemperatureCoefficient，简称：PTC）的电子陶瓷材料；具有这种特性的智能电子陶瓷元件集发热与温控于一体，具有自动控温、安全节能、自动恢复、无触点动作、无明火、寿命长等特点；产品可用于发热元器件、温度控制、过流保护、过热保护和热感应等系统，广泛应用于汽车、电子、通讯、输变电工程、空调暖风机工程、低能耗安全型家用电器以及消磁、过流保护、过热保护等领域。
最常用的PTC热敏陶瓷是BaTiO3基陶瓷材料，其居里温度是120℃。为了提高热敏陶瓷的工作温度，均以添加氧化铅或含铅化合物为居里温度移动剂、以Pb置换Ba的晶格位置来实现，此类产品为含铅量较高的（Ba，Pb）TiO3体系。铅是一种具有毒性的重金属元素，在（Ba，Pb）TiO3基热敏陶瓷的生产过程中，铅会对自然环境造成污染并对人类的身体健康造成危害。开发无铅高居里温度PTC热敏陶瓷是消除铅污染的一个途径，但是无铅高居里温度PTC热敏陶瓷的性能不太理想，难以满足应用，而且制备工艺复杂，成本高。
现有的PTC热敏陶瓷的烧结温度高，为1300℃以上，如果降低PTC热敏陶瓷的烧结温度，就会抑制氧化铅的挥发，这也是消除铅污染的另一个有效的途径。目前，我国PTC热敏陶瓷产业的发展正面临着严重的考验和挑战，低烧结温度的高居里温度PTC热敏陶瓷材料的开发已经成了一个迫在眉睫的课题。近年来，国内外许多科研人员以及生产工作者已经着手低温烧结高居里温度（居里温度大于120℃）的PTC热敏陶瓷材料的开发与研究工作，有的PTC热敏陶瓷材料的居里温度高，但是综合热敏性能不太好，无法满足实际的应用。
发明内容
本发明所要解决的技术问题是提供一种高居里温度PTC热敏陶瓷材料及其制备方法，这种PTC热敏陶瓷材料居里温度高、室温电阻率低、升阻比高、电阻温度系数（α）大，综合热敏性能好，制备时烧结温度低，可降低成本，并抑制铅的挥发，不污染环境。采用的技术方案如下：
一种高居里温度PTC热敏陶瓷材料，其特征在于由下述重量配比的原料制成：Ba0.4Pb0.6TiO3 86-95%，La2O3 0.01-2.8%，Si3N4 0.1-4.0%，CaNb2O6 0.01-1.5%，MnSiO3 0.5-2%，Li2O-B2O3-SiO2玻璃粉 0.01-2.5%，LaCrZrO5 0.02-1.5%。
一种优选方案中，上述高居里温度PTC热敏陶瓷材料由下述重量配比的原料制成：Ba0.4Pb0.6TiO3 89-94%，La2O3 0.01-2.2%，Si3N4 0.1-3.0%，CaNb2O6 0.01-1.3%，MnSiO3 0.5-1.6%，Li2O-B2O3-SiO2玻璃粉 0.01-2.2%，LaCrZrO5 0.02-1.2%。
另一种优选方案中，上述高居里温度PTC热敏陶瓷材料由下述重量配比的原料制成： Ba0.4Pb0.6TiO3 90-94%，La2O3 0.01-2.0%，Si3N4 0.1-2.5%，CaNb2O6 0.01-1.2%，MnSiO30.5-1.4%, Li2O-B2O3-SiO2玻璃粉0.01-2.2%，LaCrZrO5 0.02-1.2%。
优选上述Ba0.4Pb0.6TiO3、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉、LaCrZrO5分别采用常规化学原料以固相法合成。
上述Ba0.4Pb0.6TiO3可采用如下工艺制备：按0.4：0.6：1的摩尔比配备BaCO3、PbO和TiO2，然后对BaCO3、PbO和TiO2进行研磨并混合均匀，再将BaCO3、PbO和TiO2的混合物料放入刚玉坩埚内，于1100-1150℃下保温120分钟，得到Ba0.4Pb0.6TiO3。得到的Ba0.4Pb0.6TiO3冷却后，经研磨并过200目筛，备用。
上述CaNb2O6可采用如下工艺制备：按1:1的摩尔比配备CaCO3和Nb2O5，然后对CaCO3和Nb2O5进行研磨并混合均匀，再将CaCO3和Nb2O5的混合物料放入氧化铝坩埚内，于1000-1030℃保温120分钟，得到CaNb2O6。得到的CaNb2O6冷却后，经研磨并过200目筛，备用。
上述MnSiO3可采用如下工艺制备：按1:1的摩尔比配备MnCO3和SiO2，然后对MnCO3和SiO2进行研磨并混合均匀，再将MnCO3和SiO2的混合物料放入氧化铝坩埚内，于1200-1250℃下保温120分钟，得到MnSiO3。得到的MnSiO3冷却后，经研磨并过200目筛，备用。
上述Li2O-B2O3-SiO2玻璃粉可采用如下工艺制备：按1：3：0.5的摩尔比配备Li2CO3、B2O3和SiO2，然后对Li2CO3、B2O3和SiO2进行研磨并混合均匀，再将Li2CO3、B2O3和SiO2的混合物料放入刚玉坩埚内，在810-840℃下保温40分钟，冷却后经研磨并过200目筛，得到Li2O-B2O3-SiO2玻璃粉。
上述LaCrZrO5可采用如下工艺制备：按1/2：1/2：1的摩尔比配备La2O3、Cr2O3和ZrO2，然后对La2O3、Cr2O3和ZrO2进行研磨并混合均匀，再将La2O3、Cr2O3和ZrO2的混合物料放入刚玉坩埚内，于1200-1250℃下保温120分钟，得到LaCrZrO5。得到的LaCrZrO5冷却后，经研磨并过200目筛，备用。
本发明还提供上述高居里温度PTC热敏陶瓷材料的一种制备方法，其特征在于包括下述步骤：
（1）按比例配备Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5；
（2）将步骤（1）所配备的Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5粉碎并混合均匀，得到混合粉料；
（3）将步骤（2）得到的混合粉料在烘箱中烘干，得到干粉料；
（4）向干粉料中加入粘结剂并进行造粒，得到颗粒状物料；
（5）将步骤（4）得到的颗粒状物料压制成生坯片；
（6）将生坯片置于1050-1100℃下保温1-3小时，使生坯片排出粘结剂并烧结，得到所述高居里温度PTC热敏陶瓷材料。
得到的高居里温度PTC热敏陶瓷材料为陶瓷片，在520-550℃下保温10分钟进行烧银，形成银电极；再焊引线，进行包封，即得到高居里温度PTC热敏陶瓷电阻器。
步骤（2）中，可以分别将各种原料粉碎后混合均匀；也可以将各种原料混合后进行粉碎，随后边粉碎边混合，或粉碎后再使各种原料混合均匀。粉碎设备可采用球磨，也可以采用其它粉碎设备。优选采用行星球磨机对配备好的原料进行球磨，被球磨的原料、所用球、所用水的重量比例为：原料:球:水=1:3:(0.6-1.0)，球磨过程持续4-8小时。水可采用蒸馏水或去离子水。
步骤（4）的粘结剂可采用聚乙烯醇水溶液（即PVA溶液）。优选步骤（4）的粘结剂采用重量百分比浓度为10%的聚乙烯醇溶液，所加入的聚乙烯醇溶液的重量为干粉料的重量的8-10%。
步骤（4）中，可在造粒后过40目筛。
优选步骤（5）中，在20-30Mpa压力下对颗粒状物料进行干压成型，得到生坯片。
本发明与现有技术相比，具有如下优点：
（1）本发明的PTC热敏陶瓷材料的居里温度高（居里温度达到360-365℃），室温电阻率低（室温电阻率为88-91Ω·cm），升阻比（lg(Rmax/Rmin)）高（升阻比达到5.2以上，为5.3-5.6），电阻温度系数（α）大（电阻温度系数达到24-25%/℃），综合热敏性能好。
（2）本发明的PTC热敏陶瓷材料烧结温度低，烧结温度为1050-1100℃，这样能大大降低高居里温度PTC热敏陶瓷的成本，抑制铅的挥发，对环境无污染。
具体实施方式
实施例1
首先，以固相法合成Ba0.4Pb0.6TiO3、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉、LaCrZrO5。
Ba0.4Pb0.6TiO3采用如下工艺制备：按0.4：0.6：1的摩尔比配备BaCO3、PbO和TiO2，然后对BaCO3、PbO和TiO2进行研磨并混合均匀，再将BaCO3、PbO和TiO2的混合物料放入刚玉坩埚内，于1130℃下保温120分钟，得到Ba0.4Pb0.6TiO3。得到的Ba0.4Pb0.6TiO3冷却后，经研磨并过200目筛，备用。
CaNb2O6采用如下工艺制备：按1:1的摩尔比配备CaCO3和Nb2O5，然后对CaCO3和Nb2O5进行研磨并混合均匀，再将CaCO3和Nb2O5的混合物料放入氧化铝坩埚内，于1020℃保温120分钟，得到CaNb2O6。得到的CaNb2O6冷却后，经研磨并过200目筛，备用。
MnSiO3采用如下工艺制备：按1:1的摩尔比配备MnCO3和SiO2，然后对MnCO3和SiO2进行研磨并混合均匀，再将MnCO3和SiO2的混合物料放入氧化铝坩埚内，于1220℃下保温120分钟，得到MnSiO3。得到的MnSiO3冷却后，经研磨并过200目筛，备用。
Li2O-B2O3-SiO2玻璃粉采用如下工艺制备：按1：3：0.5的摩尔比配备Li2CO3、B2O3和SiO2，然后对Li2CO3、B2O3和SiO2进行研磨并混合均匀，再将Li2CO3、B2O3和SiO2的混合物料放入刚玉坩埚内，在820℃下保温40分钟，冷却后经研磨并过200目筛，得到Li2O-B2O3-SiO2玻璃粉。
LaCrZrO5采用如下工艺制备：按1/2：1/2：1的摩尔比配备La2O3、Cr2O3和ZrO2，然后对La2O3、Cr2O3和ZrO2进行研磨并混合均匀，再将La2O3、Cr2O3和ZrO2的混合物料放入刚玉坩埚内，于1230℃下保温120分钟，得到LaCrZrO5。得到的LaCrZrO5冷却后，经研磨并过200目筛，备用。
然后，按下述步骤制备高居里温度PTC热敏陶瓷材料：
（1）按比例配备Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5；
参照表1，配备的各种原料的重量百分比如下：Ba0.4Pb0.6TiO3 90%，La2O3 2.2%，Si3N42.8%，CaNb2O6 1.0%，MnSiO3 0.8%，Li2O-B2O3-SiO2玻璃粉 2.0%，LaCrZrO5 1.2%；
（2）将步骤（1）所配备的Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5粉碎并混合均匀，得到混合粉料；
本实施例中，采用行星球磨机对配备好的原料进行球磨，被球磨的原料、所用球、所用水的重量比例为：原料:球:水=1:3:0.8，球磨过程持续6小时；
（3）将步骤（2）得到的混合粉料在烘箱中烘干，得到干粉料；
（4）向干粉料中加入粘结剂并进行造粒（在造粒后过40目筛），得到颗粒状物料；
本步骤（4）的粘结剂采用重量百分比浓度为10%的聚乙烯醇溶液，所加入的聚乙烯醇溶液的重量为干粉料的重量的9%；
（5）将步骤（4）得到的颗粒状物料压制成生坯片；
本步骤（5）中，在25Mpa压力下对颗粒状物料进行干压成型，得到生坯片；
（6）将生坯片置于1080-1100℃下保温2小时，使生坯片排出粘结剂并烧结，得到所述高居里温度PTC热敏陶瓷材料。
得到的高居里温度PTC热敏陶瓷材料为陶瓷片，在540℃下保温10分钟进行烧银，形成银电极；再焊引线，进行包封，即得到高居里温度PTC热敏陶瓷电阻器。实际生产中也可以选用其它电极材料（如铝电极等）替代银电极。
实施例2
首先，以固相法合成Ba0.4Pb0.6TiO3、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉、LaCrZrO5。
Ba0.4Pb0.6TiO3采用如下工艺制备：按0.4：0.6：1的摩尔比配备BaCO3、PbO和TiO2，然后对BaCO3、PbO和TiO2进行研磨并混合均匀，再将BaCO3、PbO和TiO2的混合物料放入刚玉坩埚内，于1100℃下保温120分钟，得到Ba0.4Pb0.6TiO3。得到的Ba0.4Pb0.6TiO3冷却后，经研磨并过200目筛，备用。
CaNb2O6采用如下工艺制备：按1:1的摩尔比配备CaCO3和Nb2O5，然后对CaCO3和Nb2O5进行研磨并混合均匀，再将CaCO3和Nb2O5的混合物料放入氧化铝坩埚内，于1030℃保温120分钟，得到CaNb2O6。得到的CaNb2O6冷却后，经研磨并过200目筛，备用。
MnSiO3采用如下工艺制备：按1:1的摩尔比配备MnCO3和SiO2，然后对MnCO3和SiO2进行研磨并混合均匀，再将MnCO3和SiO2的混合物料放入氧化铝坩埚内，于1200℃下保温120分钟，得到MnSiO3。得到的MnSiO3冷却后，经研磨并过200目筛，备用。
Li2O-B2O3-SiO2玻璃粉采用如下工艺制备：按1：3：0.5的摩尔比配备Li2CO3、B2O3和SiO2，然后对Li2CO3、B2O3和SiO2进行研磨并混合均匀，再将Li2CO3、B2O3和SiO2的混合物料放入刚玉坩埚内，在840℃下保温40分钟，冷却后经研磨并过200目筛，得到Li2O-B2O3-SiO2玻璃粉。
LaCrZrO5采用如下工艺制备：按1/2：1/2：1的摩尔比配备La2O3、Cr2O3和ZrO2，然后对La2O3、Cr2O3和ZrO2进行研磨并混合均匀，再将La2O3、Cr2O3和ZrO2的混合物料放入刚玉坩埚内，于1200℃下保温120分钟，得到LaCrZrO5。得到的LaCrZrO5冷却后，经研磨并过200目筛，备用。
然后，按下述步骤制备高居里温度PTC热敏陶瓷材料：
（1）按比例配备Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5；
参照表1，配备的各种原料的重量百分比如下：Ba0.4Pb0.6TiO3 89%，La2O3 2.5%，Si3N43.0%，CaNb2O6 1.3%，MnSiO3 1.6%，Li2O-B2O3-SiO2玻璃粉 1.5%，LaCrZrO5 1.1%；
（2）将步骤（1）所配备的Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5粉碎并混合均匀，得到混合粉料；
本实施例中，采用行星球磨机对配备好的原料进行球磨，被球磨的原料、所用球、所用水的重量比例为：原料:球:水=1:3:0.6，球磨过程持续8小时；
（3）将步骤（2）得到的混合粉料在烘箱中烘干，得到干粉料；
（4）向干粉料中加入粘结剂并进行造粒（在造粒后过40目筛），得到颗粒状物料；
本步骤（4）的粘结剂采用重量百分比浓度为10%的聚乙烯醇溶液，所加入的聚乙烯醇溶液的重量为干粉料的重量的8%；
（5）将步骤（4）得到的颗粒状物料压制成生坯片；
本步骤（5）中，在20Mpa压力下对颗粒状物料进行干压成型，得到生坯片；
（6）将生坯片置于1050℃下保温3小时，使生坯片排出粘结剂并烧结，得到所述高居里温度PTC热敏陶瓷材料。
得到的高居里温度PTC热敏陶瓷材料为陶瓷片，在520℃下保温10分钟进行烧银，形成银电极；再焊引线，进行包封，即得到高居里温度PTC热敏陶瓷电阻器。实际生产中也可以选用其它电极材料（如铝电极等）替代银电极。
实施例3
首先，以固相法合成Ba0.4Pb0.6TiO3、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉、LaCrZrO5。
Ba0.4Pb0.6TiO3采用如下工艺制备：按0.4：0.6：1的摩尔比配备BaCO3、PbO和TiO2，然后对BaCO3、PbO和TiO2进行研磨并混合均匀，再将BaCO3、PbO和TiO2的混合物料放入刚玉坩埚内，于1150℃下保温120分钟，得到Ba0.4Pb0.6TiO3。得到的Ba0.4Pb0.6TiO3冷却后，经研磨并过200目筛，备用。
CaNb2O6采用如下工艺制备：按1:1的摩尔比配备CaCO3和Nb2O5，然后对CaCO3和Nb2O5进行研磨并混合均匀，再将CaCO3和Nb2O5的混合物料放入氧化铝坩埚内，于1000℃保温120分钟，得到CaNb2O6。得到的CaNb2O6冷却后，经研磨并过200目筛，备用。
MnSiO3采用如下工艺制备：按1:1的摩尔比配备MnCO3和SiO2，然后对MnCO3和SiO2进行研磨并混合均匀，再将MnCO3和SiO2的混合物料放入氧化铝坩埚内，于1250℃下保温120分钟，得到MnSiO3。得到的MnSiO3冷却后，经研磨并过200目筛，备用。
Li2O-B2O3-SiO2玻璃粉采用如下工艺制备：按1：3：0.5的摩尔比配备Li2CO3、B2O3和SiO2，然后对Li2CO3、B2O3和SiO2进行研磨并混合均匀，再将Li2CO3、B2O3和SiO2的混合物料放入刚玉坩埚内，在810℃下保温40分钟，冷却后经研磨并过200目筛，得到Li2O-B2O3-SiO2玻璃粉。
LaCrZrO5采用如下工艺制备：按1/2：1/2：1的摩尔比配备La2O3、Cr2O3和ZrO2，然后对La2O3、Cr2O3和ZrO2进行研磨并混合均匀，再将La2O3、Cr2O3和ZrO2的混合物料放入刚玉坩埚内，于1250℃下保温120分钟，得到LaCrZrO5。得到的LaCrZrO5冷却后，经研磨并过200目筛，备用。
然后，按下述步骤制备高居里温度PTC热敏陶瓷材料：
（1）按比例配备Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5；
参照表1，配备的各种原料的重量百分比如下：Ba0.4Pb0.6TiO3 95%，La2O3 1.0%，Si3N40.8%，CaNb2O6 0.5%，MnSiO3 0.6%，Li2O-B2O3-SiO2玻璃粉 1.3%，LaCrZrO5 0.8%；
（2）将步骤（1）所配备的Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5粉碎并混合均匀，得到混合粉料；
本实施例中，采用行星球磨机对配备好的原料进行球磨，被球磨的原料、所用球、所用水的重量比例为：原料:球:水=1:3: 1.0，球磨过程持续4小时；
（3）将步骤（2）得到的混合粉料在烘箱中烘干，得到干粉料；
（4）向干粉料中加入粘结剂并进行造粒（在造粒后过40目筛），得到颗粒状物料；
本步骤（4）的粘结剂采用重量百分比浓度为10%的聚乙烯醇溶液，所加入的聚乙烯醇溶液的重量为干粉料的重量的10%；
（5）将步骤（4）得到的颗粒状物料压制成生坯片；
本步骤（5）中，在30Mpa压力下对颗粒状物料进行干压成型，得到生坯片；
（6）将生坯片置于1100℃下保温1小时，使生坯片排出粘结剂并烧结，得到所述高居里温度PTC热敏陶瓷材料。
得到的高居里温度PTC热敏陶瓷材料为陶瓷片，在550℃下保温10分钟进行烧银，形成银电极；再焊引线，进行包封，即得到高居里温度PTC热敏陶瓷电阻器。实际生产中也可以选用其它电极材料（如铝电极等）替代银电极。
实施例4-6
实施例4-6中，各种原料的用量如表1所示，利用上述原料制备高居里温度PTC热敏陶瓷材料的方法分别参照实施例1、2、3。
实施例1-6得到高居里温度PTC热敏陶瓷电阻器后，测试元件的室温电阻和电阻-温度特性，得到室温电阻率、居里温度、电阻温度系数(α)和升阻比(lg(Rmax/Rmin) )等性能如表2所示。
从表2可以看出，所制备的高居里温度PTC热敏陶瓷材料居里温度高，可以达到360-365℃；室温电阻率低，为88-91Ω·cm；升阻比（lg(Rmax/Rmin)）高，可以达到5.2以上，为5.3-5.6；电阻温度系数（α）大，可以达到24-25%/℃。
表1本发明各实施例的原料配比
注：BPT表示Ba0.4Pb0.6TiO3，LBS玻璃粉表示Li2O-B2O3-SiO2玻璃粉。
表2本发明各实施例制得的高居里温度PTC热敏陶瓷材料的性能
Claims (10)
1.一种高居里温度PTC热敏陶瓷材料，其特征在于由下述重量配比的原料制成：Ba0.4Pb0.6TiO3 86-95%，La2O3 0.01-2.8%，Si3N4 0.1-4.0%，CaNb2O6 0.01-1.5%，MnSiO3 0.5-2%，Li2O-B2O3-SiO2玻璃粉 0.01-2.5%，LaCrZrO5 0.02-1.5%。
2.根据权利要求1所述的高居里温度PTC热敏陶瓷材料，其特征在于所述高居里温度PTC热敏陶瓷材料由下述重量配比的原料制成：Ba0.4Pb0.6TiO3 89-94%，La2O3 0.01-2.2%，Si3N4 0.1-3.0%，CaNb2O6 0.01-1.3%，MnSiO3 0.5-1.6%，Li2O-B2O3-SiO2玻璃粉 0.01-2.2%，LaCrZrO5 0.02-1.2%。
3.根据权利要求1所述的高居里温度PTC热敏陶瓷材料，其特征在于所述高居里温度PTC热敏陶瓷材料由下述重量配比的原料制成：Ba0.4Pb0.6TiO3 90-94%，La2O3 0.01-2.0%，Si3N4 0.1-2.5%，CaNb2O6 0.01-1.2%，MnSiO3 0.5-1.4%, Li2O-B2O3-SiO2玻璃粉0.01-2.2%，LaCrZrO5 0.02-1.2%。
4.根据权利要求1-3任一项所述的高居里温度PTC热敏陶瓷材料，其特征在于所述Ba0.4Pb0.6TiO3采用如下工艺制备：按0.4：0.6：1的摩尔比配备BaCO3、PbO和TiO2，然后对BaCO3、PbO和TiO2进行研磨并混合均匀，再将BaCO3、PbO和TiO2的混合物料放入刚玉坩埚内，于1100-1150℃下保温120分钟，得到Ba0.4Pb0.6TiO3。
5.根据权利要求1-3任一项所述的高居里温度PTC热敏陶瓷材料，其特征在于所述CaNb2O6采用如下工艺制备：按1:1的摩尔比配备CaCO3和Nb2O5，然后对CaCO3和Nb2O5进行研磨并混合均匀，再将CaCO3和Nb2O5的混合物料放入氧化铝坩埚内，于1000-1030℃保温120分钟，得到CaNb2O6。
6.根据权利要求1-3任一项所述的高居里温度PTC热敏陶瓷材料，其特征在于所述MnSiO3采用如下工艺制备：按1:1的摩尔比配备MnCO3和SiO2，然后对MnCO3和SiO2进行研磨并混合均匀，再将MnCO3和SiO2的混合物料放入氧化铝坩埚内，于1200-1250℃下保温120分钟，得到MnSiO3。
7.根据权利要求1-3任一项所述的高居里温度PTC热敏陶瓷材料，其特征在于所述Li2O-B2O3-SiO2玻璃粉采用如下工艺制备：按1：3：0.5的摩尔比配备Li2CO3、B2O3和SiO2，然后对Li2CO3、B2O3和SiO2进行研磨并混合均匀，再将Li2CO3、B2O3和SiO2的混合物料放入刚玉坩埚内，在810-840℃下保温40分钟，冷却后经研磨并过200目筛，得到Li2O-B2O3-SiO2玻璃粉。
8.根据权利要求1-3任一项所述的高居里温度PTC热敏陶瓷材料，其特征在于LaCrZrO5采用如下工艺制备：按1/2：1/2：1的摩尔比配备La2O3、Cr2O3和ZrO2，然后对La2O3、Cr2O3和ZrO2进行研磨并混合均匀，再将La2O3、Cr2O3和ZrO2的混合物料放入刚玉坩埚内，于1200-1250℃下保温120分钟，得到LaCrZrO5。
9.权利要求1-3任一项所述的高居里温度PTC热敏陶瓷材料的制备方法，其特征在于包括下述步骤：
（1）按比例配备Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5；
（2）将步骤（1）所配备的Ba0.4Pb0.6TiO3、La2O3、Si3N4、CaNb2O6、MnSiO3、Li2O-B2O3-SiO2玻璃粉和LaCrZrO5粉碎并混合均匀，得到混合粉料；
（3）将步骤（2）得到的混合粉料在烘箱中烘干，得到干粉料；
（4）向干粉料中加入粘结剂并进行造粒，得到颗粒状物料；
（5）将步骤（4）得到的颗粒状物料压制成生坯片；
（6）将生坯片置于1050-1100℃下保温1-3小时，使生坯片排出粘结剂并烧结，得到所述高居里温度PTC热敏陶瓷材料。
10.根据权利要求9所述的高居里温度PTC热敏陶瓷材料的制备方法，其特征在于：步骤（2）中采用行星球磨机对配备好的原料进行球磨，被球磨的原料、所用球、所用水的重量比例为：原料:球:水=1:3:(0.6-1.0)，球磨过程持续4-8小时；步骤（4）的粘结剂采用重量百分比浓度为10%的聚乙烯醇溶液，所加入的聚乙烯醇溶液的重量为干粉料的重量的8-10%；步骤（5）中，在20-30Mpa压力下对颗粒状物料进行干压成型，得到生坯片。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727055A (zh) * | 2018-06-27 | 2018-11-02 | 佛山市南海蜂窝电子制品有限公司 | 一种ptc蜂窝陶瓷加热元件及其制备方法 |
| CN109133201A (zh) * | 2018-09-19 | 2019-01-04 | 北京科技大学 | 基于多组分a位共掺杂镍基钙钛矿氧化物材料及使用方法 |
| CN113651612A (zh) * | 2021-08-13 | 2021-11-16 | 湖州南木纳米科技有限公司 | 钛酸钡系ptc热敏陶瓷材料及其在锂电池中的应用 |
| CN113956038A (zh) * | 2021-12-01 | 2022-01-21 | 中国科学院新疆理化技术研究所 | 一种铈掺杂钙钛矿型高温热敏陶瓷电阻材料及其制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508730A (zh) * | 2013-10-08 | 2014-01-15 | 江苏大学 | 一种低温烧结的巨介陶瓷电容器介质及其制备方法 |
| CN103664163A (zh) * | 2013-10-08 | 2014-03-26 | 江苏大学 | 一种高介晶界层陶瓷电容器介质及其制备方法 |
| CN104557024A (zh) * | 2014-12-18 | 2015-04-29 | 天津大学 | 高居里温度无铅钛酸钡基ptcr陶瓷材料及制备和应用 |
| CN104844196A (zh) * | 2015-04-10 | 2015-08-19 | 江苏大学 | 一种高居里温度ptc热敏陶瓷材料 |
-
2017
- 2017-06-23 CN CN201710487850.2A patent/CN107117959A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508730A (zh) * | 2013-10-08 | 2014-01-15 | 江苏大学 | 一种低温烧结的巨介陶瓷电容器介质及其制备方法 |
| CN103664163A (zh) * | 2013-10-08 | 2014-03-26 | 江苏大学 | 一种高介晶界层陶瓷电容器介质及其制备方法 |
| CN104557024A (zh) * | 2014-12-18 | 2015-04-29 | 天津大学 | 高居里温度无铅钛酸钡基ptcr陶瓷材料及制备和应用 |
| CN104844196A (zh) * | 2015-04-10 | 2015-08-19 | 江苏大学 | 一种高居里温度ptc热敏陶瓷材料 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727055A (zh) * | 2018-06-27 | 2018-11-02 | 佛山市南海蜂窝电子制品有限公司 | 一种ptc蜂窝陶瓷加热元件及其制备方法 |
| CN109133201A (zh) * | 2018-09-19 | 2019-01-04 | 北京科技大学 | 基于多组分a位共掺杂镍基钙钛矿氧化物材料及使用方法 |
| CN113651612A (zh) * | 2021-08-13 | 2021-11-16 | 湖州南木纳米科技有限公司 | 钛酸钡系ptc热敏陶瓷材料及其在锂电池中的应用 |
| CN113956038A (zh) * | 2021-12-01 | 2022-01-21 | 中国科学院新疆理化技术研究所 | 一种铈掺杂钙钛矿型高温热敏陶瓷电阻材料及其制备方法 |
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