CN116715521B - 一种接触式温控器中CaYNbMnO7热敏电阻的冷辅助制备方法 - Google Patents
一种接触式温控器中CaYNbMnO7热敏电阻的冷辅助制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000005245 sintering Methods 0.000 claims abstract description 37
- 239000000919 ceramic Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 7
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 7
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000009466 transformation Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
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- 229910052697 platinum Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
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- 239000004570 mortar (masonry) Substances 0.000 claims description 5
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- 230000032683 aging Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000009770 conventional sintering Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明公开了一种接触式温控器中CaYNbMnO7热敏电阻的冷辅助制备方法，该方法以原料碳酸钙、三氧化二钇、五氧化二铌和二氧化锰利用冷烧结工艺制备相对致密的CaYNbMnO7陶瓷胚体，然后通过相对较低的烧结温度来促进相转变，并进一步提高CaYNbMnO7热敏陶瓷的致密度，得到CaYNbMnO7的热敏电阻材料。本发明所述方法具有能耗低、烧结时间短等优点，制得的CaYNbMnO7的圆片状高密度陶瓷块体材料致密度较好，温度150℃下老化200h后的老化漂移率最低为0.82%，具有负温度系数特性，适合作为工业高温热风机中温控器的热敏元件。
Description
技术领域
本发明涉及一种接触式温控器中CaYNbMnO7热敏电阻的冷辅助制备方法。
技术背景
工业高温热风机是煤炭行业、电力行业、石油行业、化工行业等领域实现高效快速完成工作的重要设备，在高温烘干、加热和熔炼等领域起着十分重要的作用。而对于工业高温热风机来说，控制系统又是整个机器的大脑，所以拥有一个精度高，测温区间宽、老化稳定性强的温控器，是保证工业高温热风机高效、耐用等特点重要因素。负温度系数热敏电阻陶瓷材料由于其精度高，体积小，响应速度快等优点使高精度、宽温区、高稳定性温控器的制备成为了可能。传统的负温度系数热敏陶瓷材料通常使用高温固相法，此种方法通常需要极高的温度(T≥1000℃)，对于资源和环境来说都是一种浪费和损害。
为解决上述问题，研究人员主要通过以下两方面策略来实现高精度，强老化稳定性的温控器中热敏材料的制备。首先用负温度系数热敏材料CaYNbMnO7对现有的铂电阻进行替换。CaYNbMnO7材料是层状类钙钛矿结构，此材料拥有较高的高温稳定性，可以直接提高温控器的使用寿命。其次是利用冷辅助烧结工艺降低负温度系数热敏电阻在制备过程中的烧结温度。冷辅助烧结是利用冷烧结技术在陶瓷烧结之前以极低的温度(T≤400℃)将陶瓷胚体致密化，然后再将相对致密的陶瓷胚体进行常规烧结，但此时的烧结温度会比固相烧结更低，烧结时间也会比常规烧结更短。既节约了烧结所用的资源，也减少了二氧化碳的排放，且烧结后的热敏陶瓷材料会比高温固相烧结后的陶瓷材料拥有更好的线性度和更低的老化漂移率。
发明内容
本发明目的在于，提供一种接触式温控器中CaYNbMnO7热敏电阻的冷辅助制备方法，该方法以原料碳酸钙、三氧化二钇、五氧化二铌和二氧化锰利用冷烧结工艺制备相对致密的CaYNbMnO7陶瓷胚体，然后通过相对较低的烧结温度来促进相转变，并进一步提高CaYNbMnO7热敏陶瓷的致密度，得到CaYNbMnO7的热敏陶瓷材料。本发明所述方法具有能耗低、烧结时间短等优点，制得的CaYNbMnO7的圆片状高密度陶瓷块体材料致密度较好，温度150℃下老化200h后的老化漂移率最低为0.82％，具有优异的负温度系数特性，适合作为工业高温热风机中温控器的热敏元件。
本发明所述的一种接触式温控器中CaYNbMnO7热敏电阻的冷辅助制备方法，该方法利用冷烧结制备相对致密的CaYNbMnO7陶瓷胚体，然后通过相对较低的烧结温度来促进相转变，具体操作按下列步骤进行：
a、按CaYNbMnO7的摩尔比，分别称取原料碳酸钙、三氧化二钇、五氧化二铌和二氧化锰，置于玛瑙研钵中混合研磨6-8h，然后于温度1350℃下煅烧3-4h，并再次研磨6h，得到分散的CaYNbMnO7粉体；
b、将取纯度为96％的NaOH作为辅助液相，与步骤a所得CaYNbMnO7粉体混合均匀，得到混合粉体，其中辅助液相添加占比为CaYNbMnO7粉体质量的0.5wt％；
c、将步骤b所得的混合粉体倒入冷烧结模具中，施加500-700MPa压力，保压10min后，以30℃/min的速率升温至350℃，并保温2-4h，得到CaYNbMnO7陶瓷胚体，即完成第一步烧结；
d、将步骤c得到的陶瓷胚体放入马弗炉中，以3℃/min的速率升温至1350℃，并保温2-4h，然后随炉冷却，即完成第二步烧结，得到CaYNbMnO7的圆片状高密度陶瓷块体材料；
e、将步骤d得到的圆片状高密度陶瓷块体材料正反两面涂覆铂浆电极，然后于温度900℃下持续退火1小时，即得到温度范围为-75-300℃，材料常数为B0℃/50℃＝2072K-2738K的中低温高稳定性CaYNbMnO7热敏电阻材料。
通过本发明所述方法获得的CaYNbMnO7热敏电阻材料，为层状钙钛矿结构，同时具备了相对较好的高温稳定性，又具备了良好的NTC性能，可用以制造工业高温热风机中温控器的热敏元件。
与现有技术相比：本发明制备CaYNbMnO7热敏电阻材料的过程中具有独特之处：
本发明采用冷辅助烧结需要加入NaOH作为液相，用来促进陶瓷胚体的致密化；
所述冷辅助烧结工艺陶瓷材料退火温度相对较低，退火时间相对较短，能够节约能源，减少大气污染；
通过本发明所述方法制备的CaYNbMnO7热敏电阻材料在温度-75-300℃时Ln(ρ)与1000/T具有良好的线性关系，皮尔森系数能够达到0.999；在温度150℃下老化200h后的老化漂移率为0.82％。
附图说明
图1为本发明制备的CaYNbMnO7热敏材料的XRD谱图；
图2本发明制备的CaYNbMnO7热敏材料的阻温特性曲线。
具体实施方式
实施例1
a、按CaYNbMnO7的摩尔比，分别称取原料碳酸钙2.321g、三氧化二钇2.592g、五氧化二铌3.051g和二氧化锰2.036g，置于玛瑙研钵中混合研磨6h，然后于温度1350℃下煅烧3h，并再次研磨6h，得到分散的CaYNbMnO7粉体10g；
b、称取0.003g纯度为96％的NaOH作为辅助液相，与步骤a所得CaYNbMnO7粉体0.6g混合均匀，得到混合粉体，其中辅助液相添加占比为CaYNbMnO7粉体质量的0.5wt％；
c、将步骤b所得的混合粉体倒入冷烧结模具中，施加500MPa压力，保压10min后，以30℃/min的速率升温至350℃，并保温2h，得到CaYNbMnO7陶瓷胚体，即完成第一步烧结；
d、将步骤c得到的陶瓷胚体放入马弗炉中，以3℃/min的速率升温，升温至1350℃，并保温4h，然后随炉冷却，即完成第二步烧结，得到CaYNbMnO7的圆片状高密度陶瓷块体材料；
e、将步骤d烧结热敏陶瓷材料正反两面涂覆铂浆电极，然后于温度900℃下持续退火1小时，即得到温度范围为-75-300℃，材料常数为B0℃/50℃＝2293K的中低温高稳定性CaYNbMnO7热敏电阻材料。
在温度150℃下老化200h后，电阻偏差的绝对值小于8.55％。
实施例2
a、按CaYNbMnO7的摩尔比，分别称取碳酸钙2.321g、三氧化二钇2.592g、五氧化二铌3.051g和二氧化锰2.036g作为原料，置于玛瑙研钵中混合研磨7h，然后于温度1350℃下煅烧4h，并再次研磨6h，得到分散的CaYNbMnO7粉体10g；
b、称取0.003g纯度为96％的NaOH作为辅助液相，与步骤a所得CaYNbMnO7粉体0.6g混合均匀，得到混合粉体，其中辅助液相添加占比为CaYNbMnO7粉体质量的0.5wt％；
c、将步骤b所得的混合粉体倒入冷烧结模具中，施加600MPa压力，保压10min后，以30℃/min的速率升温，升温至350℃，并保温4h，得到CaYNbMnO7陶瓷胚体，即完成第一步烧结；
d、将步骤c得到的陶瓷胚体放入马弗炉中，以3℃/min的速率升温，升温至1350℃，并保温2h，然后随炉冷却，即完成第二步烧结，得到CaYNbMnO7的圆片状高密度陶瓷块体材料；
e、将步骤d烧结热敏陶瓷材料正反两面涂覆铂浆电极，然后于温度900℃下持续退火1小时，即得到温度范围为-75-300℃，材料常数为B0℃/50℃＝2072K的中低温高稳定性CaYNbMnO7热敏电阻材料。
在温度150℃下老化200h后，电阻偏差的绝对值小于2.49％。
实施例3
a、按CaYNbMnO7的摩尔比，分别称取碳酸钙2.321g、三氧化二钇2.592g、五氧化二铌3.051g和二氧化锰2.036g作为原料，置于玛瑙研钵中混合研磨8h，然后于温度1350℃下煅烧4h，并再次研磨6h，得到分散的CaYNbMnO7粉体10g；
b、称取0.003g纯度为96％的NaOH作为辅助液相，与步骤a所得CaYNbMnO7粉体0.6g混合均匀，得到混合粉体，其中辅助液相添加占比为CaYNbMnO7粉体质量的0.5wt％；
c、将步骤b所得的混合粉体倒入冷烧结模具中，施加700MPa压力，保压10min后，以30℃/min的速率升温，升温至350℃，并保温3h，得到CaYNbMnO7陶瓷胚体，即完成第一步烧结；
d、将步骤c得到的陶瓷胚体放入马弗炉中，以3℃/min的速率升温，升温至1350℃，并保温3h，然后随炉冷却，即完成第二步烧结，得到CaYNbMnO7的圆片状高密度陶瓷块体材料；
e、将步骤d烧结热敏陶瓷材料正反两面涂覆铂浆电极，然后于温度900℃下持续退火1小时，即得到温度范围为-75-300℃，材料常数为B0℃/50℃＝2738K的中低温高稳定性CaYNbMnO7热敏电阻材料。
在温度150℃下老化200h后，电阻偏差的绝对值小于0.87％。
上述仅为本发明的具体实施方式，但本发明的设计构思并不局限于此。
Claims (1)
1.一种接触式温控器中CaYNbMnO7热敏电阻的冷辅助制备方法，其特征在于：利用冷烧结制备相对致密的CaYNbMnO7陶瓷胚体，然后通过相对较低的烧结温度来促进相转变，具体操作按下列步骤进行：
a、按CaYNbMnO7的摩尔比，分别称取原料碳酸钙、三氧化二钇、五氧化二铌和二氧化锰，置于玛瑙研钵中混合研磨6-8h，然后于温度1350℃下煅烧3-4 h，并再次研磨6h，得到分散的CaYNbMnO7粉体；
b、将取纯度为96%的NaOH作为辅助液相，与步骤a所得CaYNbMnO7粉体混合均匀，得到混合粉体，其中辅助液相添加占比为CaYNbMnO7粉体质量的0.5wt%；
c、将步骤b所得的混合粉体倒入冷烧结模具中，施加500-700MPa压力，保压10min后，以30℃/min的速率升温至350℃，并保温2-4h，得到CaYNbMnO7陶瓷胚体，即完成第一步烧结；
d、将步骤c得到的陶瓷胚体放入马弗炉中，以3℃/min的速率升温至1350℃，并保温2-4h，然后随炉冷却，即完成第二步烧结，得到CaYNbMnO7的圆片状高密度陶瓷块体材料；
e、将步骤d得到的圆片状高密度陶瓷块体材料正反两面涂覆铂浆电极，然后于温度900℃下持续退火1小时，即得到温度范围为-75-300℃，材料常数为B0℃/50℃= 2072 K-2738 K的中低温高稳定性CaYNbMnO7热敏电阻材料。
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