CN106977205B - 一种镧锶锰氧/氧化锌铝复相陶瓷的制备方法 - Google Patents
一种镧锶锰氧/氧化锌铝复相陶瓷的制备方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- PIRUAZLFEUQMTG-UHFFFAOYSA-N lanthanum;oxomanganese;strontium Chemical compound [Sr].[La].[Mn]=O PIRUAZLFEUQMTG-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000000919 ceramic Substances 0.000 title claims abstract description 59
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 57
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 56
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 54
- 238000005245 sintering Methods 0.000 claims abstract description 50
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000011812 mixed powder Substances 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 9
- 239000004065 semiconductor Substances 0.000 claims abstract description 7
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims abstract description 6
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 11
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 claims description 10
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 9
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 239000004411 aluminium Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000000280 densification Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XGPJPLXOIJRLJN-UHFFFAOYSA-N [Mn].[Sr].[La] Chemical compound [Mn].[Sr].[La] XGPJPLXOIJRLJN-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 238000005457 optimization Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 52
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- PUZCLCVIHPOFJS-UHFFFAOYSA-N [O].[Mn].[Sr] Chemical compound [O].[Mn].[Sr] PUZCLCVIHPOFJS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种镧锶锰氧/氧化锌铝复相陶瓷的制备方法。具体是：首先采用固相反应法制得镧锶锰氧粉体；然后分别称量镧锶锰氧粉体和氧化锌铝粉体，放入行星球磨机中，混合均匀；将混合粉置于等离子活化烧结炉中进行烧结，烧结条件为：烧结温度1000～1200℃、保温时间3～15min、烧结压力10～50MPa，最后得到镧锶锰氧/氧化锌铝复相陶瓷。本发明添加半导体氧化锌铝粉体第二相，利用其优化与镧锶锰氧基体晶粒间的界面效应、导电通道以及良好的助烧作用，能够显著提升镧锶锰氧陶瓷室温附近的低场磁电阻效应，0.5T低磁场下磁电阻≥14％。同时采用等离子活化烧结工艺，实现了镧锶锰氧/氧化锌铝复相陶瓷的低温快速致密烧结(致密度>96％)。
Description
技术领域
本发明涉及一种镧锶锰氧/氧化锌铝复相陶瓷的制备方法，具体是一种通过添加半导体氧化锌铝粉体第二相和利用等离子活化烧结工艺来提高镧锶锰氧陶瓷的烧结致密度及其低场磁电阻效应的方法。
背景技术
镧锶锰氧(La0.7Sr0.3MnO3)化合物具有氧化还原催化活性、可变辐射率、庞磁电阻效应等特性，广泛应用于燃料电池、热控器件和微电子器件等技术领域。特别是其庞磁电阻效应(是指材料的电阻率在有外加磁场时发生明显变化的物理效应)，是读取高密度磁记录信息的理想手段，可用于制作磁传感、磁记录等微电子器件，实现信息存储和快速读写。
然而，镧锶锰氧的庞磁电阻效应只有在低温和高磁场的特殊条件下才比较明显，限制了它的实际应用。已有研究，一般通过在镧锶锰氧中添加导电金属或绝缘体第二相来增强其磁电阻效应。但金属由于低电阻特性，导致镧锶锰氧的电阻率变化范围不大，因而其对磁电阻效应的增强效果并不明显(0.5T低磁场下，<10％)；添加绝缘体第二相，虽能通过与镧锶锰氧相之间的自旋极化隧道效应增强磁电阻，但会使强磁电阻效应发生在更低的温度而非室温，无法满足实际应用需求。此外，镧锶锰氧陶瓷通常采用常压烧结法制备，存在烧结体致密度差(<90％)、晶粒结晶性差等问题，而且烧结温度高(＞1400℃)，难以避免两相反应，影响镧锶锰氧陶瓷的性能。为此，需要寻找一种新的第二相材料及低温致密化烧结工艺以使镧锶锰氧陶瓷在室温附近、低磁场下具有较强的磁电阻效应。
发明内容
本发明旨在提供一种镧锶锰氧/氧化锌铝复相陶瓷的制备方法，该方法通过添加半导体氧化锌铝粉体第二相和利用等离子活化烧结工艺，提高了镧锶锰氧陶瓷的烧结致密度及其低场磁电阻效应。
本发明为实现上述目的，采用以下的技术方案：
本发明提供的镧锶锰氧/氧化锌铝复相陶瓷的制备方法，是通过添加半导体氧化锌铝粉体第二相和利用等离子活化烧结工艺，提高镧锶锰氧陶瓷的烧结致密度及其低场磁电阻效应，包括以下过程：以氧化镧、氧化锰和碳酸锶粉体为原料，通过固相反应法合成镧锶锰氧粉体；然后按氧化锌铝质量添加量的不同称取镧锶锰氧粉体和氧化锌铝粉体，经球磨混合均匀后，将其置于等离子活化烧结炉中烧结，得到镧锶锰氧/氧化锌铝复相陶瓷。
本方法是以摩尔比0.35:0.3:0.1称取氧化镧、氧化锰和碳酸锶原料粉体。
所述的合成的镧锶锰氧粉体的化学成分为La0.7Sr0.3MnO3，粉体粒径为78.4nm。
所述的氧化锌铝粉体为掺杂有质量10％铝的氧化锌。
所述的镧锶锰氧/氧化锌铝复相陶瓷中，氧化锌铝粉体的质量添加量为10～20％。
本方法是将镧锶锰氧/氧化锌铝混合粉体放入行星球磨机中进行球磨，球磨时间为3～6。
所述的等离子活化烧结工艺参数为：烧结温度1000～1200℃，保温时间3～15min，烧结压力10～50MPa。
本方法制备的镧锶锰氧/氧化锌铝复相陶瓷，结构致密，致密度≥96％，室温附近的低场磁电阻效应明显，0.5T低磁场下磁电阻≥14％。
本发明与现有技术相比，具有以下的有益效果：
首先，本发明添加的第二相为氧化锌铝粉体，它是一种半导体材料，导电性介于金属和绝缘体之间，它与镧锶锰氧形成复相陶瓷。氧化锌铝中主要成分是氧化锌，含有10％的铝，通过氧化锌与镧锶锰氧晶粒间的界面效应和磁散射以及铝在体系中提供新的导电通道，既能有效改善镧锶锰氧陶瓷的磁电阻效应，又能将此效应控制在室温及室温以上、满足实际应用需求。
此外，氧化锌铝是铝掺杂的氧化锌，而氧化锌具有明显的助烧作用；同时，等离子活化烧结技术利用脉冲电流在原料颗粒间的放电、温度场和应力场的耦合作用，可以在短时间(15min以内)内实现镧锶锰氧/氧化锌铝复相陶瓷的致密烧结，而且等离子活化烧结技术有低温烧结的优势，可以避免复相陶瓷中两相的扩散反应，提升复相陶瓷的性能。
与现有镧锶锰氧基复相陶瓷相比，本发明通过添加半导体氧化锌铝粉体第二相和利用等离子活化烧结工艺制备的镧锶锰氧/氧化锌铝复相陶瓷，其致密度更高(>96％)，室温附近的低场磁电阻效应明显，0.5T低磁场下磁电阻≥14％。从而为磁传感、磁记录等微电子器件的开发提供了一种高性能新材料。
附图说明
图1为实施例2、实施例3和实施例5所制备的镧锶锰氧/氧化锌铝复相陶瓷的物相结构(X射线衍射图谱)。
图2为实施例2中等离子活化烧结法制备的镧锶锰氧/氧化锌铝复相陶陶瓷的断面扫描图。
图3是采用传统常压烧结方法(温度1400℃，保温20h)制备的镧锶锰氧陶瓷的断面扫描图。
图4为镧锶锰氧纯相陶瓷以及发明实施例2和实施例5所制备的镧锶锰氧/氧化锌铝复相陶瓷的低场磁电阻随温度的变化曲线图。
具体实施方式
为更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
实施例1
(1)按摩尔比0.35:0.3:0.1称取氧化镧、氧化锰和碳酸锶原料粉体，采用固相合成法合成镧锶锰氧粉体(La0.7Sr0.3MnO3)，该粉体粒径为78.4nm。
(2)按氧化锌铝的质量添加量为10％，分别称取镧锶锰氧粉体和氧化锌铝粉体，放入行星球磨机中，球磨3h混合均匀，得到镧锶锰氧/氧化锌铝混合粉体。
(3)将镧锶锰氧/氧化锌铝混合粉体，置于等离子活化烧结炉中进行烧结，烧结条件是：
烧结温度1000℃、保温时间3min、烧结压力10MPa，最后得到镧锶锰氧/氧化锌铝复相陶瓷。
经阿基米德排水法检测，所得到的镧锶锰氧/氧化锌铝复相陶瓷的致密度为96.2％，使用综合物理性能测试仪测得在室温附近的低场(0.5T)磁电阻为(14.3％)。
实施例2
(1)按摩尔比0.35:0.3:0.1称取氧化镧、氧化锰和碳酸锶原料粉体，采用固相合成法合成镧锶锰氧粉体(La0.7Sr0.3MnO3)，该粉体粒径为78.4nm。
(2)按氧化锌铝的质量添加量为20％，分别称取镧锶锰氧粉体和氧化锌铝粉体，放入行星球磨机中，球磨4h混合均匀，得到镧锶锰氧/氧化锌铝混合粉体。
(3)将镧锶锰氧/氧化锌铝混合粉体，置于等离子活化烧结炉中进行烧结，烧结条件是：烧结温度1100℃、保温时间5min、烧结压力50MPa，最后得到镧锶锰氧/氧化锌铝复相陶瓷。
经阿基米德排水法检测，所得到的镧锶锰氧/氧化锌铝复相陶瓷的致密度为97.7％，使用综合物理性能测试仪测得在室温附近的低场(0.5T)磁电阻为(16.2％)。
实施例3
(1)按摩尔比0.35:0.3:0.1称取氧化镧、氧化锰和碳酸锶原料粉体，采用固相合成法合成镧锶锰氧粉体(La0.7Sr0.3MnO3)，该粉体粒径为78.4nm。
(2)按氧化锌铝的质量添加量为15％，分别称取镧锶锰氧粉体和氧化锌铝粉体，放入行星球磨机中，球磨5h混合均匀，得到镧锶锰氧/氧化锌铝混合粉体。
(3)将镧锶锰氧/氧化锌铝混合粉体，置于等离子活化烧结炉中进行烧结，烧结条件是：烧结温度1200℃、保温时间5min、烧结压力30MPa，最后得到镧锶锰氧/氧化锌铝复相陶瓷。
经阿基米德排水法检测，所得到的镧锶锰氧/氧化锌铝复相陶瓷的致密度为97.2％，使用综合物理性能测试仪测得在室温附近的低场(0.5T)磁电阻为(15.4％)。
实施例4
(1)按摩尔比0.35:0.3:0.1称取氧化镧、氧化锰和碳酸锶原料粉体，采用固相合成法合成镧锶锰氧粉体(La0.7Sr0.3MnO3)，该粉体粒径为78.4nm。
(2)按氧化锌铝的质量添加量为20％，分别称取镧锶锰氧粉体和氧化锌铝粉体，放入行星球磨机中，球磨6h混合均匀，得到镧锶锰氧/氧化锌铝混合粉体。
(3)将镧锶锰氧/氧化锌铝混合粉体，置于等离子活化烧结炉中进行烧结，烧结条件是：烧结温度1200℃、保温时间15min、烧结压力50MPa，最后得到镧锶锰氧/氧化锌铝复相陶瓷。
经阿基米德排水法检测，所得到的镧锶锰氧/氧化锌铝复相陶瓷的致密度为97.6％，使用综合物理性能测试仪测得在室温附近的低场(0.5T)磁电阻为(16.1％)。
实施例5
(1)按摩尔比0.35:0.3:0.1称取氧化镧、氧化锰和碳酸锶原料粉体，采用固相合成法合成镧锶锰氧粉体(La0.7Sr0.3MnO3)，该粉体粒径为78.4nm。
(2)按氧化锌铝的质量添加量为10％，分别称取镧锶锰氧粉体和氧化锌铝粉体，放入行星球磨机中，球磨4h混合均匀，得到镧锶锰氧/氧化锌铝混合粉体。
(3)将镧锶锰氧/氧化锌铝混合粉体，置于等离子活化烧结炉中进行烧结，烧结条件是：烧结温度1100℃、保温时间5min、烧结压力30MPa，最后得到镧锶锰氧/氧化锌铝复相陶瓷。
经阿基米德排水法检测，所得到的镧锶锰氧/氧化锌铝复相陶瓷的致密度为96.6％，使用综合物理性能测试仪测得在室温附近的低场(0.5T)磁电阻为(14.7％)。
实施例6
(1)按摩尔比0.35:0.3:0.1称取氧化镧、氧化锰和碳酸锶原料粉体，采用固相合成法合成镧锶锰氧粉体(La0.7Sr0.3MnO3)，该粉体粒径为78.4nm。
(2)按氧化锌铝的质量添加量为15％，分别称取镧锶锰氧粉体和氧化锌铝粉体，放入行星球磨机中，球磨3h混合均匀，得到镧锶锰氧/氧化锌铝混合粉体。
(3)将镧锶锰氧/氧化锌铝混合粉体，置于等离子活化烧结炉中进行烧结，烧结条件是：烧结温度1100℃、保温时间5min、烧结压力50MPa，最后得到镧锶锰氧/氧化锌铝复相陶瓷。
经阿基米德排水法检测，所得到的镧锶锰氧/氧化锌铝复相陶瓷的致密度为97.3％，使用综合物理性能测试仪测得在室温附近的低场(0.5T)磁电阻为(15.5％)。
上述所有实施例中，所制备的镧锶锰氧/氧化锌铝复相陶瓷都有较高的致密度(＞96％)，并且随着氧化锌铝的添加量增加，陶瓷的致密度增大，其结果如表1所示。
实施例2、实施例3和实施例5所制备的镧锶锰氧/氧化锌铝复相陶瓷的X射线衍射物相分析结果如图1所示。由图1可以看出，所制备的复相陶瓷只有镧锶锰氧和氧化锌铝的特征峰，不存在其它杂相，并且随着氧化锌铝添加比例的增加，氧化锌铝的特征峰更加明显。
实施例2中用等离子活化烧结技术在温度为1100℃、保温5min的条件下制备得到的镧锶锰氧/氧化锌铝复相陶瓷断面扫描图如图2所示，其结构致密，表面平整；图中小图为其热腐蚀之后的扫描图，可以看出两种颗粒只是机械共混。图3是采用常压烧结在温度为1400℃，保温20h的条件下制备得到的镧锶锰氧纯相陶瓷的断面扫描图，从图中可以看出，陶瓷结构疏松，内部缺陷多。
本发明实施例2和实施例3与镧锶锰氧(LSMO)纯相陶瓷的低场磁电阻效应的比较，其结果如图3所示：实施例2和实施例3所制备的复相陶瓷在室温附近的磁电阻效应分别为16.2％、14.7％，明显高于镧锶锰氧纯相陶瓷的低场磁电阻效应(1.4％)。
上述实施例中，采用的固相反应方法，主要是先将称好的原料倒入尼龙球磨罐中进行球磨，将球磨后的浆料在80℃烘箱中烘干得到混合原料粉；然后将混合原料粉置于1100℃低温马弗炉中预烧，保温2h；最后将预烧后粉料进行二次球磨，球磨后的粉体在温度为1300℃下煅烧2h得到La0.7Sr0.3MnO3粉体。详情可参阅：梁迪飞，杨勇，邓龙江.LSMO/SiO2复合材料变温微波吸收特性研究[J].中国稀土学报,2009,27(1):76-80.。
表1本明实施例制备的镧锶锰氧/氧化锌铝复相陶瓷的密度与致密度
Claims (3)
1.一种镧锶锰氧/氧化锌铝复相陶瓷的制备方法，其特征是通过添加半导体氧化锌铝粉体第二相和利用等离子活化烧结工艺，提高镧锶锰氧陶瓷的烧结致密度及其低场磁电阻效应，包括以下过程：以氧化镧、氧化锰和碳酸锶粉体为原料，通过固相反应法合成镧锶锰氧粉体；然后按氧化锌铝质量添加量的不同称取镧锶锰氧粉体和氧化锌铝粉体，经球磨混合均匀后，将其置于等离子活化烧结炉中烧结，得到镧锶锰氧/氧化锌铝复相陶瓷；
所述的等离子活化烧结工艺参数为：烧结温度1000~1200℃，保温时间3~15min，烧结压力10~5 0MPa；
所述合成的镧锶锰氧粉体的化学成分为La0.7Sr0.3MnO3，粉体粒径为78.4 nm；
所述的氧化锌铝粉体为掺杂有质量10%铝的氧化锌；
所述的镧锶锰氧/氧化锌铝复相陶瓷中，氧化锌铝粉体的质量添加量为10~20%。
2.根据权利要求1所述的镧锶锰氧/氧化锌铝复相陶瓷的制备方法，其特征在于将镧锶锰氧/氧化锌铝混合粉体放入行星球磨机中进行球磨，球磨时间为3~6 h。
3.根据权利要求1至2中任一所述方法制备的镧锶锰氧/氧化锌铝复相陶瓷，其特征在于该陶瓷结构致密，致密度≥ 96%，室温附近的低场磁电阻效应明显，0.5 T低磁场下磁电阻≥ 14%。
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