La_2NiMnO_6双钙钛矿陶瓷的等离子活化烧结
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摘要
针对常压烧结La_2NiMnO_6 (简称LNMO)双钙钛矿陶瓷存在的烧结温度高、致密度低、工艺周期长等问题,采用等离子活化烧结技术(PlasmaActivatedSintering,简称PAS)制备LNMO陶瓷,主要研究了烧结工艺(温度、压力)对其物相结构、显微形貌、致密度和介电性能的影响,以期得到物相单一、结构致密、性能良好的LNMO双钙钛矿陶瓷。利用X射线衍射仪、阿基米德排水法、扫描电子显微镜、阻抗分析仪等手段,系统测试表征了LNMO陶瓷的结构与性能。结果表明:升高烧结温度有利于改善LNMO陶瓷的结晶性并增大晶粒尺寸,但过高温度会导致杂相生成;增大烧结压力对物相无明显影响,但在一定程度上提升了致密度。确定了较适宜的PAS条件为:烧结温度975～1000℃、烧结压力80 MPa,在此条件下烧结得到的LNMO陶瓷为单一的正交结构,致密度为92%,具有较大的介电常数(～106)。与常压烧结相比,等离子活化技术集等离子体活化、压力、电阻加热为一体,可在更低温度(降低400～500℃)和更短时间(缩短2～20 h)内获得较为致密的LNMO陶瓷。
La_2NiMnO_6(LNMO) double-perovskite ceramics are normally prepared by the conventional pressureless sintering technique, which is difficult to produce dense structure and usually needs high sintering temperature as well as long sintering period. In this study, highly-dense La_2NiMnO_6 ceramics with good performance were prepared by a novel Plasma Activated Sintering(PAS) method. The influence of PAS parameters, including sintering temperature and pressure, on crystalline phase, microstructure, relative density and dielectric properties of the LNMO ceramics were systematically studied by the means of XRD, SEM, Archimedes method, and impedance analyzer. The results showed that the crystallinity and grain size of the LNMO ceramics increased with the increase of sintering temperature, but the impurity phases might emerge if the sintering temperature further increased above 1000 ℃. The sintering pressure had little effect on crystalline phase, while the relative density of the LNMO ceramics could be effectively enhanced with the sintering pressure increasing. LNMO ceramics in single orthorhombic structure with relative density of 92% and giant dielectric constant(～106) were successfully obtained at the optimum PAS conditions, i.e., sintering temperature of 975-1000 ℃ and sintering pressure of 80 MPa. Compared to the traditional pressureless sintering, LNMO ceramics with dense structure could be obtained by PAS at a relative lower sintering temperature(reduced by 400-500 ℃) with a shorter sintering period(reduced by 2-20 h), which should be attributed to the coupling effect of temperature and stress as well as activation during the sintering process.
La_2NiMnO_6(LNMO) double-perovskite ceramics are normally prepared by the conventional pressureless sintering technique, which is difficult to produce dense structure and usually needs high sintering temperature as well as long sintering period. In this study, highly-dense La_2NiMnO_6 ceramics with good performance were prepared by a novel Plasma Activated Sintering(PAS) method. The influence of PAS parameters, including sintering temperature and pressure, on crystalline phase, microstructure, relative density and dielectric properties of the LNMO ceramics were systematically studied by the means of XRD, SEM, Archimedes method, and impedance analyzer. The results showed that the crystallinity and grain size of the LNMO ceramics increased with the increase of sintering temperature, but the impurity phases might emerge if the sintering temperature further increased above 1000 ℃. The sintering pressure had little effect on crystalline phase, while the relative density of the LNMO ceramics could be effectively enhanced with the sintering pressure increasing. LNMO ceramics in single orthorhombic structure with relative density of 92% and giant dielectric constant(～106) were successfully obtained at the optimum PAS conditions, i.e., sintering temperature of 975-1000 ℃ and sintering pressure of 80 MPa. Compared to the traditional pressureless sintering, LNMO ceramics with dense structure could be obtained by PAS at a relative lower sintering temperature(reduced by 400-500 ℃) with a shorter sintering period(reduced by 2-20 h), which should be attributed to the coupling effect of temperature and stress as well as activation during the sintering process.
引文
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[20]CHENG C B,FAN R H,WANG Z Y,et al.Tunable and weakly negative permittivity in carbon/silicon nitride composites with different carbonizing temperatures.Carbon,2017,125:103-112.
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[22]XIE P T,ZHANG Z D,LIU K P,et al.C/SiO2 meta-composite:overcoming the l/a relationship limitation in metamaterials.Carbon,2017,125:1-8.
[23]XIE P T,SUN W,LIU Y,et al.Carbon aerogels towards new candidates for double negative metamaterials of low density.Carbon,2018,129:598-606.
[24]XIE P T,WANG Z Y,ZHANG Z D,et al.Silica microsphere templated self-assembly of a three-dimensional carbon network with stable radio-frequency negative permittivity and low dielectric loss.Journal of Materials Chemistry C,2018,6:5239-5249.
[25]XIE P T,LI H Y,HE B,et al.Bio-gel derived nickel/carbon nanocomposites with enhanced microwave absorption.Journal of Materials Chemistry C,2018,6:8812-8822.
[2]GOODENOUGH J B,WOLD A,ARNOTT R J,et al.Relationship between crystal symmetry and magnetic properties of ionic compounds containing.Physical Review,1961,124(2):373-384.
[3]GAN H,WANG C B,LI L,et al.Structural and magnetic properties of La2NiMnO6 ceramic prepared by ultra-high pressure sintering.Journal of Alloys&Compounds,2018,735:2486-2490.
[4]郭宇桥.双钙钛矿La2NiMnO6掺杂体系结构及物性研究.合肥:中国科学技术大学博士学位论文,2013.
[5]LI C N,LIU B X,HE Y Y,et al.Preparation,characterization and dielectric tunability of La2NiMnO6 ceramics.Journal of Alloys&Compounds,2014,590(2):541-545.
[6]BARBOSAA D A B,LUFASOB M W,REICHLOVA H,et al.Badoping effects on structural,magnetic and vibrational properties of disordered La2NiMnO6.Journal of Alloys&Compounds,2016,663:899-905.
[7]CHEN H,CAO Z Z,WANG L Y,et al.The giant dielectric constant and tunable properties of La2NiMnO6-x Mg O ceramics.Journal of Alloys&Compounds,2014,616:213-220.
[8]CHAIM R,CHEVALLIER G,WEIBEL A,et al.Grain growth during spark plasma and flash sintering of ceramic nanoparticles:a review.Journal of Materials Science,2018,53(5):3087-3015.
[9]MUNIR Z A,ANSELMI-TAMBURINI U,OHYANAGI M.The effect of electric field and pressure on the synthesis and consolidation of materials:a review of the spark plasma sintering method.Journal of Materials Science,2006,41(3):763-777.
[10]SHEN Z J,JOHNSSON M,ZHAO Z,et al.Spark plasma sintering of alumina.Journal of the American Ceramic Society,2010,85(8):1921-1927.
[11]LI C C,XIANG H C,CHEN J W,et al.Phase transition,dielectric relaxation and piezoelectric properties of bismuth doped La2Ti2O7ceramics.Ceramics International,2016,42(9):11453-11458.
[12]CERNEA M,VASILIU F,BARTHA C,et al.Characterization of ferromagnetic double perovskite Sr2FeMoO6 prepared by various methods.Ceramics International,2014,40(8):11601-11609.
[13]GHEORGHIU F,CURECHERIU L,LISIECKI I,et al.Functional properties of Sm2NiMnO6 multiferroic ceramics prepared by spark plasma sintering.Journal of Alloys&Compounds,2015,649(46):151-158.
[14]WANG S W,CHEN L D,HIRAI TOSHIO,et al.Recent development of pulse electric current sintering mechanism.Journal of Inorganic Materials,2001,6(16):1055-1061.
[15]DASS R I,YAN J Q,GOODENOUGH J B.Oxygen stoichiometry,ferromagnetism,and transport properties of La2-xNiMnO6+δ.Physical Review B,2003,68(6):064415.
[16]DEMINA A N,CHEREPANOV V A,PETROV A N,et al.Phase equilibria and crystal structures of mixed oxides in the La-MnNi-O System.Inorganic Materials,2005,41(7):736-742.
[17]LIN Y Q,CHEN X M,LIU X Q,et al.Relaxor-like dielectric behavior in La2NiMnO6 double perovskite ceramics.Solid State Commun,2009,149(19/20):784-787.
[18]TIRMAL P M,MANE S M,PATIL S K,et al.Effects of partial site substitution on magnetic and dielectric behavior of La2NiMnO6double perovskite.Journal of Materials Science:Materials in Electronics,2016,27(5):4314-4320.
[19]CAO Z Z,LIU X T,HE W Y,et al.Extrinsic and intrinsic contributions for dielectric behavior of La2NiMnO6 ceramic.Physica B:Condensed Matter,2015,477:8-13.
[20]CHENG C B,FAN R H,WANG Z Y,et al.Tunable and weakly negative permittivity in carbon/silicon nitride composites with different carbonizing temperatures.Carbon,2017,125:103-112.
[21]XIE P T,WANG Z Y,SUN K,et al.Regulation mechanism of negative permittivity in percolating composites via building blocks.Applied Physics Letters,2017,111:112903.
[22]XIE P T,ZHANG Z D,LIU K P,et al.C/SiO2 meta-composite:overcoming the l/a relationship limitation in metamaterials.Carbon,2017,125:1-8.
[23]XIE P T,SUN W,LIU Y,et al.Carbon aerogels towards new candidates for double negative metamaterials of low density.Carbon,2018,129:598-606.
[24]XIE P T,WANG Z Y,ZHANG Z D,et al.Silica microsphere templated self-assembly of a three-dimensional carbon network with stable radio-frequency negative permittivity and low dielectric loss.Journal of Materials Chemistry C,2018,6:5239-5249.
[25]XIE P T,LI H Y,HE B,et al.Bio-gel derived nickel/carbon nanocomposites with enhanced microwave absorption.Journal of Materials Chemistry C,2018,6:8812-8822.
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