锡钛酸钡BaSn_xTi_(1–x)O_3厚膜陶瓷的大电卡效应
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摘要
对无铅铁电材料锡钛酸钡(Ba(Sn_xTi_(1–x))O_3(BSnT))(x=5%,10%,15%,20%,摩尔比)陶瓷进行了研究,利用流延法得到锡钛酸钡膜带,采用X射线衍射技术对烧结后的厚膜陶瓷进行结构分析,利用扫描电子显微镜分析了样品形貌,测量了样品介温关系和电滞回线,并利用Maxwell关系对电卡效应进行了计算。结果表明:厚膜陶瓷BSnT在不同的Sn~(4+)掺杂量下的电卡效应有明显的差异,在x=0.05及外加电场10 MV/m时,绝热温变(?T)可达到2.1 K,且x=0.05的样品在5 MV/m的电卡效率最高达到0.24×10~6 K·m·V~(–1)。无铅铁电陶瓷拥有大的电卡效应可望在制冷器件上作为制冷剂使用。
Lead-free ferroelectric materials of Sn~(4+) ions doped barium titanate(Ba_xSn_(1–x)TiO_3(BSnT)) with Sn~(4+) ionic contents of 5%, 10%, 15%, and 20%(in mole fraction) were prepared, and the thick film ceramics were fabricated by a tape casting method. The microstructure of the BSnT ceramics after sintering was characterized by X-ray diffraction. The morphologies of the ceramics were analyzed by scanning electron microscopy. The dielectric constant and loss as a function of temperature, and the hysteresis loop as a function of electric field and temperature were measured. The electrocaloric effect(ECE) was calculated based on the Maxwell equations. The results indicate that the electrocaloric effect of the thick film ceramics is affected by Sn~(4+) ionic content. As x=0.05, ?T can reach 2.1 K when E=10 MV/m. The maximum elctrocaloric efficiency is up to 0.24×10~(–6) K·m·V~(–1) when E=5 MV/m for the composition as x=0.05. The lead-free ceramics with the great ECE have a promising potential application as a refrigerant in the future cooling devices.
Lead-free ferroelectric materials of Sn~(4+) ions doped barium titanate(Ba_xSn_(1–x)TiO_3(BSnT)) with Sn~(4+) ionic contents of 5%, 10%, 15%, and 20%(in mole fraction) were prepared, and the thick film ceramics were fabricated by a tape casting method. The microstructure of the BSnT ceramics after sintering was characterized by X-ray diffraction. The morphologies of the ceramics were analyzed by scanning electron microscopy. The dielectric constant and loss as a function of temperature, and the hysteresis loop as a function of electric field and temperature were measured. The electrocaloric effect(ECE) was calculated based on the Maxwell equations. The results indicate that the electrocaloric effect of the thick film ceramics is affected by Sn~(4+) ionic content. As x=0.05, ?T can reach 2.1 K when E=10 MV/m. The maximum elctrocaloric efficiency is up to 0.24×10~(–6) K·m·V~(–1) when E=5 MV/m for the composition as x=0.05. The lead-free ceramics with the great ECE have a promising potential application as a refrigerant in the future cooling devices.
引文
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[2]VALANTM.Electrocaloricmaterialsforfuturesolid–state refrigeration technologies[J]. Progr Mater Sci, 2012, 57(6):980–1009.
[3]鲁圣国,唐新桂,伍尚华,等.铁电材料中的大电卡效应[J].无机材料学报. 2014(1):6–12.LU Shengguo, TANG Xingui, WU Shanghua, et al. J Inorg Mater(in Chinese), 2014(1):6–12.
[4]LINES M E, GLASS A M. Principles and applications of ferroelectrics and related materials[M]. New York:Oxford University Press, 1977.
[5]MITSUT,TATSUZAKII.Introductiontothephysicsof ferroelectricity[M]. London:Gordon and Breaeh, 1976.
[6]KOBECO P, KURTCHATOV J. Dielectric properties of Rochelle salt crystal[J]. Z Phys, 1930, 66:192–205.
[7]WisemanGG,KueblerJK.Electrocaloriceffectinferroelectric Rochelle salt[J]. Phys Rev, 1963, 131(5):2023–2027.
[8]POHLRO,TAYLOVL.Electrocaloriceffectindopedalkali halides[J]. Phys Rev Lett, 1968, 178(3):1431–1436.
[9]SHEPERDI,FEHERG.Coolingbytheadiabaticdepolarizationof OH–molecules in KCL[J]. Phys Rev Lett, 1965, 15(5):194–198.
[10]SHEBANOVL,BORMANK.Onlead-scandiumTantalatesolid solutionswithhighelectrocaloriceffect[J].Ferroelectrics,1992,127:1143–1148.
[11]MISCHENKO A S, ZHANG Q, SCOTT J F, et al. Giant electrocaloric effectinthin–filmPbZr0.95Ti0.05O3[J].Science,2006,311(5765):1270–1271.
[12]NEESEB,CHUBJ,LuSG,etal.LargeElectrocaloricEffectin FerroelectricPolymersNearRoomTemperature[J].Science,2008:821–823.
[13]COLE M W, NGO E,HIRSCH S,etal. The fabrication and material properties of compositionally multilayered Ba1–xSrxTi O3 thin films for realization of temperature insensitive tunable phase shifter devices[J]. J Appl Phys, 2007, 102:034104.
[14]ZHOULQ,VILARINHOPM,BAPTISTAJL.Dependenceofthe structuralanddielectricpropertiesofBa1–xSrxTi O3ceramicsolid solutionsonrawmaterialprocessing[J].JEurCeramSoc,1999,99:2015–2020.
[15]简晓东,路标,李丹丹,等.BaZr0.2Ti0.8O3无铅厚膜陶瓷的电卡效应[J].硅酸盐学报. 2017, 45(3):333–338.JIANXiaodong,LUBiao,LIDandan,etal.JChinCeramSoc.2017,45(3):333–338.
[16]REHRIGPW,PARKSE,TROLIER–MCKINSTRYS,etal.Piezoelectricpropertiesofzirconium-dopedbariumtitanatesingle crystalsgrownbytemplatedgraingrowth[J].JApplPhys,1999,86:1657.
[17]HENNINGS D, SCHNELL A, SIMON G J. Diffuse ferroelectric phase transitioninBa(Ti1-yZry)O3ceramics[J].JAmCeramSoc,1982,65:539.
[18]ANWAR S, SAGDEOPR, LALLA N P. Ferroelectric relaxor behavior inhafniumdopedbarium–titanateceramic[J].SolidStateCommun,2006, 138:331–336.
[19]TIAN H Y, WANG Y, MIAO J, et al. Preparation and characterization ofhafniumdopedbariumtitanateceramics[J].JAlloyCompd,2007,431:197–202.
[20]PAYNE W H, TENNERY V J. Dielectric and structural investigations of the system BaTiO3–BaHfO3[J]. J Am Ceram Soc, 1965:413–417.
[21]ANGC,JINGZ,YUZ.FerroelectricrelaxorBa(Ti,Ce)O3[J].J Phys–Conden Mat, 2002, 14:8901–8912.
[22]CURECHERIU L P, DELUCA M, MOCANU Z V, et al. Investigation of the ferroelectric-relaxor crossover in Ce-doped BaTiO3 ceramics by impedancespectroscopyandRamanstudy[J].Phasetransit,2013,86(7):703–714.
[23]LUSG,XUZK,CHENH.Tunabilityandrelaxorpropertiesof ferroelectric barium stannate titanate ceramics[J]. Appl Phys Lett, 2004, 85(22):5319.
[24]HORCHIDANN,IANCULESCUAC,CURECHERIULP,etal.Preparationandcharacterizationofbariumtitanatestannatesolid solutions[J]. J Alloys Compd, 2011, 509(14):4731–4737.
[25]WEI X, FENG Y J, YAO X. Dielectric relaxation behavior in barium stannate titanate ferroelectric ceramics with diffused phase transition[J].Appl Phys Lett, 2003, 83:2031–2033.
[26]HORCHIDANN,IANCULESCUAC,VASILESCUCA,etal.Multiscalestudyofferroelectric-relaxorcrossoverinBa SnxTi1–xO3ceramics[J]. J Eur Ceram Soc, 2014, 34(15):3661–3674.
[27]LUO Z D, ZHANG D W, LIU Y et al. Enhanced electrocaloric effect inlead-freeBa Ti1–xSnxO3ceramicsnearroomtemperature[J].Appl Phys Lett, 2014, 105:102904.
[28]JINL,LIF,ZHANGSJ.Decodingthefingerprintofferroelectric loops:comprehensionofthematerialpropertiesandstructures[J].J Am Ceram Soc, 2014, 97(1):1–27.
[29]LU S G, CAI Z H, OUYANG Y X, et al. Electrical field dependence of electrocaloric effect in relaxor ferroelectrics[J]. Ceram Inter, 2015, 41:S15–S18.
[30]LUSG,RO?I?B,ZHANGQM,etal.Electrocaloriceffectin ferroelectric polymers[J]. Appl Phys A, 2012, 107(3):559–566.
[31]MorimotoK,UematsuA,SawaiS,etal.SimultaneousMeasurement of specific heat capacity, thermal conductivity and thermal diffusivity offerroelectricBa(Ti1-x,Snx)O3 ceramicsbythermalradiation calorimetry[J]. Jpn J Appl Phys, 2002, 41:6943–6947.
[32]BAIY,HANX,DINGK,etal.Combinedeffectsofdiffusephase transitionandmicrostructureontheelectrocaloriceffectin Ba1–xSrxTi O3 ceramics[J]. Appl Phys Lett, 2013, 103:162902.
[33]LIX,QIANXS,GUH,etal.Giantelectrocaloriceffectin ferroelectricpoly(vinylidenefluoride–trifluoroethylene)copolymers near a first–order ferroelectric transition[J]. Appl Phys Lett, 2012, 101:132903.
[34]THACHERPD.Electrocaloriceffectsinsomeferroelectricand antiferroelectricPb(Zr,Ti)O3compounds[J].JApplPhys,1968,39:1996–2002.
[35]BAIY,HANX,QIAOLJ.Optimizedelectrocaloricrefrigeration capacity in lead–free(1–x)BaZr0. 2Ti0. 8O3–x Ba0. 7Ca0. 3Ti O3 ceramics[J].Appl Phys Lett, 2013, 102:252904.
[36]KAR–NARAYANS,MATHURND.Directandindirect electrocaloricmeasurementsusingmultilayercapacitors[J].JPhysD Appl Phys, 2010, 43:032002.
[37]WANGJF,YANGT,CHENS,etal.NonadiabaticDirect MeasurementElectrocaloricEffectinLead-FreeBa,Ca(Zr,Ti)O3Ceramics[J]. J Alloy Compd, 2013, 550:561–563.