阻抗渐变高介电钛酸钡/聚酰亚胺复合薄膜的设计与制备

人体皮肤与空气间在介电常数上有着失配性,可穿戴设备所用的材料需要与人体皮肤有良好的匹配性能,而单一的材料与结构已不能满足这种需求。利用原位聚合法合成了一系列钛酸钡(BaTiO_3)/聚酰亚胺(PI)混合溶液,通过逐层流延涂覆的方法设计制备了一种具有阻抗渐变性质的多层BaTiO_3/PI复合薄膜。结果表明:BaTiO_3纳米粒子可在复合薄膜中均匀分散,调节无机粒子的含量,能够有效地控制复合薄膜的介电常数在2.5~34.0之间变化;同时,BaTiO_3/PI复合薄膜对外加电场的频率具有不敏感性,也具有良好的力学性能,能够满足可穿戴设备对材料的要求。     

晶粒尺寸对细晶钛酸钡陶瓷介电、压电和铁电性能的影响

以采用水热法制备的BaTiO₃粉体作为原料, 利用普通烧结法和两步烧结法制备出晶粒尺寸为0.25~10.15 μm的BaTiO₃陶瓷, 研究了晶粒尺寸效应对BaTiO₃陶瓷的介电、压电以及铁电性能的影响。结果表明: BaTiO₃陶瓷的四方相含量随着陶瓷晶粒尺寸的增大而增加; 当晶粒尺寸在1 μm以上时, 室温相对介电常数(ε° )和压电系数(d₃₃)随着晶粒尺寸的减小而增大, 并在晶粒尺寸为1.12 μm时分别达到最大值5628和279 pC/N, 然后两者随着晶粒尺寸的进一步减小而迅速下降。BaTiO₃陶瓷的剩余极化强度P_r随晶粒尺寸的增大而提高, 而矫顽场E_c却呈现出相反的趋势。晶粒尺寸对介电性能和压电性能的影响是由于90°电畴尺寸和晶界数量的变化。晶粒的晶体场和晶粒表面钉扎作用的变化影响了电畴, 进而改变电滞回线。     

Dielectric spectroscopy of nano BaTiO3 confined in MCM-41 mesoporous molecular sieve materials.

Dielectric properties of barium titanate (BaTiO3) particles, synthesized directly in the pores of MCM-41 materials, have been investigated in the frequency range from 20 Hz to 1 MHz for temperature intervals from 100 K to 500 K. The dielectric spectra of BaTiO3 confined in these molecular sieves were compared with the results obtained from the investigation of pure MCM-41 materials. Obtained results confirmed successful incorporation of BaTiO3 into porous matrix, but no phase transition from paraelectric to ferroelectric phase was observed due to the particle size being smaller than the critical size. Also, the overall dielectric response of investigated materials is strongly influenced by adsorbed water molecules.     

多巴胺改性BaTiO_3对BaTiO_3/PVDF复合材料击穿场强的影响

为了提高BaTiO3/PVDF复合材料的击穿场强。首先,利用多巴胺对BaTiO3进行表面功能化处理,得到多巴胺改性的BaTiO3(Dopa@BaTiO3);然后,将其与聚偏氟乙烯(PVDF)混合,采用液相浇铸法制得Dopa@BaTiO3/PVDF复合材料;最后,测量了不同Dopa@BaTiO3添加量的Dopa@BaTiO3/PVDF复合材料的击穿场强和介电性能。结果表明:与改性前的BaTiO3/PVDF复合材料相比,Dopa@BaTiO3/PVDF复合材料在击穿场强显著提高的同时,介电常数基本保持不变;当Dopa@BaTiO3添加量为3vol%时,击穿场强为210kV/mm,比改性前的复合材料的提高了78%;当Dopa@BaTiO3添加量为10vol%时,击穿场强为180kV/mm,比改性前的合材料的提高了88%。研究解决了BaTiO3/PVDF复合材料击穿场强较低的问题,可为同时提高复合材料的介电常数和击穿场强提供参考。     

原料预处理对BaTiO3压电陶瓷的物性影响

BaCO₃微粉原料通常由尺寸较大的棒状颗粒所组成, 这些棒状颗粒在一次球磨过程中由于不容易粉碎, 从而对经预烧、二次球磨所得到的BaTiO₃陶瓷微粉的化学组分的均匀性和颗粒度产生影响, 进而影响后序烧结制备的BaTiO₃陶瓷的微观组织结构和压电性能。本研究重点探讨了以BaCO₃和TiO₂为原料、通过固相反应途径制备BaTiO₃陶瓷时, 实施原料预处理对所制备的BaTiO₃压电陶瓷物性的影响。研究发现, 配料前对BaCO₃原料实施球磨预处理可明显地降低棒状颗粒的尺寸, 从而可获得颗粒度细化的BaTiO₃陶瓷微粉, 进而制备致密度更高和晶粒尺寸更小而压电性能更高的BaTiO₃陶瓷材料。研究中对BaCO₃微粉进行不同时间的球磨预处理, 然后制备钛酸钡陶瓷, 考察了其压电性能、介电性质、铁电性能和微观结构等物理性质。利用同样的BaCO₃微粉原料, 未经球磨预处理所制备的BaTiO₃陶瓷的压电系数d₃₃最高值为410 pC/N, 而实施合适的球磨预处理制备的BaTiO₃陶瓷的压电系数d₃₃最高值可达470 pC/N。     

添加BaTiO3的热压烧结Si3N4陶瓷的力学和介电性能

本研究以Al₂O₃和Nd₂O₃为烧结助剂, 采用热压烧结法制备Si₃N₄陶瓷, 系统研究了添加BaTiO₃对Si₃N₄陶瓷力学和介电性能的影响。研究结果表明, 随着BaTiO₃含量的增加, 相对密度、抗弯强度和维氏硬度都随之降低, 而断裂韧性有所升高; 即使添加5wt%~20wt%的BaTiO₃, Si₃N₄陶瓷的抗弯强度依然可以保持在600 MPa以上。Si₃N₄陶瓷的介电常数可以提高到9.26~11.50, 而介电损耗保持在10^-3量级。在Si₃N₄陶瓷中未检测到BaTiO₃结晶相, 可以认为Si₃N₄陶瓷介电常数的提高主要来源于烧结过程中形成的TiN。这些结果有助于拓展Si₃N₄陶瓷的应用领域。     

核-双壳BT@TiO_(2)@PDA纳米粒子的制备及其复合薄膜的介电性能EI北大核心CSCD

为改善聚酰亚胺(PI)基复合薄膜界面相容性,达到提高其介电性能的目的,利用钛酸正丁酯的水解反应在钛酸钡纳米粒子(BT)表面包覆水合TiO_(2)。采用聚多巴胺(PDA)进一步包覆改性粒子,制备出具有核-双壳结构的钛酸钡纳米粒子(BT@TiO_(2)@PDA)。利用核-双壳结构形成双重梯度缓冲层,减小高介电钛酸钡纳米粒子和低介电聚合物之间由于介电常数差异造成的电场畸变。通过溶液流延法制备一系列含有不同质量分数的改性钛酸钡/聚酰亚胺复合薄膜(BT@TiO_(2)@PDA/PI)。结果表明:核-双壳结构可以改善钛酸钡纳米粒子在聚酰亚胺基体中的分散性及二者的界面相容性。当填料质量分数为40%时,BT@TiO_(2)@PDA/PI复合薄膜的介电常数κ提高到8.8(1 kHz),约为纯聚酰亚胺的2.7倍,为钛酸钡/聚酰亚胺复合薄膜(BT/PI)的1.4倍。介电-温度和介电-频率测试证实,BT@TiO_(2)@PDA/PI复合薄膜具有良好的温度和频率稳定性。在100 kHz的频率范围内,复合薄膜的介电损耗均小于0.010;当填料的质量分数低于40%时,温度从25℃增加到160℃,复合薄膜介电常数的降低数值均不超过0.6(1 kHz)。     

BaTiO3纳米线的制备及其复合物介电和储能性能研究

采用两步水热法合成钛酸钡(BaTiO₃)纳米线, 并以此为填充物, 聚偏氟乙烯六氟丙烯(P(VDF-HFP))为聚合物基体制备介电复合物, 研究不同含量BaTiO₃纳米线对复合物的介电及储能性能的影响。采用X射线衍射仪、扫描电镜、透射电镜、阻抗分析仪和铁电工作站等表征BaTiO₃纳米线及其复合物的物相、微观结构、介电和储能性能。结果表明: BaTiO₃纳米线具有典型的四方相, 且在聚合物基体中具有良好的分散性与相容性。相同频率下, 复合物的介电常数随着BaTiO₃纳米线含量的增加而增加。含量为20vol%的复合物, 在1 kHz频率下其介电常数取得最 大值30.69。含量为5vol%的复合物, 在场强为240 kV/mm时, 获得了最大的储能密度与放电能量密度, 分别为4.89和2.58 J/cm³。     

BaTiO3陶瓷的低温冷烧结制备及性能研究

近年来, 冷烧结低温制备陶瓷引起了很大关注, 并在BaTiO₃陶瓷的制备上取得了一定进展。为了提高冷烧结BaTiO₃陶瓷性能, 本研究采用水热法制备了分散性好、粒径为100 nm的四方相(晶格参数c/a为1.0085) BaTiO₃粉末。采用0.1 mol/L的乙酸在100 ℃/1 h的条件下对粉末进行水热活化处理。以质量分数10% Ba(OH)₂·8H₂O为熔剂, 在350 MPa、400 ℃/1 h的条件下对粉体进行冷烧结, 最后经600 ℃/0.5 h退火获得了相对密度为96.62%、晶粒尺寸为180 nm, 常温介电(ε_r)为2836, 介电损耗(tanδ)低至0.03的BaTiO₃陶瓷。乙酸处理后高活性粉末表面形成的非晶钛层有效促进了陶瓷的致密化, 抑制了杂相的生成和晶粒长大, 提高了介电性能, 大幅改善了冷烧结BaTiO₃陶瓷出现的介电弥散现象, 从而实现了BaTiO₃陶瓷的低温冷烧结制备。     

硅片上集成高介电调谐率的柱状纳米晶BaTiO3铁电薄膜

钛酸钡(BaTiO₃)具有优异的介电、铁电、压电和热释电等性能, 在微电子机械系统和集成电路领域具有广泛的应用。降低BaTiO₃薄膜的制备温度使其与现有的CMOS-Si工艺兼容, 已成为应用研究和技术开发中亟需解决的问题。本研究引入与BaTiO₃晶格常数相匹配的LaNiO₃作为缓冲层, 以调控其薄膜结晶取向, 在单晶Si(100)基底上450 ℃溅射制备了结构致密的柱状纳米晶BaTiO₃薄膜。研究表明：450 ℃溅射温度在保持连续柱状晶结构和(001)择优取向的前提下, 能获得相对较大的柱状晶粒(平均晶粒直径27 nm), 一定残余应变也有助于其获得了较好的铁电和介电性能。剩余极化强度和最大极化强度分别达到了7和43 μC·cm^-2。该薄膜具有良好的绝缘性, 在 0.8 MV·cm^-1电场下, 漏电流密度仅为10^-5 A·cm^-2。其相对介电常数ε_r展现了优异的频率稳定性：在1 kHz时ε_r为155, 当测试频率升至1 MHz, ε_r仅轻微降低至145。薄膜的介电损耗较小, 约为0.01~0.03 (1 kHz ~ 1 MHz)。通过电容-电压测试, 该薄膜材料展示出高达51%的介电调谐率, 品质因子亦达到17(@1 MHz)。本研究所获得的BaTiO₃薄膜在介电调谐器件中有着良好的应用前景。     

纳米BiVO4/BaTiO3复合材料光催化降解性能

通过混合烧结法将BiVO₄与BaTiO₃复合获得BiVO₄/BaTiO₃复合光催化剂。采用XRD和FTIR分析了产物的物相,可知,BiVO₄/BaTiO₃复合材料中仅含有BiVO₄和BaTiO₃,无杂相生成。TEM观察发现,粒径约为55 nm的纳米BaTiO₃颗粒较好地附着在平均颗粒尺寸为~400 nm的BiVO₄颗粒表面,形成异质结构。选用酸性橙7（AO7）作为反应物模型,以模拟太阳光作为光源,研究了BiVO₄/BaTiO₃复合材料的光催化降解性能。结果表明:与BaTiO₃相比,BiVO₄/BaTiO₃复合材料的光催化降解活性显著提高;当BiVO₄的含量为8wt%时,BiVO₄/BaTiO₃复合材料的光催化效果最佳,光照6 h染料的降解率可达~68%,为BaTiO₃的1.9倍。BiVO₄/BaTiO₃复合材料的光催化性能较为稳定,循环使用3次后AO7的降解率仍有~62%。催化机制分析说明,BaTiO₃与BiVO₄复合后,光生电子和空穴能够向对方迁移,促进了光生电荷的分离,有利于光催化效率的提高。      

Deposition of BaTiO3 thin films by plasma MOCVD

Barium titanium trioxide (BaTiO₃) thin films were deposited on fused silica or silicon wafer substrate from barium dipivaloylmethanate (II) (Ba(dpm)₂) and titanium tetraisopropoxide (IV) (TTIP) used as precursors in an oxygen microwave plasma. The substrates were dielectrically heated and the substrate temperatures were around 900 K during the film deposition. The deposition was performed for 15 min and the deposits were identified as BaTiO₃ by means of X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy, and ellipsometry. Oxygen and barium atoms and TiO and CO molecules were identified in the plasma. These species would produce higher deposition rates at lower substrate temperatures than those did in the usual thermal metalorganic chemical vapor deposition (MOCVD). The dielectric constant of the BaTiO₃ thin film that was directly deposited on the silicon wafer substrate was as low as 10¹ order of magnitude. Because the deposit reacted with the substrate and an interdiffusional layer was formed, the platinum layer was coated on the silicon wafer substrate in order to prevent the formation of an interdiffusional layer. The dielectric constant then increased to 10³ order of magnitude.     

Domain size dependence of d33 piezoelectric properties for barium titanate single crystals with engineered domain configurations

Engineered domain configuration was induced into barium titanate (BaTiO₃) single crystals, and the d₃₃ piezoelectricity was investigated as a function of domain size. First, for the BaTiO₃ single-domain crystals, piezoelectric constant d₃₃ along [1 1 1]_c direction was calculated as 224 pC/N. Prior to the domain engineering, the dependence of domain configuration on the temperature and the electric-field was investigated, and above Curie temperature (T_c), when the electric-field over 6 kV/cm was applied along [1 1 1]_c direction, the fine engineered domain configuration appeared. On the basis of the above information, the 33 resonators with different domain sizes were successfully prepared. Their piezoelectric measurement revealed that the d₃₃ of the 33 resonators with fine engineered domain configurations was higher than that of BaTiO₃ single-domain crystals. Moreover, d₃₃ increased with decreasing domain sizes. The highest d₃₃ of 289 pC/N was obtained in the BaTiO₃ crystal with a domain size of 13 μm.     

Gelatin/BaTiO3核壳复合粒子的制备及电场响应性能研究

以平均粒径为0.7~0.9 mm的明胶(Gelatin)微球为基核, 通过定向沉积自组装法成功制备了以Gelatin为核、BaTiO₃为壳的Gelatin/BaTiO₃核壳复合粒子。利用TEM、XRD、FT-IR、TG和光学接触角测量等技术对复合粒子的形貌、结构、组成及表面亲水性能进行了研究。结果表明, 复合粒子为球形微粒, 具有良好的表面亲水性和分散稳定性, BaTiO₃壳层约占粒子总质量的18.8%, 具有立方相晶相结构。将粒子分散到水凝胶弹性体中, 测量在有/无电场作用下得到的弹性体的储能模量, 借以考察复合粒子在弹性体中的电场响应性能, 发现Gelatin/BaTiO₃复合粒子的电场响应性能明显强于纯BaTiO₃粒子。说明将BaTiO₃包覆在聚合物上能显著提高BaTiO₃粒子的电场响应性能。     

EPR studies on donor doped BaTiO3 grain boundary layer ceramic dielectrics

Donor doped BaTiO₃ ceramics become insulating₅ under controlled conditions with effective dielectric constants >10. The changes in EPR signals indicate that a certain fraction of the donor doped BaTiO₃ is cubic even at room temperature and that the cubic fraction increases with the donor content. X-ray powder diffraction data support the EPR results. The coexistence of both the phases over a range of temperature is characteristic of diffused phase transition. The effect of grain size variation on EPR signal intensities indicate that the boundary layers surrounding the grains may constitute the cubic phase as a result of higher Ba-vacancies and donor contents at the grain boundary layer than in the bulk. Since the acceptor states arising from the Ba-vacancies and the impurities are activated in the cubic phase, they capture electrons from the conduction band, rendering the cubic phase electrically more insulating than the semiconductive tetragonal grain interiors. Thus, the cubic grain boundary layers act as effective dielectric media where the field tends to concentrate.     

核-壳结构界面对纳米Ag掺杂BaTiO3@PDA/P(VDF-HFP)复合膜介电和储能性能影响

为改善聚偏氟乙烯（PVDF）基复合材料界面相容性,提高其电性能,利用聚多巴胺（PDA）成功包覆了纳米钛酸钡（BaTiO₃）,并引入纳米Ag离子制备出具有核-壳结构的Ag镶嵌BaTiO₃@PDA-Ag颗粒。以介电聚合物聚偏氟乙烯-六氟丙烯（P（VDF-HFP））为基体,采用溶液流延法制备了BaTiO₃@PDA-Ag/P（VDF-HFP）复合材料厚膜。利用FTIR和XPS验证了BaTiO₃@PDA-Ag/P（VDF-HFP）复合材料结构和形貌,并用宽频介电频谱仪和铁电测试仪分别比较了PDA包覆前后的不同BaTiO₃含量的BaTiO₃@PDA-Ag/P（VDF-HFP）复合膜在低电场下的介电性能和高电场下的电极化性能。结果表明,BaTiO₃@PDA-Ag质量分数为20wt%的BaTiO₃@PDA-Ag/P（VDF-HFP）复合膜在10 Hz下介电常数（ε_r）达到了25,介电损耗（tanδ）仅为0.1,在175 M·Vm-1电场下电极化强度（D_m）为6.2 μC·cm-2,200 M·Vm-1时储能密度（U_e）达到了6.9 J·cm-3,高于其它界面未处理复合膜。以上结果可为此类介电复合材料界面结构处理和电性能研究提供参考。      

Line-focus acoustic microscopy measurements ofNb2O5/MgO and BaTiO3/LaAlO3thin-film/substrate configurations

Line-focus acoustic microscopy has been used to measure the phase velocities of surface acoustic waves on bare MgO and bare LaAlO₃ , and on Nb₂O₅/MgO and BaTiO₃/LaAlO₃ thin-film/substrate configurations. The thin films are polycrystalline materials. The substrates are anisotropic single-crystals. The measured angular variation of the surface acoustic wave velocities has been used to determine the elastic constants of MgO substrate and Nb₂O₅ thin-film. It has been assumed that the Nb₂O₅ films may be considered as essentially isotropic. The measurements for LaAlO₃ and BaTiO₃/LaAlO₃ show anomalies which are attributed to twinning in the LaAlO₃ substrate     

添加Ni和Ag纳米颗粒对BaTiO3/PVDF复合材料击穿场强的影响

选用金属Ni和Ag纳米颗粒作为导体相,采用共混法分别制备了击穿场强较高的Ni-BaTiO₃/聚偏氟乙烯（Ni-BaTiO₃/PVDF）和Ag-BaTiO₃/PVDF三相复合材料。研究了导体相Ni和Ag添加量、粒径及导体种类对复合材料击穿场强的影响,发现Ni-BaTiO₃/PVDF和Ag-BaTiO₃/PVDF三相复合材料的击穿场强均随导体添加量的增加呈现先升高后降低的趋势,且在适宜的导体添加量下复合材料均表现出高于未添加导体相的BaTiO₃/PVDF两相复合材料的击穿场强;添加同类导体Ni时,Ni粒径越小,三相复合材料的击穿场强提高越明显;导体添加量与粒径均相同时,Ni-BaTiO₃/PVDF复合材料的击穿场强较高,当粒径50 nm的Ni添加量为体积分数1.90%时,其击穿场强可达200 kV/mm,储能密度比BaTiO₃/PVDF两相复合材料提高4倍。这些结果可用库仑阻塞效应很好地解释。     

Domain patterns on ferroelectric Rh:BaTiO3 single crystals

Single crystal growth and domain structure of Rh:Barium titanate (BaTiO₃) have been investigated. Rh doping in BaTiO₃ is effective for the growth of bulk crystals without twin formation. Atomic force microscope (AFM) and optical microscope studies reveal the formation 180° and 90° domains on the grown crystals. It has been observed that the complex 180° domain structure with typical size of around 20 μm exists in the c-domain of {0 0 1} face of Rh doped BaTiO₃ crystals.     

异质结型BaTiO3/TiO2复合纳米纤维的制备及光催化性能

以静电纺丝技术制备的TiO₂纳米纤维为模板和反应物, 采用水热法原位合成了具有异质结构的BaTiO₃/TiO₂复合纳米纤维。利用X射线衍射(XRD)、扫描电镜(SEM) 和高分辨透射电镜(HRTEM)等分析测试手段对样品的结构和形貌进行表征。结果表明: BaTiO₃纳米微粒均匀地生长在TiO₂纳米纤维表面, 制备了异质结型BaTiO₃/TiO₂复合纳米纤维。材料的光催化性能利用罗丹明B和苯酚的脱色降解反应测试。BaTiO₃/TiO₂复合纳米纤维材料, 在紫外光照射下, 光催化降解活性较纯锐钛矿TiO₂纳米纤维有明显提高, 罗丹明B和苯酚在该复合纳米纤维材料上的光催化降解反应遵循一级反应动力学。且易于分离、回收和再利用, 循环使用5次, 罗丹明B的脱色率仍保持在96%以上。