铌酸钠钾基压电陶瓷的结构与性能研究

采用传统的固相反应合成法制备了结构较为致密的0.9(K0.5Na0.5)NbO3-0.1LiSbO3(KNN-LS)无铅压电陶瓷,研究了其相结构、压电、介电、损耗以及铁电性质.常温下的压电陶瓷具备四方钙钛矿结构,具有较高的压电系数d33=131pC/N和低的介电损耗tanδ=0.09(10kHz)等优点.另外,常温下的KNN-LS陶瓷存在着较为饱满的电滞回线,其剩余极化率Pr为16.1μC/cm2,矫顽场为EC=14.8kV/cm.性能较KNN压电陶瓷有了较大的提高.     

LiTaO3掺杂对K0.5Na0.5NbO3基无铅压电陶瓷性能的影响

采用传统陶瓷工艺制备了LiTaO3掺杂的K0.5Na0.5NbO3基无铅压电陶瓷(记为KNN xLT,x=0～8%(摩尔分数)),并研究了陶瓷的晶相、显微结构和压电、铁电等性能.研究结果表明,KNN xLT陶瓷的正交相-四方相准同型相界(MPB)位于4%＜x＜6%处.随着LiTaO3含量的增加,陶瓷的正交→四方结构相变温度(TO-T)向低温方向移动,而四方→立方结构相变温度(Tc)向高温方向移动.陶瓷的压电常数d33和机电耦合系数kp随LiTaO3含量的增加均先增大后减小,而剩余极化强度Pr则随之逐渐减小,矫顽场Ec逐渐增大.当x=6%时,陶瓷具有较好的压电和铁电性能:d33=190pC/N,kp=40.0%,Pr=22.0μC/cm2,Ec=1.78kV/mm,Tc=440℃.该体系陶瓷具有较高的压电常数和比较大的平面机电耦合系数,是一种应用前景良好的压电铁电材料.     

CuO掺杂的(Na_(0.66)K_(0.34))NbO_3无铅压电陶瓷性能研究

采用传统工艺制备了CuO掺杂的无铅压电陶瓷(Na0.66K0.34)NbO3,研究了CuO掺杂对其压电、介电、铁电等性质的影响。实验结果显示,CuO掺杂促进了晶粒生长,降低了样品的烧结温度,适量掺杂能够显著提高陶瓷样品的密度。当掺杂量为0.5%(摩尔分数)时,样品的密度为4.26g/cm3,品质因子Qm提高到400,介电损耗tanδ降低至0.8%。实验结果还显示,CuO掺杂使得陶瓷变硬,起到硬性添加剂的作用。随着CuO掺杂量的增加,样品的居里点(TC)、正交-四方相变温度(TT-O)、压电常数d33以及机电耦合系数kp均明显降低,而矫顽场显著增加。对于不掺杂的(Na0.66K0.34)NbO3陶瓷,其d33高达107pC/N,该陶瓷优异的压电性能表明,除了具有准同型相界结构的(Na0.5K0.5)NbO3外,(Na0.66K0.34)NbO3也是一种具有研究潜力的无铅压电陶瓷组分。     

(K0.5Na0.5)NbO3-LiNbO3无铅压电陶瓷的烧结特性和压电性能研究

采用传统陶瓷烧结工艺制备了(1-x)(K0.5Na0.5)NbO3-xLiNbO3无铅压电陶瓷,研究了陶瓷的结构、烧结特性及电性能特征.制备的(K0.5Na0.5)NbO3-LiNbO3陶瓷为单一的钙钛矿结构,室温下其相结构随LiNbO3含量增加逐渐由正交相向四方相转变,显微结构也由于LiNbO3含量的不同而表现出很大差异.与(K0.5Na0.5)NbO3陶瓷相比,(K0.5Na0.5)NbO3-LiNbO3陶瓷的烧结温度降低,烧结特性得到改善. (K0.5Na0.5)NbO3-LiNbO3陶瓷表现出优越的压电性能,其中0.94(K0.5Na0.5)NbO3-0.06LiNbO3(x=0.06)陶瓷的压电常数d33达到205pC/N,机电耦合系数kp为40.3%,kt达到49.8%.     

Na0.5 Bi0.5 TiO3-K0.5 Bi0.5 TiO3系铁电体的相变研究

研究了(Na1-xKx)0.5Bi0.5TiO3体系x分别为0、0.08、0.16和0.20时陶瓷不同频率下的介电温谱,发现材料为弛豫型铁电体,材料的介电谱在室温到500℃的温度范围内存在一个介电常数-温度"台阶",一个介电常数-温度峰和一个介电损耗-温度峰,通过分析陶瓷不同温度下的电滞回线验证陶瓷在升温过程中产生了铁电-反铁电-顺电相变,采用铁电体成分起伏理论和内电场理论解释了这类弛豫型铁电体相变的原因.     

(K_(0.5)Na_(0.5))_(1-x)Li_xNb_(1-y)Sb_yO_3系无铅压电陶瓷的弥散相变研究

采用传统陶瓷工艺制备了(K0.5 Na0.5)1-xLixNb1-ySbyO3(KNLNSx-y,x=0～10%(摩尔分数),y=2%～8%(摩尔分数))系无铅压电陶瓷,研究了Li+和Sb5+的取代对KNLNSx-y系材料的相变弥散性的影响.结果表明,在所研究的组成范围内,KNLN-Sx-y,陶瓷都形成了单一的钙钛矿结构,Li+和Sb5+蚪进入了KNN晶格形成固溶体;随着Li含量的增加,KNLNSx-5陶瓷四方-立方相变的弥散性有所减弱;随着Sb含量的增加,KNLNS2-y,陶瓷四方-立方相变的弥散性有所增强.采用修正的居里-外斯定律能够较好的描述KNLNSx-y陶瓷在高于居里温度情况下的介电常数与温度的关系;利用有序-无序理论对该介电弥散现象进行了解释.     

一种改性铌酸盐系无铅压电陶瓷的合成与特性研究

K0.5Na0.5NbO3(KNN)系铌酸盐是一类可能替代铅基压电陶瓷的无铅压电陶瓷.利用Ta和Sb掺杂或者取代KNN中的相关离子,在陶瓷的准同型相界(MPB)处显现出高的压电和介电性能.利用传统技术制作出一种新的致密度较高的无铅压电陶瓷(1-x)(K0.5Na0.5)(Nb0.96Sb0.04)O3-xLiTaO3(简记为KNNS-LT).所有的组分在MPB处都存在纯的钙钛矿结构,主要压电性能在MPB处达极大值,其机电耦合系数kp为40%,压电常数d33为225pC/N,居里温度Tc为355℃.     

0.84(K_(0.48)Na_(0.52))NbO_3-0.16K_(0.56)Li_(0.38)NbO_(2.97)无铅压电陶瓷的多层膜工艺研究

采用多层膜工艺制备了0.84(K0.48Na0.52)NbO3-0.16K0.56Li0.38NbO2.97无铅压电陶瓷,研究了不同烧结温度和保温时间对陶瓷的密度、物相、微观形貌以及介电和压电性能的影响。结果表明,所有烧结条件下得到的陶瓷都是钙钛矿结构和少量钨青铜结构的混合相,而且室温下陶瓷都处于多型相变区域。1050℃烧结8 min得到的陶瓷断面晶粒均匀,相对密度达到95%以上,并且获得最优的介电和压电性能:介电常数为εr=618,介电损耗为tanδ=0.03,压电常数为d33=112 pC/N。与传统制备工艺相比,多层膜工艺大大降低了烧结温度,缩短了烧结时间,有效地抑制了K、Na的挥发。     

(1-x)(K_(0.5)Na_(0.5))NbO_3-x(Sr_(0.4)Ba_(0.6))_(0.7)Bi_(0.2)TiO_3无铅铁电陶瓷介电性能研究

采用传统固相烧结法,在铌酸钾钠陶瓷基体中掺入Sr、Ba、Bi和Ti元素,制备了(1-x)(K0.5Na0.5)-NbO3-x(Sr0.4Ba0.6)0.7Bi0.2TiO3((1-x)KNN-xBSBT)(0.01≤x≤0.04)陶瓷。XRD测试结果表明,(1-x)KNNxBSBT(0.01≤x≤0.04)为纯钙钛矿相;介电温谱表明,(1-x)KNN-xBSBT为弛豫铁电体;0.97KNN-0.03BSBT陶瓷介电常数具有很好的温度稳定性,在室温至400℃介电常数变化很小。     

(Na0.55K0.45)1-xLixNb1-xSbxO3压电陶瓷偏离两相共存区的性能研究

使用传统陶瓷烧结工艺制备了(Na0.55K0.45)1-xLixNb1-xSbxO3体系无铅压电陶瓷中偏离两相共存区的0.97(Na0.55K0.45)NbO3-0.03LiSbO3(简记为97KNN-3LS)陶瓷,分析了在不同烧结温度下其结构与电学性能.研究结果表明,当在适当的烧结温度时,该组分陶瓷具有良好的压电与铁电性能,其中,压电常数d33=166pC/N,平面机电耦合系数κP=46.7%,动态电阻R1=63Ω.该体系陶瓷在常温附近具有较高的κP与较低的R1,是一种很有应用前景的无铅压电陶瓷.     

Piezoelectric properties in (K0.5Bi0.5)TiO 3-(Na0.5Bi0.5)TiO3-BaTiO 3 lead-free ceramics

Lead-free piezoelectric ceramics with compositions around the morphotropic phase boundary (MPB) x(Na_0.5Bi_0.5)TiO _3-y(K_0.5Bi_0.5)TiO₃-zBaTiO ₃ [x + y + z = 1; y:z = 2:1] were synthesized using conventional, solid-state processing. Dielectric maximum temperatures of 280degC and 262degC were found for tetragonal 0.79(Na_0.5Bi_0.5)TiO₃-0.14(K_0.5 Bi_0.5)TiO₃-0.07BaTiO$ d3 (BNBK79) and MPB composition 0.88(Na_0.5Bi_0.5)TiO₃-0.08(K _0.5Bi_0.5)TiO₃-0.04BaTiO$ d3 (BNBK88), with depolarization temperatures of 224degC and 162degC, respectively. Piezoelectric coefficients d₃₃ were found to be 135 pC/N and 170 pC/N for BNBK79 and BNBK88, and the piezoelectric d₃₁ was determined to be -37 pC/N and -51 pC/N, demonstrating strong anisotropy. Coercive field values were found to be 37 kV/cm and 29 kV/cm for BNBK79 and BNBK88, respectively. The remanent polarization of BNBK88 (~40 muC/cm²) was larger than that of BNBK79 (~29 muC/cm²). The piezoelectric, electromechanical, and high-field strain behaviors also were studied as a function of temperature and discussed     

Crystal and magnetic study of the disordered perovskites Ca(Mn0.5Sb0.5)O3 and Ca(Fe0.5Sb0.5)O3

We have investigated the double perovskites Ca₂MSbO₆ (M = Mn, Fe) that have been prepared by solid-state reaction (M = Fe) and wet chemistry procedures (M = Mn). The crystal and magnetic structures have been studied from X-ray (XRD) and neutron powder diffraction (NPD) data. Rietveld refinements show that the crystal structures are orthorhombic (space group Pbnm) with complete disorder of M and Sb cations, so the formula should be rewritten as Ca(M_0.5Sb_0.5)O₃. Due to this disorder no evidences of Jahn-Teller distortion can be observed in the MnO₆ octahedra of Ca(Mn_0.5Sb_0.5)O₃, in contrast with the ordered double perovskite Sr₂MnSbO₆. Ca(Fe_0.5Sb_0.5)O₃ behaves as an antiferromagnet with an ordered magnetic moment for Fe³⁺ of 1.53(4)μ_B and a propagation vector k = 0, as investigated by low-temperature NPD. The antiferromagnetic ordering is a result of the high degree of Fe/Sb anti-site disorder of the sample, which originates the spontaneous formation of Fe-rich islands, characterized by the presence of strong Fe-O-Fe antiferromagnetic couplings with enough long-range coherence to produce a magnetic contribution perceptible by NPD. By contrast, the magnetic structure of Ca(Mn_0.5Sb_0.5)O₃ cannot be observed by low-temperature NPD because the magnitude of the ordered magnetic moments is below the detection threshold for neutrons.     

Alkoxide route to La0.5Sr0.5CoO3 epitaxial thin films on SrTiO3

An all alkoxide based sol–gel route was investigated for preparation of epitaxial La_0.5Sr_0.5CoO₃ (LSCO) films on 100 SrTiO₃ (STO) substrates. Films with 20–30 to 80–100 nm thickness were prepared by spin-coating 0.2–0.6 M (metal) solutions on the STO substrates and heat treatment to 800 °C at 2 °C min^− 1, 30 min, in air. The films were epitaxial with a cube-on-cube alignment and the LSCO cell was strained to match the STO substrate of 3.905 Å closely; a and b = 3.894 Å and 3.897 Å for the 20–30 and 80–100 nm films, respectively. The c-axis was compressed to 3.789 Å and 3.782 Å for the 20–30 and 80–100 nm films, respectively, which resulted in an almost unchanged cell volume as compared to polycrystalline film and nano-phase powders prepared in the same way. The SEM study showed mainly very smooth, featureless surfaces, but also some defects. A film prepared in the same way on an -Al₂O₃ substrate was dense and polycrystalline with crystallite sizes in the range 10–50 nm and gave cubic cell dimensions of a_c = 3.825 Å. The conductivity of the ca 30–40 nm thick polycrystalline film was 1.7 mΩcm, while the epitaxial 80–100 nm film had a conductivity of around 1.9 mΩcm.     

Dielectric Investigations of 0.945(Bi0.5Na0.5) TiO3-0.055BaTiO3

Dielectric properties of 0.945(Bi_0.5Na_0.5) TiO₃-0.055BaTiO₃(BNBT5.5) (a composition close to the rhombohedral- tetragonal morphotropic phase boundary) ceramics are studied. It is shown that BNBT5.5 is a relaxor with a characteristic relaxation time that follows Vogel-Fulcher's law. The following Vogel-Fulcher parameters of the relaxation time were calculated: pi0 = (2.0 plusmn 2.4)middot10^-14 s, E/^kB = (1620 plusmn 270) K, T₀ = (262 plusmn 9) K.     

Magnetoelectric and dielectric properties of Ni0.5Cu0.5Fe2O4–Ba0.5Pb0.5Ti0.5Zr0.5O3 ME composites

The (x) Ni_0.5Cu_0.5Fe₂O₄ + (1−x) Ba_0.5Pb_0.5Ti_0.5Zr_0.5O₃ ME composites have been synthesized by a standard ceramic method. The presence of single phase in x = 0 and x = 1 as well as two phases in x = 0.15, 0.30 and 0.45 composites has been confirmed by XRD. The dielectric constant (ε′) and dielectric loss (tan δ) have been studied as a function of temperature and frequency. These composite materials exhibit maximum dielectric constant with a variation of frequency and temperature. The composite 15% Ni_0.5Cu_0.5Fe₂O₄ + 85% Ba_0.5Pb_0.5Ti_0.5Zr_0.5O₃ had the highest magnetoelectric voltage coefficient of 0.248 mV/cm Oe at room temperature among the studied composites.     

Lattice Dynamics and Phase Transitions in KNbO3 and K0.5Na0.5NbO3 Ceramics

Phonons in both ceramic samples KNbO₃ (KN) and K_0.5Na_0.5NbO₃ (KNN-50) were investigated from 10 to 900 K by means of Raman, infrared, and THz spectroscopy. First-order transitions from cubic to tetragonal phases were detected at about 755 K (in KN) and 710 K (in KNN-50), where the first component of the polarization appears. Transitions from the tetragonal to the orthorhombic phases take place around 510 and 475 K, respectively. The last transitions from orthorhombic to rhombohedral phases are strongly first-order type. T_C is shifted from 200 K in KN to about 90 K in KNN-50. All Raman active modes below 200 cm^-1. disappear in KN but not in KNN-50. The overdamped soft mode present at high temperatures in the THz range changes its dielectric strength at each phase transition (when the corresponding component jumps to higher frequencies) and abruptly disappears from THz spectra in the rhombohedral phase, because it stiffens up to 200 cm^-1. This mode has lower frequency and higher dielectric strength in KNN-50.     

Structural engineering of Ba0.5Sr0.5TiO3 epitaxial films

Ba_0.5Sr_0.5TiO₃ single-layered and multilayered films were epitaxially grown on a (001) LaAlO₃ substrate using single target and dual target pulsed laser deposition, respectively. Compared to the single-layered films, the multilayered films exhibited broader phase transition and improved thermo-stability. The microstructure of these epitaxial films was investigated using high-resolution transmission electron microscopy in details. Misfit and threading dislocations were observed in the single-layered film, while the threading dislocations were dramatically decreased and no misfit dislocations were found in the multilayered film. It is suspected that the difference in dislocation densities is responsible for the different behaviors of the permittivity with temperature.     

Temperature dependence of ferroelectric and dielectric properties of textured 0.98(0.94Na0.5Bi0.5TiO3–0.06BaTiO3)–0.02K0.5Na0.5NbO3 thick film

Textured 0.98(0.94Na_0.5Bi_0.5TiO₃–0.06BaTiO₃)–0.02K_0.5Na_0.5NbO₃ thick film was prepared by reactive templated grain growth (RTGG) method. The effect of temperature on ferroelectric and dielectric behaviors of the thick film was investigated. Its dielectric constant as a function of temperature displayed typical relaxation behavior, which was similar to that of NBT-based bulk ceramics. Remnant polarization, saturation polarization, and coercive field of the thick film all decreased with increasing temperature. Dielectric constant and tunability of the film were also dependent on temperature. Electric field dependence of dielectric constant of the thick film suggested a transition from ferroelectric to antiferroelectric phase at around the depolarization temperature. A strong increase in leakage current density with increasing temperature was observed, which could be related to the enhanced activity of conductivity carriers.     

Effects of BiAlO3 on structure and electrical properties of K0.5Na0.5NbO3-LiSbO3 lead-free piezoceramics

(1−x)(0.948 K_0.5Na_0.5NbO₃-0.052LiSbO₃)-xBiAlO₃ (KNNLS-xBA) lead-free piezoceramics were synthesized by conventional solid state reaction method. The compositional dependence of phase structure and electrical properties of the ceramics was systemically studied. XRD patterns revealed that all the ceramic samples possessed pure perovskite structure. In addition, polymorphic phase transition (PPT) for the ceramics with BA doping could not be observed in the measuring range from room temperature to 500 °C. Within the studied range of BA addition, the ceramics with x = 0.002 represented a relatively desirable balance between the degradation of the piezoelectric properties, improvement in temperature stability and mechanical quality factor. It was found that the KNNLS-0.002BA ceramics exhibited optimum overall properties (d₃₃ = 233 pC/N, k_p = 35%, tanδ = 0.047, P_r = 27.3 μC/cm², Q_m = 56 and T_c = 349 °C), suggesting that this material should be a promising lead-free piezoelectric candidate for piezoelectric applications.