Properties of Sr- and Sb-doped PZT–Portland cement composites

Lead zirconate titanate (PZT) ceramic-cement-based composites have increasingly been recognized as an attractive new composite material for use as a sensor in structural applications. In this work, PZT was doped with Sr and Sb (PSZT) to give it greater dielectric constant (ε _r) and higher piezoelectric coefficient (d ₃₃) values than normal PZT and is the first time that it is mixed with normal Portland cement to produce a 0–3 connectivity PSZT–Portland cement composite using PSZT contents of 50% and 70% by volume. Scanning electron micrographs show PSZT ceramic particles closely surrounded by the hydrated cement matrix where a dense microstructure can be observed in the interfacial zone. Both the ε _r and d ₃₃ values were found to increase with PSZT content and the values are amongst the highest so far for these types of composites, where the ε _r and d ₃₃ values reached 590 and 48 pC/N, respectively.     

The effect of annealing temperature on the morphology and piezoelectric characteristics of BaTiO3 nanofibers and domain switching under different temperatures

Effects of annealing temperature (600–750 °C) on crystalline structure, the morphology and piezoresponse hysteresis loops of BaTiO₃ nanofibers prepared by electrospinning are characterized by X-ray diffraction, scanning electronic microscopy, transmission electron microscope and piezoresponse force microscope. When the annealing temperature is 700 °C, the nanofibers become smoother and have a diameter of 100–300 nm. Meanwhile the typical butterfly-shaped amplitude loop and 180°phase change represents the best ferroelectric and piezoelectric properties at 700 °C. So the 700 °C was found to be optimum for good piezoelectric characteristics at annealing temperature of 600 °C–750 °C. In order to give more clear evolution of domain states at different external fields, the three dimensional topographic and phase images of the nanofiber at different temperatures are observed by piezoresponse force microscope. The 90° domain switching is observed during heating from room temperature to 125 °C and the domain switching tends to be stable when the temperature exceeds a critical value. The thermal stress due to the high temperatures is responsible for switching mechanism from the perspective of equilibrium state free energy. This work suggests that the temperature variation should be considered while designing the ferroelectric devices based on one dimensional material.     

Piezoelectric cement-based 1-3 composites

This paper presents a new functional material for smart structure applications. Piezoelectric PZT/cement 1-3 composites that have good compatibility with civil engineering structural materials have been studied. The composites with different volume fractions of PZT ranging from 0.25 to 0.77 were fabricated by the dice-and-fill method. It was found that the 1-3 composites have good piezoelectric properties that agreed quite well with theoretical modeling. The thickness electromechanical coupling coefficient could reach 0.55 in the composite with a ceramic volume fraction of 0.25. Those composites have potential to be used as sensors in civil structure health monitoring systems. PACS 77.65.-j; 77.84.Lf     

UV laser micromachining of piezoelectric ceramic using a pulsed Nd:YAG laser

UV laser (=355 nm) ablation of piezoelectric lead zirconate titanate (PZT) ceramics in air has been investigated under different laser parameters. It has been found that there is a critical pulse number (N=750). When the pulse number is smaller than the critical value, the ablation rate decreases with increasing pulse number. Beyond the critical value, the ablation rate becomes constant. The ablation rate and concentrations of O, Zr and Ti on the ablated surface increase with the laser fluence, while the Pb concentration decreases due to the selective evaporation of PbO. The loss of the Pb results in the formation of a metastable pyrochlore phase. ZrO₂ was detected by XPS in the ablated zone. Also, the concentrations of the pyrochlore phase and ZrO₂ increase with increasing laser fluence. These results clearly indicate that the chemical composition and phase structure in the ablated zone strongly depend on the laser fluence. The piezoelectric properties of the cut PZT ceramic samples completely disappear due to the loss of the Pb and the existence of the pyrochlore phase. After these samples were annealed at 1150 °C for 1 h in a PbO-controlled atmosphere, their phase structure and piezoelectric properties were recovered again. Finally, 1–3 and concentric-ring 2–2 PZT/epoxy composites were fabricated by UV laser micromachining and their thickness modes were measured by impedance spectrum analysis and a d₃₃ meter. Both composites show high piezoelectric properties. PACS 81.40.Gh; 77.84.-s     

Nanoembossing and piezoelectricity of ferroelectric Pb(Zr0.3,Ti0.7)O3 nanowire arrays

Arrays of ferroelectric PZT nanowires with lateral size down to 200 nm were fabricated by nanoembossing technology. Structural characterization of the embossed PZT film was studied by Raman spectroscopy. Multidomain configurations of a single nanowire have been explored by vertical mode piezoresponse force microscopy (VPFM). The local electric polarization of the individual ferroelectric nanowire has also been investigated. Excellent ferroelectric and piezoelectric characteristics observed in the embossed PZT nanowires suggest nanoembossing technique proposed in this work is promising to become a useful method for ferroelectric nanowires fabrication.     

Fabrication and piezoelectricity of 0–3 cement based composite with nano-PZT powder

Lead zirconate titanate (Pb(Zr_0.52Ti_0.48)O₃) (PZT) nano-powder with a perovskite structure was fabricated using sol–gel process. The average crystallite diameter of the PZT powder is calculated to be 23.6 nm and the average agglomerate size is about 200 nm. The 0–3 cement based nano-PZT composites were obtained by pressing the mixture of white cement and the nano-PZT powders under a high pressure followed by steam curing. The properties of the nano-PZT/cement piezoelectric composites have been measured and compared to the PZT/cement composites incorporated with ground coarse PZT particles. The enhanced piezoelectricity of the nano-PZT/cement composites can be attributed to the good connectivity between the nano-PZT particles among the cement matrix.     

Dielectric and piezoelectric properties of PZT–silica fume cement composites

PZT–silica fume cement (PZT–SFC) composites were produced using PZT (at 50% and 60% by volume) and silica fume cement (cement containing silica fume of 5% and 10% by weight). PZT–Portland cement with no silica fume was also produced to allow comparison of the results. Dielectric constants of PZT–SFC composites are found to be higher than that of PZT–PC composite where ε_r value was found to increase with increasing SF content (ε_r values of composite with SF at 0%, 5% and 10% are 117, 125 and 178, respectively). PZT–SFC composites were successfully poled and d₃₃ results of PZT–SFC composites (d₃₃ = 18 pC/N) were found to be marginally higher than that of PZT–PC composite (d₃₃ = 17 pC/N). SEM micrograph also shows a dense matrix of SFC hydration product surrounding the PZT particles. From the results, these PZT–SFC composites are therefore promising materials for use in structural applications and should be ideal for high strength structures where SFC is used in the host structure.     

Piezoelectric and bonding properties of a cement-based composite for dental application

A cement-based piezoelectric composite was introduced as real-time health monitoring systems to dentin. Lithium sodium potassium niobate and zinc polycarboxylate cement were mixed and made piezoelectric under different poling conditions. X-ray diffraction and scanning electron microscope confirmed the component and microstructure of the cement. The bonding force of the composites was compared to that of pure cement by analysis of variance. The optimum poling method was determined and the influencing factors of piezoelectric coefficient were discussed.     

Nanoscale imaging of surface piezoresponse on GaN epitaxial layers

Surfaces of GaN films were investigated by atomic force microscopy (AFM) with implemented piezoelectric force microscopy technique. A model of PFM based on the surface depletion region in GaN films is discussed. The local piezoelectric effect of the low frequency regime was found to be in phase with the applied voltage on large domains, corresponding to a Ga-face of the GaN layer. Low piezoresponse is obtained within the inter-domain regions. The use of frequencies near a resonance frequency enhances very much the resolution of piezo-imaging, but only for very low scanning speed the piezo-imaging can follow the local piezoelectric effect. An inversion of the PFM image contrast is obtained for frequencies higher than the resonance frequencies. The effect of a chemical surface treatment on the topography and the piezoresponse of the GaN films was also investigated. Textured surfaces with very small domains were observed after the chemical treatment. For this kind of surfaces, piezo-induced torsion rather than bending of the AFM cantilever dominates the contrast of the PFM images. A small memory effect was observed, and explained by surface charging and confinement of the piezoelectric effect within the carrier depletion region at the GaN surface.     

Study of 1-3 PZT fibre/epoxy composite force sensor

Lead zirconate titanate (PZT) fibres were prepared by a powder-based extrusion method. Pre-sintered PZT powder mixed with poly(acrylic acid) was spun in a spinnerette to produce fibres. The fibre of ∼400 μm diameter was used to fabricate 1-3 PZT fibre/epoxy composite discs with different volume fractions (ϕ) of PZT. Since the ceramic fibres are rather brittle, their elastic properties cannot be measured directly. In order to determine the properties of the ceramic fibres, effective properties of the fibres/epoxy 1-3 composite were measured. By using a modified series and parallel model, the properties of 1-3 composites can be calculated. Then, the elastic coefficient s_33,fibre^E, relative permittivity ε_33,fibre^T and piezoelectric strain coefficient d_33,fibre of the ceramic fibre could be found. Ring-shaped PZT fibre/epoxy materials composites with different ϕ were fabricated to be used as the sensing material in force sensor applications. The ring-shape composite with ϕ=0.5 was installed into a housing and the sensor was calibrated by different methods and its sensitivity was found to be 144 pC/N within the frequency range of 0.5–6.4 kHz which is much higher than that of a quartz force sensor with a similar structure. PACS 07.07.Df; 72.80.Tm; 77.84.Dy     

不同晶化工艺对非晶PZT纳米薄膜形核取向生长机理的影响

射频磁控溅射法室温下在Pt/Ti/SiO2/Si上制备非晶Pb(Zr048Ti052)O3薄膜，非晶PZT薄膜分别经常规炉退火(CFA)处理和快速热退火(RTA)处理晶化为（100），（111）不同择优取向的多晶薄膜. 采用x射线衍射测定了薄膜相组分、择优取向度；用原子力显微镜和压电响应力显微镜观察了薄膜表面形貌，以及对应区域由自发极化形成的铁电畴像，观察了不同取向薄膜的电畴分布特征. 结果表明，RTA晶化过程钙钛矿结构PZT结晶主要以PZT/Pt界面处的PtPb化合物为成核点异质形核并类似外延的结晶生长，沿界面结晶速率远大于垂直膜面结晶速率，而CFA晶化样品成核发生在膜内杂质缺陷处，以同质成核为主. 不同的成核机理导致了不同晶面择优取向生长. 关键词： PZT薄膜 结晶 形核 力显微技术     

YMnO_3薄膜的铁电行为及其纳米尺度铁电畴的研究

六方YMnO_3是一种特殊的多铁性材料,因其具有介电常数低、单一极化轴、无挥发性元素等特点,在磁电领域具有独特的优势,但目前关于YMnO_3薄膜的铁电性特别是畴结构的研究相对较少.本文采用溶胶-凝胶法在Si(100)基片上制备了多铁性YMnO_3薄膜,利用掠入射X-射线衍射、原子力显微镜对薄膜的结构及表面形貌进行了分析,用压力显微镜(PFM)技术研究了纳米尺度畴结构及微区电滞行为,并通过I-V,P-E曲线进一步研究了薄膜的漏电流和宏观电滞行为.结果表明,该薄膜为六方钙钛矿结构,YMnO_3晶粒大小均匀并且结晶性较好,薄膜表面粗糙度为7.209 nm.PFM图显示出清晰的电畴结构,结合典型的微区振幅蝴蝶曲线和相位电滞回线,证实该YMnO_3薄膜具有较好的铁电性.由于受内建电场的作用,振幅曲线和相位曲线都向正向偏移,表现出非对称特征.该薄膜的漏电流密度低于10~(-6)A·cm~(-2),因而其电滞回线基本能够达到饱和.     

100-nm lateral size ferroelectric memory cells fabricated by electron-beam direct writing

A fundamental limitation in the recent development of non-volatile ferroelectric memories of 64-Mbit to 4-Gbit densities was found to be the problem to scale ferroelectric capacitor cell sizes down below 1 7m². In this paper we report on the preparation of ferroelectric memory cells with lateral sizes down to 100 nm using electron-beam direct writing. Switching of single 100-nm cells was achieved and piezoelectric hysteresis loops were recorded using a scanning force microscope working in piezoresponse mode. The piezoelectricity and its hysteresis acquired for 100-nm PZT cells demonstrate that a further decrease in lateral size under 100 nm appears to be possible and that the size effects do not fundamentally limit the increase of the density of non-volatile ferroelectric memories in the Gbit range.     

电泳辅助制备伪1-3陶瓷/聚合物压电复合材料

1-3压电复合材料的压电、介电及铁电性能要远远优于0-3压电复合材料.在制备传统的0-3复合材料过程中引入电泳技术,使得压电颗粒在聚合物基体中取向排列,制备得到伪1-3复合材料.实验结果表明:在制备PZT/环氧树脂0-3复合压电材料固化过程中,采用500 V/mm,4 kHz的电场对其进行电泳辅助取向,可使得颗粒呈现珍珠串状排列,得到伪1-3复合材料;其压电、介电、铁电性能均比原来的0-3复合材料有显著的提高.电泳辅助制备技术用于制备伪1-3复合压电材料具有操作简单、成本低廉、压电、介电、铁电性能显著提高等优点,在智能传感领域具有很好的实际应用前景.     

Properties of PZT/PZT ceramic piezocomposites

A method for obtaining PZT/PZT ceramic piezocomposites is developed. Samples of piezocomposites with a volume fraction of components from 0 to 100% are prepared and investigated. Various types of PZT type piezoceramics powders and milled PZT piezoceramics particles, as well as presintered piezoceramic granules, are used as matrix and filling components, respectively. Sets of complex elastic, dielectric, and piezoelectric parameters of piezocomposites are measured. The microstructure of the obtained ceramic composites is investigated.     

Observation of mechanical fracture and corresponding domain structure changes of polycrystalline PbTiO3 nanotubes

PbTiO₃ (PTO) nanotubes (NTs) were synthesized at various temperatures by gas phase reaction between PbO gas and anatase TiO₂ NTs and characterized by piezoresponse force microscopy (PFM). PTO ferroelectric phase was synthesized at as low as 400 °C as evidenced by PFM domain images and piezoresponse hysteresis loop measurement. Furthermore, the PTO NTs fabricated at above 500 °C underwent mechanical fracture through development of nanocracks due to grain growth, leading to ferroelectric domains with larger size and lower aspect ratio. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dielectric and piezoelectric properties of PZT–cement composites

Lead zirconate titanate (PZT) and cement composites of 0–3 connectivity were produced using PZT of 30–90% by volume. The effects of PZT on dielectric and piezoelectric properties of the composites were then investigated. The dielectric constant (ε_r) of the composites was found to increase with increasing PZT content. The ε_r value of 90% PZT composite obtained was 291 which is noticeably higher than that of PC sample (ε_r = 79). The dielectric loss (tan δ) was found to decrease with PZT content and the tan δ value was lowest at 0.63 for 90% PZT composite. Piezoelectric coefficient (d₃₃) was found to increase with PZT content as expected. However, the effects were most significant at two stages, first at 30% PZT volume content (14 pC/N) and then at very high PZT content (90% by volume) where d₃₃ value reached 43 pC/N.     

基体电导率对0-3型铁电复合材料高压极化行为及损耗的影响

提出了一个0-3型聚合物基铁电复合材料的直流高压极化模型.模型中考虑了聚合物/铁电陶瓷界面处自由电荷的积聚及极化初始时刻的真实情况,利用拉普拉斯静电场方程,并结合边界条件,得到了直流高压极化过程中复合材料的极化强度、界面电流密度等随时间的演化方程,同时得到介电常数、介质损耗等物理特性的表达式.此外,实验制备了分别以环氧树脂E-44和铁电共聚物P(VDF-TrFE)为基体的两种0-3型铁电复合材料.从理论和实验两方面研究了基体电导率对极化行为以及介质损耗的影响.两方面结果均表明：随基体电导率增加,极化时间缩短,陶瓷相的极化强度及复合材料的整体电性能提高,但是漏电流及介质损耗增加.而且实验结果与直流高压极化模型的预测结果符合. 关键词： 铁电复合材料 电导率 极化 介质损耗     

Electromechanical response of 2-2 layered piezoelectric composites: A micromechanical model based on the asymptotic homogenization method

A micromechanical model based on the asymptotic homogenization technique has been developed to predict the complete elastic, dielectric and piezoelectric properties of a general 2-2 layered piezoelectric composite where the constituent phases are elastically anisotropic and piezoelectrically active. Two classes of layered piezoelectric composites (i.e. longitudinally and transversely layered) are considered in two widely different ceramic- and polymer-based systems and their effective properties are obtained in the limits of both large-volume (i.e. bulk) and small-volume (i.e. thin-film) systems. It is demonstrated that: (i) in the bulk, ceramic–ceramic layered composite system, the elastic, piezoelectric, and dielectric properties of the composites vary linearly with volume fraction of the second phase, while in the bulk ceramic–polymer layered composite system, the corresponding properties vary non-linearly with volume fraction of the second phase; (ii) in the prismatic (thin-film) layered piezoelectric composite system, the non-vanishing, effective elastic, piezoelectric and dielectric properties vary linearly with the volume fraction of the second phase for both the longitudinally and transversely layered composite structures in the ceramic–ceramic and the ceramic–polymer composite systems; (iii) the ceramic–polymer piezoelectric layered composites that incorporate a low density polymeric phase with lower acoustic impedance generally exhibit enhanced piezoelectric coupling constants and lowered acoustic impedance; (iv) the longitudinally layered composites exhibit higher piezoelectric coupling constants and lower acoustic impedance compared to that of the transversely layered composites; and (v) the best combination of properties for applications such as hydrophones (i.e. the highest piezoelectric coupling constants and the lowest acoustic impedance) is obtained in the ceramic–polymer, longitudinally layered, thin-film, piezoelectric composites.     

Investigation of the mechanism of polarization switching in ferroelectric capacitors by three- dimensional piezoresponse force microscopy

A mechanism for the switching behavior of (111)-oriented Pb(Zr,Ti)O₃-based 1×1.5 m² capacitors has been investigated using three-dimensional piezoresponse force microscopy (3D-PFM). A combination of vertical and lateral piezoresponse force microscopy (VPFM and LPFM) has been used to map the out-of-plane and the in-plane components of the polarization. The three-dimensional polarization distribution was reconstructed by quantitative analysis of the PFM amplitude images of poled PZT capacitors while taking into account contrast variations in the PFM phase images. The switching behavior of the capacitors was determined by comparison of the static domain patterns in the same capacitors after both positive and negative poling. While 180° degree switching was observed, surprisingly, the switching process was dominated by 90° polarization vector rotation. Furthermore, central regions of the capacitors were characterized by the presence of charged domain boundaries, which could lead to imprint (preference of one polarization state over another). PACS 85.50.Gk; 77.80.Fm; 77.80.Dj; 68.37.Ps