La2Zr2O7的增韧及陶瓷纤维的制备

La2Zr2O7是一种近年来才提出的新型热障涂层材料，该材料熔点高，在熔点以下不发生相变，热导率低，抗烧结及没有氧传输发生，这些特点使得它作为一种高温下应用的热障涂层材料越来越引起人们的重视。但是，由于该材料的热膨胀系数和断裂韧性比较低，它的实际应用受到了限制。 在本论文中，使用高压烧结的方法获得了致密化的纳米La2Zr2O7块体材料，并对其断裂韧性和热膨胀系数进行了研究。得到的La2Zr2O7纳米材料的断裂韧性和热膨胀系数分别为1.98MPam1/2和9.6×10-6K-1 (200-1000℃)，这些数值明显高于非纳米的La2Zr2O7陶瓷(断裂韧性和热膨胀系数分别为1.40 MPam1/2 和 9.1×10-6 K-1，该结果表明纳米化是一种提高材料断裂韧性和热膨胀系数的有效方法。在La2Zr2O7纳米粉末中加入8YSZ纳米颗粒，高压烧结后使其颗粒充分生长，在得到的复相化合物中观察到形成了类似棒状晶体的自增韧相，使得复合材料的断裂韧性(1.88 MPam1/2)比La2Zr2O7有所提高，甚至超过了同样条件下制备的8YSZ样品的断裂韧性。 La2Zr2O7的断裂韧性也可以通过在基体中添加BaTiO3铁电材料得到明显的提高。当添加BaTiO3的体积含量达到10vol％时，4.5GPa，1450℃高压烧结10min得到的复合材料断裂韧性达1.98 MPam1/2，明显高于同条件下烧结的La2Zr2O7 (1.60MPam1/2)。应力诱导下BaTiO3的电畴转向是主要的增韧原因。随着BaTiO3颗粒添加的体积含量增加，复相化合物的热膨胀系数也明显提高。当掺杂20vol％BaTiO3时，得到的复合材料平均热膨胀系数达到10.2×10-6K-1 (150~1200℃)。 我们通过在4.5GPa, 1650℃高压烧结5min的方法还获得了掺杂YAG纳米颗粒的La2Zr2O7纳米复相陶瓷。在室温下测量了材料的维氏硬度，并通过压痕裂纹长度计算出了材料的断裂韧性。随着YAG纳米颗粒体积含量的增加，纳米复相陶瓷的断裂韧性和维氏硬度都依次增加，当添加20vol％的YAG纳米颗粒时达到最大，分别为1.93 MPam1/2和11.45GPa。断裂韧性增加的机理可归结为以下三点：一是YAG纳米颗粒的添加提高了La2Zr2O7基体的晶界强度，二是基体晶粒尺寸变化的影响，三是YAG纳米颗粒对裂纹的偏转和钉扎作用。添加微米YAG颗粒的复相化合物因为和纳米复相陶瓷具有不同的增韧机制，因此断裂韧性的变化趋势也不相同，在掺入10vol％的YAG微米颗粒时，复合材料的断裂韧性最大，而后降低，当掺入YAG微米粒子的体积含量达到20vol％时，断裂韧性甚至低于La2Zr2O7。 从20世纪90年代开始，电纺作为一种合成纤维的办法越来越吸引人们的注意。其合成的纤维长度长，直径均匀，并且组成范围很广。最初，电纺只是被用来合成一些有机聚合物的纤维，最近，很多研究组开始致力于使用电纺的方法合成复合纤维或者陶瓷纤维。 在本论文中，我们使用电纺的方法获得了La2Zr2O7纳米纤维和SiC单晶纳米线。1000℃煅烧得到的La2Zr2O7纳米纤维具有烧绿石结构，直径在200~500nm之间。同样的温度煅烧时得到的La2Zr2O7纳米纤维的比表面积要明显高于粉末样品的，表明纤维的抗烧结性能比粉末的高。得到的SiC纳米线直径在50~100nm之间，表面有一约5nm厚的无定形的SiO2薄层。 使用电纺的方法，恰当的控制煅烧条件，我们获得了La2Ce2O7， La2(Zr0.745Ce0.386)2O7.524和8YSZ中空纤维。这种中空结构减小了粒子之间的接触面积，提高了材料的抗烧结性能。在扫描电镜分析的基础上，我们总结了这些中空纤维的形成过程。

Electronic structure of microporous titanosilicate ETS-10

The electronic structure of a microporous titanosilicate framework, ETS-10 is calculated by means of a first-principles self-consistent method. It is shown that without the inclusion of the alkali atoms whose positions in the framework are unknown, ETS-10 is an electron deficient system with 32 electrons per unit cell missing at the top of an otherwise semiconductor-like band structure. The calculated density of slates are resolved into partial components. It is shown that the states of the missing electrons primarily originate from the Ti-O bond. The local density of states of the Ti-3d orbitals in the ETS-10 framework is quite different from the perovskite BaTiO3. The possibilities of ETS-10 crystal being ferroelectric or having other interesting properties are discussed.

Preparation and properties of polyimide films codoped with barium and titanium oxides

Polyimide hybrid films containing bimetalic compounds were obtained by codoping poly(amic acid) with a barium and titanium precursor prepared from BaCO3, Ti(OBu)(4), and lactic acid followed by casting and thermal curing. FTIR, WAXD, and XPS measurements showed that barium and titanium precursor could be transformed to BaTiO3 at a temperature above 650 degreesC, while the mixed oxides were only found in hybrid films. The measurements of TEM and AFM indicated a homogeneous distribution of inorganic phase with particle sizes less than 50 nm. The hybrid films exhibited fairly high thermal stability, good optical transparency, and promising mechanical properties. The incorporation of 10 wt % barium and titanium oxide lowered surface and volume electrical resistivity by 2 and 5 orders, respectively, increasing dielectric constant from 3.5 to 4.2 and piezoelectric constant from 3.8 to 5.2 x 10(-12) c/N, relative to the nondoped polyimide film.

聚酰亚胺/无机物纳米杂化材料的研究Ⅱ.聚酰亚胺(TDPA/ODA)-BaTiO_3纳米杂化物的合成与表征

由碳酸钡、钛酸丁酯和乳酸制得钛酸钡多晶相.WAXD和TEM 分析表明, 该钛酸钡具有典型的钙钛矿结构, 粒径为30～50 nm . 此钛酸钡纳米粉被成功地分散于聚酰胺酸中并制得聚酰亚胺(TDPA/ODA) 杂化材料. TEM 和AFM 表明低含量 (< 1% BaTiO3) 的杂化膜, 无机物是以< 50 nm的球状颗粒均匀分散于聚酰亚胺基体中, 高含量 (如30% ) 杂化膜是具有光滑表面的韧性薄膜. 后者介电常数与压电常数比纯聚酰亚胺提高了近一倍.

Domains in three-dimensional ferroelectric nanostructures

We report the experimental measurement of domains in single- crystal nanocolumns of ferroelectric BaTiO3, together with a theory of domain size scaling in three- dimensional structures which explains the observations.

Nanoscale ferroelectrics machined from single crystals

This paper summarises some of the most recent work that has been done on nanoscale ferroelectrics as a result of a joint collaborative research effort involving groups in Queen's University Belfast, the University of Cambridge and the University of St. Andrews. Attempts have been made to observe fundamental effects of reduced size, and increasing morphological complexity, on ferroelectric behaviour by studying the functional response and domain characteristics in nanoscale single crystal material, whose size and morphology have been defined by Focused Ion Beam (FIB) patterning. This approach to nanoshape fabrication has allowed the following broad statements to be made: (i) in single crystal BaTiO3 sheets, permittivity and phase transition behaviour is not altered from that of bulk material down to a thickness of similar to 75 nm; (ii) in single crystal BaTiO3 sheets and nanowires changes in observed domain morphologies are consistent with large scale continuum modeling.

Thin film capacitor cut from single crystals using focused ion beam milling

The focused ion beam microscope (FIB) has been used to fabricate thin parallel-sided ferroelectric capacitors from single crystals of BaTiO3 and SrTiO3. A series of nano-sized capacitors ranging in thickness from similar to660 nm to similar to300 nm were made. Cross-sectional high resolution transmission electron microscopy (HRTEM) revealed that during capacitor fabrication, the FIB rendered around 20 nm of dielectric at the electrode-dielectric interface amorphous, associated with local gallium impregnation. Such a region would act electrically in series with the single crystal and would presumably have a considerable negative influence on the dielectric properties. However, thermal annealing prior to gold electrodes deposition was found to fully recover the single crystal capacitors and homogenise the gallium profile. The dielectric testing of the STO ultra-thin single crystal capacitors was performed yielding a room temperature dielectric constant of similar to300, as is the case in bulk. Therefore, there was no evidence of a collapse in dielectric constant associated with thin film dimensions.

Size Effects on Thin Film Ferroelectrics: Experiments on Isolated Single Crystal Sheets

Thin lamellae were cut from bulk single crystal BaTiO3 using a Focused Ion Beam Microscope. They were then removed and transferred onto single crystal MgO substrates, so that their functional properties could be measured independent of the original host bulk ferroelectric. The temperature dependence of the capacitance of these isolated single crystal films was found to be strongly bulk-like, demonstrating a sharp Curie anomaly, as well as Curie-Weiss behaviour. In addition, the sudden change in the remanent polarisation as a function of temperature at TC was characteristic of a first order phase change. The work represents a dramatic improvement on that previously published by M. M. Saad, P. Baxter, R. M. Bowman, J. M. Gregg, F. D. Morrison & J. F. Scott, J. Phys: Cond. Matt., 16 L451-L456 (2004), as critical shortcomings in the original specimen geometry, involving potential signal contributions from bulk BaTiO3, have now been obviated. That the functional properties of single crystal thin film lamellae are comparable to bulk, and not like those of conventionally deposited heteroegenous thin film systems, has therefore been confirmed.

Origin of Ferroelastic domains in Free-Standing Single Crystal Ferroelectric Films

The origin of the unusual 90 degrees ferroelectric/ferroelastic domains, consistently observed in recent studies on mesoscale and nanoscale free-standing single crystals of BaTiO3 [Schilling , Phys. Rev. B 74, 024115 (2006); Schilling , Nano Lett. 7, 3787 (2007)], has been considered. A model has been developed which postulates that the domains form as a response to elastic stress induced by a surface layer which does not undergo the paraelectric-ferroelectric cubic-tetragonal phase transition. This model was found to accurately account for the changes in domain periodicity as a function of size that had been observed experimentally. The physical origin of the surface layer might readily be associated with patterning damage, seen in experiment; however, when all evidence of physical damage is removed from the BaTiO3 surfaces by thermal annealing, the domain configuration remains practically unchanged. This suggests a more intrinsic origin, such as the increased importance of surface tension at small dimensions. The effect of surface tension is also shown to be proportional to the difference in hardness between the surface and the interior of the ferroelectric. The present model for surface-tension induced twinning should also be relevant for finely grained or core-shell structured ceramics.

The Influence of Point Defects and Inhomogeneous Strain on the Functional Behaviour of Thin film Ferroelectrics

An attempt has been made to unequivocally identify the influence that inhomogeneous strain fields, surrounding point defects, have on the functional properties of thin film ferroelectrics. Single crystal thin film lamellae of BaTiO3 have been integrated into capacitor structures, and the functional differences between those annealed in oxygen and those annealed in nitrogen have been mapped. Key features, such as the change in the paraelectric-ferroelectric phase transition from first to second order were noted and found to be consistent with mean field modeling predictions for the effects of inhomogeneous strain. Switching characteristics appeared to be unaffected, suggesting that point defects have a low efficacy in domain wall pinning.

Effect of wall thickness on the ferroelastic domain size of BaTiO3

Extremely regular self-organized patterns of 90^o ferroelastic domains have been reported in freestanding single crystal thin films of ferroelectric BaTiO₃. Lukyanchuk et al. [Phys Rev B 79, 144111 (2009)] have recently shown that the domain size as a function of thickness for such free standing films can be well described assuming that the domains are due to stress caused by a surface tension layer that does not undergo the paraelectric–ferroelectric transition. From the starting point of Lukyanchuk’s model, it is shown here that the ‘‘universal’’relationship between domain size and domain wall thickness previously observed in ferroelectrics, ferromagnets and multiferroics is also valid for ferroelastic domains.Further analysis of experimental data also shows that the domain wall thickness can vary considerably (an order of magnitude) from sample to sample even for the same material (BaTiO₃), in spite of which the domain size scaling model is still valid, provided that the correct,sample dependent, domain wall thickness is used.

Domains in Ferroelectric Nanodots

Almost free-standing single crystal mesoscale and nanoscale dots of ferroelectric BaTiO3 have been made by direct focused ion beam patterning of bulk single crystal material. The domain structures which appear in these single crystal dots, after cooling through the Curie temperature, were observed to form into quadrants, with each quadrant consisting of fine 90° stripe domains. The reason that these rather complex domain configurations form is uncertain, but we consider and discuss three possibilities for their genesis: first, that the quadrant features initially form to facilitate field-closure, but then develop 90° shape compensating stripe domains in order to accommodate disclination stresses; second, that they are the result of the impingement of domain packets which nucleate at the sidewalls of the dots forming “Forsbergh” patterns (essentially the result of phase transition kinetics); and third, that 90° domains form to conserve the shape of the nanodot as it is cooled through the Curie temperature but arrange into quadrant packets in order to minimize the energy associated with uncompensated surface charges (thus representing an equilibrium state). While the third model is the preferred one, we note that the second and third models are not mutually exclusive.

The Effect of Antinotches on Domain Wall Mobility in Single Crystal Ferroelectric Nanowires

Changes in domain wall mobility, caused by the presence of antinotches in single crystal BaTiO3 nanowires, have been investigated. While antinotches appeared to cause a slight broadening in the distribution of switching events, observed as a function of applied electric field (inferred from capacitance-voltage measurements), the effect was often subtle. Greater clarity of information was obtained from Rayleigh analysis of the capacitance variation with ac field amplitude. Here the magnitude of the domain wall mobility parameter (R) associated with irreversible wall movements was found to be reduced by the presence of antinotches - an effect which became more noticeable on heating toward the Curie temperature. The reduction in this domain wall mobility was contrasted with the noticeable enhancement found previously in ferroelectric wires with notches. Finite element modeling of the electric field, developed in the nanowires during switching, revealed regions of increased and decreased local field at the center of the notch and antinotch structures, respectively; the absolute magnitude of field enhancement in the notch centers was considerably greater than the field reduction in the center of the antinotches and this was commensurate with the manner in, and degree to, which domain wall mobility appeared to be affected. We therefore conclude that the main mechanism by which morphology alters the irreversible component of the domain wall mobility in ferroelectric wire structures is via the manner in which morphological variations alter the spatial distribution of the electric field.