Probing nanoscale ferroelectricity by ultraviolet Raman spectroscopy

We demonstrated that ultraviolet Raman spectroscopy is an effective technique to measure the transition temperature (Tc) in ferroelectric ultrathin films and superlattices. We showed that one-unit-cell-thick BaTiO3 layers in BaTiO3/SrTiO3 superlattices are not only ferroelectric (with Tc as high as 250 kelvin) but also polarize the quantum paraelectric SrTiO3 layers adjacent to them. Tc was tuned by approximately 500 kelvin by varying the thicknesses of the BaTiO3 and SrTiO3 layers, revealing the essential roles of electrical and mechanical boundary conditions for nanoscale ferroelectricity.     

Enhancement of ferroelectricity in strained BaTiO3 thin films

Biaxial compressive strain has been used to markedly enhance the ferroelectric properties of BaTiO3 thin films. This strain, imposed by coherent epitaxy, can result in a ferroelectric transition temperature nearly 500 degrees C higher and a remanent polarization at least 250% higher than bulk BaTiO3 single crystals. This work demonstrates a route to a lead-free ferroelectric for nonvolatile memories and electro-optic devices.     

Femtoscale magnetically induced lattice distortions in multiferroic TbMnO₃

Magneto-electric multiferroics exemplified by TbMnO(3) possess both magnetic and ferroelectric long-range order. The magnetic order is mostly understood, whereas the nature of the ferroelectricity has remained more elusive. Competing models proposed to explain the ferroelectricity are associated respectively with charge transfer and ionic displacements. Exploiting the magneto-electric coupling, we used an electric field to produce a single magnetic domain state, and a magnetic field to induce ionic displacements. Under these conditions, interference between charge and magnetic x-ray scattering arose, encoding the amplitude and phase of the displacements. When combined with a theoretical analysis, our data allow us to resolve the ionic displacements at the femtoscale, and show that such displacements make a substantial contribution to the zero-field ferroelectric moment.     

Femtosecond resolution of soft mode dynamics in structural phase transitions

The microscopic pathway along which ions or molecules in a crystal move during a structural phase transition can often be described in terms of a collective vibrational mode of the lattice. In many cases, this mode, called a "soft" phonon mode because of its characteristically low frequency near the phase transition temperature, is difficult to characterize through conventional frequency-domain spectroscopies such as light or neutron scattering. A femtosecond time-domain analog of light-scattering spectroscopy called impulsive stimulated Raman scattering (ISRS) has been used to examine the soft modes of two perovskite ferroelectric crystals. The low-frequency lattice dynamics of KNbO(3) and BaTiO(3) are clarified in a manner that permits critical evaluation of microscopic models for their ferroelectric transitions. The results illustrate the advantages of ISRS over conventional Raman spectroscopy of low-frequency, heavily damped soft modes.     

Axial oxygen-centered lattice instabilities and high-temperature superconductivity

Copper K-edge x-ray absorption data indicate that an axial oxygen-centered lattice instability accompanying the 93 K superconducting transition in YBa(2)Cu(3)O(7) is of a pseudo-(anti)ferroelectric type, in that it appears to involve the softening of a double potential well into a structure in which the difference between the two copper-oxygen distances and the barrier height have both decreased. This softer structure is present only at temperatures within a fluctuation region around the transition. A similar process involving the analogous axial oxygen atom also accompanies the superconducting transition in T1Ba(2)Ca(3)Cu(4)O(11), where the superconducting transition temperature T(c) is ~120 K. The mean square relative displacement of this oxygen atom in YBa(2)Cu(3)O(7) is also specifically affected by a reduction in the oxygen content and by the substitution of cobalt for copper, providing further evidence for the sensitivity of the displacement to additional factors that also influence the superconductivity. On the basis of the implied coupling of this ionic motion to the superconductivity, a scenario for high-temperature superconductivity is presented in which both phonon and electronic (charge transfer) channels are synergistically involved.     

Epitaxial cuprate superconductor/ferroelectric heterostructures

Thin-film heterostructures of Bi(4)Ti(3)O(12)Bi(2)Sr(2)CuO(6+x), have been grown on single crystals of SrTiO(3), LaAlO(3), and MgAl(2)O(4) by pulsed laser deposition. X-ray diffraction studies show the presence of c-axis orientation only; Rutherford backscattering experiments show the composition to be close to the nominal stoichiometry. The films are ferroelectric and exhibit a symmetric hysteresis loop. The remanent polarization was 1.0 microcoulomb per square centimeter, and the coercive field was 2.0 x 10(5) volts per centimeter. Similar results were obtained with YBa(2)Cu(3)O(7-x) and Bi(2)Sr(2)CaCu(2)O(8+x), and single-crystal Bi(2)Sr(2)CuO(6+x)as the bottom electrodes. These films look promising for use as novel, lattice-matched, epitaxial ferroelectric film/electrode heterostructures in nonvolatile memory applications.     

磁性负载型光催化材料TiO2/Fe3O4的制备、改性及表征

采用溶胶-凝胶法制备核-壳式结构的TiO2/Fe3O4负载型光催化剂,并对其进行中间层改性,制备出TiO2/SiO2/Fe3O4光催化材料.研究了pH等制备条件对TiO2/Fe3O4材料光催化性能的影响,并对比了改性前后降解甲基橙的光催化性能,通过X射线衍射仪(XRD)、红外光谱仪(FT-IR)、振动样品磁强计(VSM)和透射电子显微镜(TEM)对改性前后颗粒的磁性能、晶相和形貌进行了表征.研究表明:磁性负载光催化剂TiO2/Fe3O4和TiO2/SiO2/Fe3O4均为超顺磁性,且光催化性能较高,在1 h内甲基橙脱色率达90%以上,其降解反应均属于一级动力学反应;SiO2中间层的引入可显著提高材料的饱和磁化强度、光催化速率和循环使用的光催化活性.     

胺基化磁性壳聚糖微球的制备及其对苹果渣多酚的吸附研究

【目的】以苹果渣中多酚类化合物为吸附模型,制备一种可有效吸附分离苹果多酚的磁性高分子材料,并研究其吸附性能。【方法】采用化学共沉淀法制得Fe₃O₄磁核,与壳聚糖混合均匀后利用反相悬浮交联法制得磁性壳聚糖微球,并进行胺基化改性;采用单因素试验得到制备胺基化磁性壳聚糖微球的最佳工艺参数;通过透射电镜、超顺磁性对Fe₃O₄磁核进行表征,利用扫描电镜对胺基化磁性壳聚糖微球的表面特征进行观察。【结果】胺基化磁性壳聚糖微球对苹果渣多酚的吸附效果最佳;制备胺基化磁性壳聚糖微球的工艺参数为：2 mL 体积分数25%的戊二醛、5 mL/g的环氧氯丙烷和3 mL/g的乙二胺,按此条件制备的胺基化磁性壳聚糖微球对苹果多酚的饱和吸附率达到81.94%;电镜观察表明,制得的胺基化磁性壳聚糖微球达到微米级,呈规则球形,有良好的分散性。【结论】胺基化磁性壳聚糖微球是一种良好的苹果渣多酚吸附剂,有较好的工业化应用前景。     

Coupled superconducting and magnetic order in CeCoIn5

Strong magnetic fluctuations can provide a coupling mechanism for electrons that leads to unconventional superconductivity. Magnetic order and superconductivity have been found to coexist in a number of magnetically mediated superconductors, but these order parameters generally compete. We report that close to the upper critical field, CeCoIn5 adopts a multicomponent ground state that simultaneously carries cooperating magnetic and superconducting orders. Suppressing superconductivity in a first-order transition at the upper critical field leads to the simultaneous collapse of the magnetic order, showing that superconductivity is necessary for the magnetic order. A symmetry analysis of the coupling between the magnetic order and the superconducting gap function suggests a form of superconductivity that is associated with a nonvanishing momentum.     

采用变温X射线衍射技术对六方钛酸钡陶瓷材料的结构监控

对于由冷压陶瓷技术所开发的纯六方Ba（Ti0.95Fe0.05）O3-δ陶瓷，采用变温XRD技术测量该陶瓷在不同温度下的XRD谱，鉴定晶体结构．澄清了六方钛酸钡（BaTiO3）介电陶瓷材料的晶体结构是否在BaTiO3的居里温度（n=130℃）发生结构相变，并验证开发的变温X射线衍射（XRD）技术在无机粉体材料结构监控的可行性．结果表明：BaTiO3陶瓷在Tc发生四方-立方的结构相变，以45°附近两个分立的（002）／（200）衍射峰演变为单一对称的（200）衍射峰为标志；而六方Ba（Ti0.95Fe0.05）O3-δ陶瓷直到300℃都不发生结构相变．对于六方Ba（Ti0.95Fe0.05）O3-δ陶瓷，升高温度并不能导致吸附环境氧来填充氧空位，Fe3＋Vo-Fe3＋缺陷复合体所维持的晶格电中性仍占据统治地位，六方-立方结构相变不发生．该项研究为变温XRD技术在工业生产上对无机粉体材料的监控应用提供了技术依据．     

荒漠化地区温室芹菜水肥耦合效应量化管理指标

采用3因素二次回归通用旋转组合设计,探讨灌水量、氮肥、钾肥的耦合效应对芹菜的影响,得到芹菜产量对3因素的回归数学模型.结果表明: 3因素影响芹菜产量的程度为施氮量>灌水量>施钾量.各因素间存在交互作用,水量与N、水量与K2O、N和K2O在低于0.500和1.682、0.500和0.501、1.688和-1.343水平时与产量呈正相关关系,在分别高于以上水平时又会呈负相关关系.经过计算机模拟,得到芹菜最高产量达82.44 t/hm2时,相对应的灌水量、施氮量、施钾量分别为 1 050 m3/hm2、637 kg/hm2、847 kg/hm2.对试验结果进行验证,结果显示构建的模型准确可靠.     

Fe3 O4／TiO2复合物的制备

[目的]以钛铁矿为原料,制备包覆性Fe_3O_4/TiO_2磁性光催化剂。[方法]研究不同温度、反应时间、钛铁矿颗粒大小、是否冷凝回流等条件下钛铁矿的溶解情况以及TiO_2、Fe_3O_4/TiO_2的产率和催化效果,并采用X射线粉末衍射仪(XRD)、红外光谱(FT-IR)、扫描电镜(SEM)、透射电镜(TEM)等对催化剂产物进行表征,且验证催化剂的磁性能。[结果]该方法可以制备出磁性良好、包覆效果好、较纯净的Fe_3O_4/TiO_2包覆性光催化材料。[结论]制备出的Fe_3O_4/TiO_2复合物保持了Fe_3O_4的磁性,是一种性能优良的包覆性光催化材料。     

Epitaxial BiFeO3 multiferroic thin film heterostructures

Enhancement of polarization and related properties in heteroepitaxially constrained thin films of the ferroelectromagnet, BiFeO3, is reported. Structure analysis indicates that the crystal structure of film is monoclinic in contrast to bulk, which is rhombohedral. The films display a room-temperature spontaneous polarization (50 to 60 microcoulombs per square centimeter) almost an order of magnitude higher than that of the bulk (6.1 microcoulombs per square centimeter). The observed enhancement is corroborated by first-principles calculations and found to originate from a high sensitivity of the polarization to small changes in lattice parameters. The films also exhibit enhanced thickness-dependent magnetism compared with the bulk. These enhanced and combined functional responses in thin film form present an opportunity to create and implement thin film devices that actively couple the magnetic and ferroelectric order parameters.     

纳米Fe3O4对红壤微生物数量、酶活性及2,4-D降解的影响

 【目的】从磁致效应的角度考察纳米四氧化三铁(Fe3O4)对红壤微生物数量和酶活性的影响,研究纳米Fe3O4处理对红壤中2,4-D的降解效果,为纳米磁处理技术用于污染土壤修复提供依据。【方法】采用不同剂量的纳米Fe3O4处理红壤,用稀释平板法和化学比色法测定处理前后微生物数量和酶活性的变化;利用高效液相色谱(HPLC)测定土壤中2,4-D浓度的变化。【结果】纳米Fe3O4对细菌和放线菌有激活效应,但对真菌存在抑制作用,且当纳米Fe3O4投加量为80 g•kg-1时磁致效应最显著;同样,纳米Fe3O4对淀粉酶、脲酶、中性磷酸酶和过氧化氢酶也具有激活效应,但对不同酶活性的影响程度存在差异;经纳米Fe3O4处理后红壤中2,4-D的降解率明显高于未处理组,7 d内2,4-D的降解率可达84%。【结论】纳米Fe3O4处理后红壤中的微生物数量和酶活性显著增加,且红壤对2,4-D的降解能力明显增强。     

洗涤废水的处理技术研究

[目的]拓展超声辐射在废水处理方面的应用,探索降解洗涤废水的新途径。[方法]采用对比试验研究超声辐射、Fenton试剂氧化及超声-Fenton试剂耦合法对洗涤废水的降解效果;采用正交试验研究超声时间、pH值、FeSO4投加量、H2O2投加量对超声-Fenton试剂耦合法降解洗涤废水的影响。[结果]超声辐射和Fenton试剂氧化对洗涤废水的降解率都不高,超声-Fenton试剂耦合对洗涤废水的降解率在反应的前10 min随着时间的增加而急剧增加,10 min后趋于稳定,降解完全;各因素对超声-Fenton试剂耦合法降解洗涤废水的影响次序为:反应时间>H2O2投加量>FeSO4投加量>pH值。[结论]在超声-Fenton试剂耦合法降解洗涤废水过程中,当反应时间为10 min,pH值为4,FeSO4投加量为1.0 g/L、H2O2投加量为2 ml/L时,对废水的降解率最高,可达91.2%。     

Ferroelectric Field Effect in Epitaxial Thin Film Oxide SrCuO2/Pb(Zr0.52Ti0.48)O3 Heterostructures

A ferroelectric field effect in epitaxial thin film SrCuO(2)/Pb(Zr(0.52)Ti(0.48))O(3) heterostructures was observed. A 3.5 percent change in the resistance of a 40 angstrom SrCuO(2) layer (a parent high-temperature superconducting compound) was measured when the polarization field of the Pb(Zr(0.52)Ti(0.48))O(3) layer was reversed by the application of a pulse of small voltage (<5 volts). This effect, both reversible and nonvolatile, is attributed to the electric field-induced charge at the interface of SrCuO(2) and Pb(Zr(0.52)Ti(0.48))O(3). This completely epitaxial thin film approach shows the possibility of making nonvolatile, low-voltage ferroelectric field effect devices for both applications and fundamental studies of field-induced doping in novel compounds like SrCuO(2).     

High-temperature molecular magnets based on cyanovanadate building blocks: spontaneous magnetization at 230 k

The molecular-based magnetic materials Cs(2)Mn(||)[V(||)(CN)(6)] (1) and (Et(4)N)(0.5)Mn(l.25)- [V(CN)(5)].2H(2)O (2) (where Et is ethyl) were prepared by the addition of manganese(II) triflate to aqueous solutions of the hexacyanovanadate(II) ion at 0 degrees C. Whereas 1 crystallizes in a face-centered cubic lattice, 2 crystallizes in a noncubic space group. The cesium salt (1) has features characteristic of a three-dimensional ferrimagnet with a Néel transition at 125 kelvin. The tetraethylammonium salt (2) also behaves as a three-dimensional ferrimagnet with a Néel temperature of 230 kelvin; only two other molecular magnets have higher magnetic ordering temperatures. Saturation magnetization measurements indicate that in both compounds the V(II) and high-spin Mn(II) centers are antiferromagnetically coupled. Both 1 and 2 exhibit hysteresis loops characteristic of soft magnets below their magnetic phase-transition temperatures. The high magnetic ordering temperatures of these cyano-bridged solids confirm that the incorporation of early transition elements into the lattice promotes stronger magnetic coupling by enhancing the backbonding into the cyanide pi* orbitals.     

桉树单板化学着色研究

以氯化铁、硫酸铁、硫酸铜、重铬酸钾、重铬酸钠和高锰酸钾等化学试剂为原料进行桉树单板化学着色的药剂配制,获得16种药剂配方。根据着色处理后试件的着色效果和着色渗透深度,筛选出1种适合桉树单板着色的药剂配方处理,代号PBC-1。以PBC-1为处理药剂,采用多因素正交设计分析常压条件下影响桉树单板着色的因素。结果表明:影响桉树单板着色的各因素主次顺序为:药液浓度>处理时间>药液温度>浴比;桉树单板化学着色最佳工艺参数为:药液浓度0.8%,浴比15∶1,药液温度70℃,处理时间10 h;采用所确定的药剂配方和处理工艺,处理后的桉树单板颜色均匀,呈棕褐色,类似柚木色,并且能够很好克服桉树单板表面因节疤所引起的色差问题。     

Bond order and charge localization in nucleoside phosphorothioates

In the recent literature on nucleoside phosphorothioate anions the structural formulas show a double bond between phosphorus and sulfur and a single bond between phosphorus and oxygen with a negative charge localized on oxygen. However, a review of physical data on these compounds shows the reverse to be the case; that is, in phosphorothioate anions the P-S bond is a single bond with a negative charge localized on sulfur, while the P-O bond order for exocyclic and nonbridging oxygens is greater than 1, approaching 2 in O-alkyl phosphorothioate monoanions and O,O-dialkyl phosphorothioates. The P-O bond orders in phosphorothioate dianions and trianions approach 1 1/2 and 1 1/3, respectively, owing to delocalization of negative charge among two or three oxygens. These conclusions are based on bond lengths obtained from x-ray crystallographic data and electron diffraction, the magnitudes of the effects of 18O on the 31P-nuclear magnetic resonance chemical shifts of phosphorus in nucleoside [18O]phosphorothioates, the pH-dependence of 17O-NMR chemical shifts in [17O]phosphate and [17O]thiophosphate, the vibrational spectra of thiophosphate di- and trianions, and the pKa (dissociation constant) values for phosphoric and thiophosphoric acids.     

BST铁电移相器材料的制备及其性能研究

基于铁电移相器材料的应用,通过掺入MgO和La2O3,以进一步优化BST材料性能。采用XRD、SEM测试手段对La2O3掺杂的BST/MgO复合陶瓷材料进行了微观结构分析。用电容法和谐振腔微扰法测试其介电性能。测试结果表明,掺入MgO和La2O3能显著降低BST材料的介电常数和损耗,而且样品在2kV/mm的电场下调谐率能达到10%以上,基本能满足用于制备铁电移相器材料的要求。