氮掺杂微球的制备及其光催化性能

以尿素作为氮源,盐酸(HCl)为钛酸丁酯(TBT)的保护剂,采用溶剂热法合成氮掺杂TiO2微球。用扫描电镜、X射线、能谱仪、多功能电子能谱仪、紫外-可见分光光度计等手段表征了盐酸加入量对微球形貌、物相、成分和催化性能的影响。实验结果表明该方法不仅能合成形貌较好的TiO2微球,同时实现了氮掺杂;盐酸加入量对微球形貌、物相和催化性能有较大影响,发现m(HCl)∶m(TBT)为2.6∶1时光催化效果最佳,在紫外灯和可见灯照射下催化效率均超过Degussa P25。     

Whispering-gallery mode lasers with doped silica microspheres

Light can be confined efficiently in the high-Q, small-volume whispering-gallery-modes observed in silica microspheres. The properties of these modes have allowed us to obtain laser action with very low thresholds in Nd-doped silica microspheres. After a brief introduction to the physics of the whispering-gallery modes, we describe our recent experiments on the lasing properties of doped microspheres at room temperature and their extension at 2 K. Further projects in the field of non-linear Optics and Cavity Quantum Electrodynamics are discussed in the conclusion.     

Biocompatible magnetic microspheres for Use in PDT and hyperthermia

Loaded microspheres with a silicon (IV) phthalocyanine derivative (NzPC) acting as a photosensitizer were prepared from polyhydroxybutyrate-co-valerate (PHBHV) and poly(ecaprolactone) (PCL) polymers using the emulsification solvent evaporation method (EE). The aim of our study was to prepare two systems of these biodegradable PHBHV/PCL microspheres. The first one containing only photosensitizer previously incorporated in the PHBHV and poly(ecaprolactone) (PCL) microspheres and the second one with the post magnetization of the DDS with magnetic nanoparticles. Magnetic fluid is successfully used for controlled incorporation of nanosized magnetic particles within the micron-sized template. This is the first time that we could get a successful pos incorporation of nanosized magnetic particles in a previously-prepared polymeric template. This procedure opens a great number of possibilities of post-functionalization of polymeric micro or nanoparticles with different bioactive materials. The NzPC release profile of the systems is ideal for PDT, the zeta potential and the size particle are stable upon aging in time. In vitro studies were evaluated using gingival fibroblastic cell line. The dark citotoxicity, the phototoxicity and the AC magnetic field assays of the as-prepared nanomagnetic composite were evaluated and the cellular viability analyzed by the classical test of MTT.     

Carboxymethyldextran/magnetite hybrid microspheres designed for hyperthermia

Recently, organic–inorganic hybrids composed of derivatives of dextran, a polysaccharide, and magnetite nanoparticles have attracted much attention as novel thermoseeds. If they can be fabricated into microspheres of size 20–30 μm, they are expected to show not only hyperthermia effects but also embolization effects in human liver and kidney cancers. In this study, we examined the fabrication of carboxymethyldextran/magnetite microspheres using a water/oil emulsion as the reaction medium. Improvement of the chemical stability of the microcapsules by coating with silica using a sol–gel process was also investigated. The obtained hollow microspheres contained particles of size 20–30 μm. Silica coating using an appropriate catalyst for hydrolysis and polycondensation of alkoxysilanes was found to be effective for preventing dissolution and collapse in simulated body environments.     

Preparation and characterization of composite microspheres for brachytherapy and hyperthermia treatment of cancer

Composite microspheres were prepared by coating yttrium-aluminum-silicate (YAS) glass microspheres (20-30 μm) with a layer of Fe₃O₄ nanoparticles and evaluated for potential use in brachytherapy and hyperthermia treatment of cancer. After neutron activation to form the β-emitting ⁹⁰Y radionuclide, the composite microspheres can be injected into a patient to destroy cancerous tumors; at the same time, the composite microspheres can generate heat upon application of a magnetic field to also destroy the tumors. The results showed that the composite microspheres were chemically durable when immersed in a simulated body fluid (SBF), with ~ 0.25% weight loss and ~ 3.2% yttrium dissolved into the SBF after 30 days at 37 °C. The composite microspheres also showed ferromagnetic properties as a result of the Fe₃O₄ coating; when immersed in water at 20 °C (20 mg in 1 mL of water), the application of an alternating magnetic field produced a temperature increase from 20 °C to 38−46 °C depending on the thickness of the Fe₃O₄ coating. The results indicate that these composite microspheres have promising potential in combined brachytherapy and hyperthermia treatment of cancerous tumors.     

Hole-pinned defect-dipoles induced colossal permittivity in Bi doped SrTiO_3 ceramics with Sr deficiency

Bi doped Sr TiO_3 ceramics with Sr deficiency, i.e. Sr_(1-1.5 x)Bi_xTiO_3(x=0, 0.01, 0.05, 0.1), were prepared via conventional solid-state reaction route. A colossal permittivity(CP) over 104 with low dielectric loss less than 0.05 was obtained in x=0.05 Sr_(1-1.5 x)Bi_xTiO_3 ceramics. In addition, the dielectric constant is maintained at a value greater than 10~4 in the range of 10~2-10~5 Hz and almost frequency independent. Phase structure analysis and density functional theory calculations suggest that the Bi_(Sr)~·-V_(Sr)-Bi_(Sr)~·defect complex with hole-pinned defect-dipoles maybe responsible for the high-performance CP properties. This work gives a new way to achieve high performance CP materials in ABO_3 perovskite ceramics.     

Synthesis and characterizations of manganese ferrites for hyperthermia applications

In the last few years, magnetic nanoparticles have turned out to offer great potential in biomedical applications. This study was focused on Mn_xFe_1−xFe₂O₄ ferrite particles series with x ranging between 0 and 1. Manganese ferrites nanoparticles were prepared by co-precipitation method that allows a good control of their shape and size. The X-ray analysis indicated a crystallite size of the particles in the nanometers domain increasing with the Mn cation substitution level. Average grain size of the nanoparticles calculated from transmission electron microscopy images of the samples was ranging between 10.5 and 19.0 nm suggesting that the majority of the nanoparticles are monodomain. The hydrodynamic diameter of the water dispersed nanoparticles measured by dynamic light scattering was ranging between 60 and 105 nm proving the tendency of agglomeration. Vibrating sample magnetometer measurement confirmed the superparamagnetic behavior of the powders. The magnetic properties were analyzed considering the proposed cation distribution and Yafet–Kittel angles, while the specific absorption rate (SAR) measurement at 1.95 MHz frequency confirmed the influence of substitution level on magnetic properties and thermal transfer rate. From our results the highest value for specific absorption rate was 148.4 W g⁻¹ for Mn₂Fe₂O₄ at an AC field of 4500 A m⁻¹.     

Remanence properties of substituted Ba-ferrite particles for highdensity magnetic recording

In this paper, the remanence properties of Co-Sn, Co-Ti and Co-Ti-Sn substituted Ba-ferrite (BaF) oriented particulate samples are compared with those of some oriented acicular particulate samples. A new parameter, the minor remanence distribution (MRD), is proposed to review the remanence properties of magnetic particles and the capabilities for resisting the recording demagnetization of magnetic recording media. It is shown that the MRD values of the oriented BaF particulate samples were smaller compared to oriented Co-γ-Fe₂O₃ samples, even though the squareness ratios (SR) of some of the BaF samples were smaller than those of the Co-γ-Fe₂O₃ samples. It Is the small MRD, SFD_r, IRS and large DH _r of a medium that can result in a large resistance to the effects of recording demagnetization and therefore in superior characteristics for high density magnetic recording. Since Co-Sn substituted BaF platelet-shaped particles exhibit these characteristics and have a very low temperature coefficient of coercivity, these particles can be expected to be a promising candidate for high density magnetic recording     

PSS-VS共聚物掺杂PEDOT的合成与表征

以苯乙烯磺酸钠(SSS)和乙烯磺酸钠(SVS)的共聚物PSS-VS为掺杂剂,过硫酸铵(APS)为氧化剂,采用化学氧化法制备了PEDOT/PSS-VS分散体,研究了PSS-VS的共聚比、分子量和用量等因素对PEDOT/PSS-VS导电性能及平均粒径的影响,分析了PEDOT/PSS-VS粒子形成过程。结果表明,SSS/SVS共聚摩尔比为5/5,单体与APS摩尔比为60时制得的PSS-VS掺杂PEDOT具有较好的导电性和分散稳定性,SO3-/EDOT=2,APS/EDOT=1.5,PEDOT/PSS-VS固含量为2.8%时制得的PEDOT/PSS-VS电导率可达11.74S/cm,分散体平均粒径为447nm。     

掺杂Ti的纳米CrSi_2薄膜的制备

利用多靶磁控溅射设备交替沉积Cr、Ti和Si层,并通过随后的真空退火处理,制备了掺杂Ti的CrSi2薄膜。交替沉积薄膜500℃退火2h,薄膜中除含有(Cr,Ti)Si2相外,还有部分残留的沉积Si相和少量反应生成的CrSi相;退火时间增加,沉积Si相和CrSi相减少而(Cr,Ti)Si2相增多;500℃退火6h及以上时,薄膜中仅有(Cr,Ti)Si2相。测量薄膜X射线衍射峰半高宽,利用谢乐公式估算薄膜平均晶粒尺寸表明,退火时间从2h增加到8h,薄膜中(Cr,Ti)Si2相晶粒尺寸由68nm近似线性增加到81nm。退火获得的(Cr,Ti)Si2薄膜具有纳米结构和(111)面单一取向。随着掺杂Ti原子分数的增加,薄膜X射线衍射谱中(Cr,Ti)Si2(111)晶面衍射角逐渐向低角度方向移动,这反映(Cr,Ti)Si2相的晶格常数a和c逐渐增大。晶格常数的变化与掺杂Ti的原子分数近似呈线性关系,这是结构中半径较大的Ti原子替换半径较小的Cr原子所造成的。计算分析显示,单晶Si(100)上(Cr,Ti)Si2(111)晶面外延生长是它们的界面晶格畸变能较低的结果;Ti原子分数增加,(Cr,Ti)Si2薄膜的(111)晶面择优取向程度下降。     

Synthesis and characterization of pure and doped (Na, Ca, Sr) nanograined LaMnO3 magnetoresistive ceramics

Pure and Na, Ca, and Sr doped lanthanum manganites (LaMnO3, La0.85Na0.15MnO3, La0.7Ca0.3 MnO3, La0.7Sr0.3MnO3) were prepared in form of bulk nano-structured materials through a two-step process. Nanometric powders were synthesized by the Pechini method and subsequently densified by Spark Plasma Sintering at 1273 K for 5 minutes under a pressure of 140 MPa. The method allowed the preparation of single phase manganites with a theoretical density above 98% together with a very limited growth of the grain size. Grain sizes below 70 nm were obtained for all materials except La0.85Na0.15MnO3 which showed a much larger grain size. Curie temperatures (Tc) and magnetoresistivity properties of the samples were measured by a Superconducting Quantum Interference Device (SQUID). The decrease in the resistivity below Tc occurred in a much wider range of temperature compared to ceramics having micron-size grains.     

Synthesis of nanostructured bismuth titanate microspheres

A hydrothermal method was developed for the synthesis of bismuth titanate nanostructured microspheres. The precursor powder was prepared using a diethylene glycol mediated coprecipitation method. The as-synthesized nanostructured microspheres consisting of granular nanoparticles and nano-platelets were obtained through a hydrothermal treatment of the precursor powder in aqueous sodium hydroxide solution. Tailoring of the morphology was achieved by changing the precursor quantity, sodium hydroxide concentration, and reaction time. The formation mechanism of the nanostructured microspheres probably involves aggregation, followed by dissolution and recrystallization. X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy were used to characterize the phase purities, morphologies, and composition of the products.     

Synthesis and luminescence of nano-insulators doped with lanthanide ions

This paper reviews the syntheses, particle-size measurements and various aspects of the optical spectra of lanthanide ion doped insulating nanomaterials, with the focus upon the sesquioxides, and it contrasts their behaviour with bulk materials.     

Synthesis of hollow CuS nanostructured microspheres with novel surface morphologies

Hollow CuS nanostructured microspheres with novel surface morphologies were synthesized by a facile precipitate-converting reaction. The products were characterized by SEM, XRD, BET measurements and size analysis. The surfaces of the hollow CuS microspheres showed acicular, rod-like, concavo-convex and flat morphologies respectively when using different amounts of thioacetamide as precipitants. The diameters of the hollow CuS microspheres could be tuned to a certain extent by using Cu₂(OH)₂CO₃ microspheres with different sizes as precursors. A solid–solution–solid mechanism for the formation of the hollow CuS nanostructured microspheres was discussed. The method reported here also could be applied for the synthesis of other nanostructured microspheres.     

Synthesis and photocatalytic activity of titania microspheres with hierarchical structures

A combined sol-gel and solvothermal process was introduced to fabricate the titania microspheres with hierarchical structures by using lauryl alcohol as the structure-directing agent. Scanning electron microscope, high-resolution transmission electron microscope, Fourier transform infrared spectrograph and powder X-ray powder diffraction indicated that the molar ratio of lauryl alcohol, water and tetra-n-butyl titanate was the key factor for the formation of the mono-dispersed titania with anatase phase and the optimal ratio was 1.2:4:1. The diameter of the end-product was 523 ± 74 nm and it was composed of smaller nanoparticles with about 6.8 nm size in diameter. Photocatalytic activity of the end-product was investigated by employing Rhodamine B and Methylene blue as the model compounds. The target microspheres exhibited the higher photocatalytic efficiency compared with commercial Degussa P25 titania and this result might be due to the hierarchical structures of microspheres according to the analysis of Brunauer-Emmett-Teller specific surface areas.     

Synthesis of hollow lead sulfide microspheres

Lead sulfide (PbS) uniform hollow spheres have been successfully synthesized by γ-irradiating PMMA–CS₂–ethanol aqueous solution that contains Pb(CH₃COO)₂·3H₂O at room temperature. X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), transmission electron micrograph (TEM), and high-resolution transmission electron micrograph (HRTEM) experimental results show that the diameter of PbS hollow spheres, the thickness of sphere shell, and the size of these crystallites are about 500, 20, and 10 nm, respectively. Room temperature UV–vis absorption spectrum of the PbS hollow spheres gives its peak centered at around 238 nm and a weak shoulder peak centered at about 322 nm. The obvious blue shift of the absorption peak may be attributed to the small dimension of the PbS bricks of the spheres wall. A possible growth mechanism of PbS hollow sphere is also presented. The successful preparation of PbS hollow spheres in large scale under mild conditions could be of interest for both applications and fundamental studies.     

Ce3+掺杂聚苯胺中空微球/环氧涂层防腐蚀研究

聚苯胺作为一种新型的防腐蚀材料,在钢铁防腐蚀领域具有良好的应用前景.通过自组装法在聚(2-丙烯酰胺基-2-甲基丙磺酸)(PAMPS)水溶液中制备了聚苯胺(PANI)中空微球,将稀土Ce~(3+)掺杂到聚苯胺中空微球表面制备了一种新型的Ce~(3+)掺杂修饰的聚苯胺中空微球(PANI-Ce~(3+)).以PANI-Ce~(3+)中空微球为防腐填料添加到环氧树脂(EP)中,制备Ce~(3+)掺杂修饰的聚苯胺中空微球/环氧(PANI-Ce~(3+)/EP)防腐涂层.采用FT-IR、UV-Vis、SEM、XRD等对PANI-Ce~(3+)中空微球进行表征,通过动电位极化法、交流阻抗测试探究PANI-Ce~(3+)/EP涂层的防腐蚀性能.结果表明:PANI-Ce~(3+)/EP涂层具有较高的腐蚀电压(Ecorr=-0.414 V)和较小的腐蚀电流密度(I_(corr)=0.676×10~(-5)μA/cm~2);PANI-Ce~(3+)/EP涂层低频区阻抗模量随浸泡时间呈现先减小后增大的变化趋势,在质量分数3.5%的NaCl水溶液中经过1 680 h腐蚀后,阻抗模量保持在106.6Ω·cm~2;表面有划伤的PANI-Ce~(3+)/EP涂层在质量分数3.5%的Na Cl水溶液进行1 680 h腐蚀实验后,涂层表面不起泡,仅在划痕处有少量铁锈.PANI-Ce~(3+)/EP涂层表现出优异的耐腐蚀性能.     

Nest-like structures of Sr doped Bi2WO6: Synthesis and enhanced photocatalytic properties

A series of Sr-doped Bi₂WO₆ with three-dimensional (3D) nest-like structures were synthesized through simple hydrothermal route and characterized by XRD, FESEM, TEM, XPS, UV-vis DRS, etc. Morphology observation revealed that the as-synthesized Bi₂WO₆ were self-assembled three-dimensional (3D) nest-like structures, which were constructed from nanoplates. UV-vis diffuse reflectance spectra indicated that the samples had absorption in both UV and visible light areas. Their photocatalytic activities were evaluated by photodegradation of rhodamine B (RhB) under UV and visible light irradiation (λ > 420 nm). The photocatalytic properties were enhanced after Sr doping. Samples subsequently thermal treated at 500 °C showed higher photocatalytic activities. The reasons for the differences in the photocatalytic activities of these nest-like Bi₂WO₆ microstructures were further investigated.     

N,N''''-亚甲基双丙烯酰胺交联淀粉微球的合成与表征

以可溶性淀粉为原料,K2S2O8-Na2SO3为引发剂,用反相悬浮法合成了N,N'-亚甲基双丙烯酰胺交联淀粉微球CSM.研究了交联剂质量分数、反应温度和引发剂浓度对微球产率、溶胀度、平均粒径的影响规律.用扫描电镜观测了样品形貌,用FT-IR对其结构进行了表征,用XRD、DSC以及TGA对其物理性质进行了分析.结果表明,所合成的交联淀粉微球形态圆整,表面光滑,粒度均匀,微球中存在酰氨基结构.与可溶性淀粉相比,淀粉微球结晶度降低,热稳定性增加.