BaTiO_3@Cu核-壳复合粒子电/磁双响应性能

以平均粒径约为500nm的BaTiO_3微球为基核,通过"一步法"成功地制备了BaTiO_3@Cu核-壳复合粒子。利用SEM、TEM、XPS、介电测量分析仪和阻抗分析仪等对复合粒子的组成、结构、介电性能和磁性能进行测定。另外将纯BaTiO_3和BaTiO_3@Cu核-壳复合粒子分别分散到水凝胶中,通过测量和分析在有/无电场、磁场和电磁复合场作用下得到的水凝胶的储能模量,考察粒子在水凝胶中的电、磁和电磁响应性能。结果表明,BaTiO_3@Cu复合粒子具有完整清晰的核-壳结构,在整个表面壳层铜元素中,Cu(0)的原子分数达到了90at%,具有优良的介电性能和磁性能。BaTiO_3@Cu核-壳复合粒子是一种对外加电场和磁场作用都具有响应性能的多功能新型智能材料,且其电磁复合响应性能显著强于纯BaTiO_3粒子。     

Synthesis of aligned porous poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) composite microspheres

We synthesized poly(ε-caprolactone) (PCL)/hydroxyapatite (HA) composite microspheres with an aligned porous structure and evaluated their potential applications in bone tissue engineering. A range of HA particles (0, 5, 10 and 20 wt.% in relation to the PCL polymer) were added to a PCL solution in order to improve the biocompatibility of the porous PCL/HA composite microspheres. All the synthesized microspheres showed that the HA particles were distributed well in the PCL matrix, while preserving their aligned porous structure. The average size of the PCL/HA composite microspheres increased from 62 ± 7 to 179 ± 95 μm with increasing HA content from 0 to 20 wt.%. The incorporation of the HA particles to the PCL polymer led to a considerable improvement in in vitro bioactivity, which was assessed by immersing the PCL/HA composite microspheres in simulated body fluid (SBF). A number of apatite crystals could be precipitated on the surface of the aligned porous PCL/HA composite microspheres after soaking in the SBF for 7 days.     

非均相悬浮法制备多孔羟基磷灰石微球

为了获得具有吸附和生物学功能的多孔羟基磷灰石(HA)微球,以自制的纳米羟基磷灰石(HA)粉体为原料,用非均相悬浮法制备了HA/明胶微球,将微球在1 250℃下焙烧,成功制备了直径100~500μm的多孔HA微球.采用光学显微镜、SEM分析、XRD分析和BET氮吸附法研究了微球形貌、尺寸、物相组成、比表面积和孔径,测定了微球对水中F-离子的吸附性能.结果表明:微球具有良好球形形貌和相互贯通的纳米微孔;尺寸比较均匀,分散性良好;微球的主要结晶相为羟基磷灰石;BET表面积为1.867 0~2.089 5 m~2/g,孔径6.53~6.85 nm;对氟离子的平衡吸附容量为1.909~1.940 mg/g.通过控制m(HA)/m(明胶)比例、油温、搅拌速度和搅拌时间,可以在一定范围内控制微球直径和比表面积.     

A novel solid-stabilized emulsion approach to CuO nanostructured microspheres

Nanostructured CuO microspheres were prepared by a novel solid-stabilized emulsion for the first time. SEM, TEM, XRD, size analysis and BET measurement were used to characterize the CuO microspheres. The average diameter of the CuO microspheres was 2.8 μm. The surfaces of the CuO microspheres were made of pin-like nanostructures with a pin diameter of 95 nm and a pin length of at least 600 nm. The XRD analysis indicated that the CuO nanostructured microspheres were of monoclinic lattice. The specific surface area of the CuO nanostructured microspheres was about 56.8 m²/g. A mechanism for the formation of the CuO microspheres with nanostructured surfaces was proposed.     

Controllable synthesis and characterization of novel copper-carbon core-shell structured nanoparticles

A facile hydrothermal method was developed for preparing copper-carbon core-shell structured particles through a reaction at 160 °C in which glucose, copper sulfate pentahydrate and cetyltrimethylammonium bromide were used as starting materials. The original copper-carbon core-shell structured particles obtained were sized of 100-250 nm. The thickness of carbonaceous shells was controlled ranging from 25 to 100 nm by adjusting the hydrothermal duration time and the concentrations of glucose in the process. Products were characterized with transmission electron microscopy, X-ray diffraction, energy dispersive spectroscopy, Fourier transform infrared spectroscopy. Since no toxic materials were involved in the preparation, particles with stable carbonaceous framework and reactive surface also showed promising applications in medicine, electronics, sensors, lubricant, etc.     

Fabrication and characterization of porous hydroxyapatite microspheres by spray-drying method

In the present paper, porous hydroxyapatite (HA) microspheres were fabricated using gelatin as a pore-forming agent by spray-drying method. The mean particle size of the microspheres is about 7 μm and the surface area is about 53.4 m²/g. The experimental results showed that the porosity of the prepared microspheres is higher and the pores are more interconnected compared with the microspheres obtained without any additives.     

Facile fabrication of SiO2/Al2O3 composite microspheres with a simple electrostatic attraction strategy

SiO₂/Al₂O₃ composite microspheres with SiO₂ core/Al₂O₃ shell structure and high surface area were prepared by depositing Al₂O₃ colloid particles on the surface of monodispersed microporous silica microspheres using a simple electrostatic attraction and heterogeneous nucleation strategy, and then calcined at 600 °C for 4 h. The prepared products were characterized with differential thermal analysis and thermogravimetric analysis (DTA/TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption and X-ray photoelectron spectroscopy (XPS). It was found that uniform alumina coating could be deposited on the surface of silica microspheres by adjusting the pH values of the reaction solution to an optimal pH value of about 6.0. The specific surface area and pore volume of the SiO₂/Al₂O₃ composite microspheres calcined at 600 °C were 653 m² g⁻¹ and 0.34 ml g⁻¹, respectively.     

HRTEM observations on composites of tin and tin dioxide nanoparticles dispersed on carbon nanotubes by single-atoms-to-clusters method

Nano-composites of tin and tin dioxide particles were synthesized on carbon nanotubes by the single-atoms-to-clusters (SAC) method, and their structures were investigated by high-resolution transmission electron microscopy. By changing the heat-treatment temperature during the SAC process, two different types of samples were obtained. The samples prepared around 450 K were aggregates of 2-4 nm-sized tin dioxide nanoparticles, and their size distributions on carbon nanotubes are in the range 20-40 nm. The other samples formed above 600 K had a core-shell structure of diameter 20-40 nm. The core and shell were made of tin single crystal and disordered oxidized tin, respectively. The thickness of the oxidized layers was ca. 4 nm.     

Controlled preparation of hollow zinc oxide microspheres from aqueous solution using hexamethylenetetramine and cysteine

Zinc oxide particles were synthesized by precipitation from an aqueous solution of zinc nitrate tetrahydrate, R-(+)-cysteine and hexamethylenetetramine (HMTA, urotropine). Hollow microspheres of ZnO-cysteine hybrid material with a diameter of ca. 1 μm and a wall thickness ca. 50 nm were obtained. After heating up to 850 °C pure ZnO microspheres of roughly the same size were formed. The particles were characterized by XRD, SEM, FT-IR and TGA.     

Porous biomedical composite microspheres developed for cell delivering scaffold in bone regeneration

Microspherical particles have attracted great interest as a delivery system of tissue cells in regenerative engineering. For hard tissue regeneration, here we exploited porous biomedical composite microspheres of hydroxyapatite-polycaprolactone (HA-PCL). The pore channels within the microsphere was facilitated by using camphene as the porogen, where the initial HA-PCL-camphene mixture in chloroform was solidified and the camphene was then sublimed to leave pore channels within the HA-PCL microspheres. The pore size increased with increasing camphene concentration, resulting in the generation of macropores (> 50 μm). Rat bone marrow mesenchymal stem cells were shown to proliferate actively on the porous microspheres penetrating deeply into the pore channels. Results suggest future applications of the porous composite microsphere as a cell delivery scaffold for bone tissue regeneration.     

Fabrication of high conductivity dual multi-porous poly (l-lactic acid)/polypyrrole composite micro/nanofiber film

Dual multi-porous PLLA (poly(l-lactic acid))/H₂SO₄-doped PPy (polypyrrole) composite micro/nano fiber films were fabricated by combining electrospinning with in situ polymerization. The morphologies and structures of the resulting samples were analyzed by scanning electron microscopy (SEM). It was found that the composite micro/nano fibers exhibited a core-shell structure and the composite fiber film had a dual multi-pore structure composed of pores both in the fibers and among the fibers. Semiconductor parameter analyzer was used to characterize the electrical properties of the samples. It was interesting to find that all the PLLA/H₂SO₄-doped PPy composite micro/nano fiber films had higher conductivity than H₂SO₄-doped PPy particles when the polymerization time up to 180 min. Effects of the pyrrole synthesis conditions on the pore size and the conductivity of PLLA/PPy composite fiber film were assessed. By optimizing the polymerization conditions, the max conductivity of this composite fiber film was about 179.0 S cm⁻¹ with a pore size of about 250 μm. The possible mechanism of PLLA/H₂SO₄-doped PPy composite micro/nano fiber films had much higher conductivity than H₂SO₄-doped PPy particles was discussed.     

Effect of particle size and weight fraction on the flexural strength and failure mode of TiO2 particles reinforced epoxy

Effect of inclusions size and weight fraction on flexural strength and failure mode of composite containing SC-15 epoxy resin and TiO₂ particles has been studied in this investigation. The sizes of particles varied from macro (0.02 mm) to nano (5 nm) scale, and these particles were infused into the part-A of SC-15 through sonic cavitations and then mixed with part-B of SC-15 by using a high speed mechanical agitator. Three-point bending tests were performed on unfilled, 0.5 wt.%, 1.0 wt.% and 1.5 wt.% particles filled SC-15 epoxy to identify the loading effect on mechanical properties of the composites. Results show that 1.0 wt.% nanoparticles reinforced epoxy exhibit the highest mechanical performance. Higher than 1.0%, strength of composite decreased because of poor dispersion. Experimental results also shown that micro-sized particles have little effect on strength of epoxy at such low loading, and strength of composite increased as the size of particles decreased to nano scale. However, degradation in strength was found in 5 nm TiO₂/epoxy system due to agglomeration.     

MgO nanostructured microspheres synthesized by an interfacial reaction in a solid-stabilized emulsion

Nanostructured MgO microspheres were prepared by a novel solid-stabilized emulsion for the first time. SEM, XRD, size analysis and BET measurement were used to characterize the MgO microspheres. The diameter of the MgO microspheres was in a range of 5.1 to 5.4 μm. The surfaces of the MgO microspheres were made of leaf-like nanostructures with a leaf thickness of 65 nm. The XRD analysis indicated that the MgO nanostructured microspheres were of cubic lattice. The specific surface area of the MgO nanostructured microspheres was about 105.8 m²/g. The MgO microspheres with nanostructured surfaces had a larger specific surface area than the MgO polyhedral particles prepared by the comparing experiment (via a conventional homogeneous precipitation route). An interfacial reaction mechanism for the formation of the MgO microspheres with nanostructured surfaces was proposed.     

Preparation of uniform Silicalite-1 microspheres with large secondary pore architecture using monodisperse porous polystyrene particles as template

A new method was developed for preparation of silicalite-1 microspheres with uniform diameter about 2.5 μm using monodispersed micron-sized poly- styrene-co-divinylbenzene (PSD) porous particles as template. In this method, the PSD particles were impregnated first with tetraethoxysilane (TEOS) and then with tetrapropylammonium hydroxide (TPAOH). After crystallization and calcination, the silicalite-1 microspheres, possessing a regularly spherical morphology similar to the original silicalite-1, were successfully synthesized. More importantly, the silicalite-1 microspheres have large secondary pores in the range of 40 to 120 nm and high pore volume up to 0.7 cm³g^− 1. All these would facilitate the applications of microspheres in catalysis avoiding diffusion limitation.     

Synthesis of ultrafine lanthanum ferrite (LaFeO3) fibers via electrospinning

Ultrafine one-dimensional LaFeO₃ nanofibers were synthesized by electrospinning utilizing sol-gel precursors. The surface morphology, microstructure and crystal structure were investigated by scanning electron microscopy, X-ray diffraction and transmission electron microscopy. The nanofibers with smaller diameter were continuous and uniformly distributed. Typical fiber diameter was between 180 nm and 220 nm and the average diameter was 200 nm. The fibers consisted of many single-crystal LaFeO₃ grains and the grain size was about 20-50 nm. The relationship between the diameter of as-synthesized fibers and the PVP concentration of the precursor was investigated. The experimental results indicated that the PVP concentration had a great impact on the fiber size and 5.89 wt.% PVP concentration in sol-gel precursors was advantageous to the formation of more uniform electrospun composite fibers with smaller diameter.     

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.     

Carbon microspheres with embedded magnetic iron oxide nanoparticles

Narrow-size disperse porous carbon microspheres with embedded magnetite nanoparticles were prepared by annealing Fe(III)-containing microspheres composed of a copolymer of acrylic acid and divinylbenzene at 800 °C under inert atmosphere. The Fe(III)-containing microspheres were prepared by uptake of Fe²⁺ ions through ion exchange process by poly(acrylic acid-divinylbenzene) microspheres that were prepared by distillation-precipitation polymerization, followed by annealing at 250 °C at ambient atmosphere. The carbonization of the microspheres created micropores with a maximum pore diameter of about 0.38 nm and a BET surface area of ~ 200 m²/g. The saturation magnetization of the magnetic carbon microspheres was 31.5 emu/g with a low remnant magnetization and coercivity.     

Gelatin/BaTiO3核壳复合粒子的制备及电场响应性能研究

以平均粒径为0.7~0.9 mm的明胶(Gelatin)微球为基核, 通过定向沉积自组装法成功制备了以Gelatin为核、BaTiO₃为壳的Gelatin/BaTiO₃核壳复合粒子。利用TEM、XRD、FT-IR、TG和光学接触角测量等技术对复合粒子的形貌、结构、组成及表面亲水性能进行了研究。结果表明, 复合粒子为球形微粒, 具有良好的表面亲水性和分散稳定性, BaTiO₃壳层约占粒子总质量的18.8%, 具有立方相晶相结构。将粒子分散到水凝胶弹性体中, 测量在有/无电场作用下得到的弹性体的储能模量, 借以考察复合粒子在弹性体中的电场响应性能, 发现Gelatin/BaTiO₃复合粒子的电场响应性能明显强于纯BaTiO₃粒子。说明将BaTiO₃包覆在聚合物上能显著提高BaTiO₃粒子的电场响应性能。     

Formation of core-type microstructure in Al-Bi monotectic alloys

The macroscopic morphologies and core-shell dimensional accuracy for Al-Bi immiscible alloys were investigated. Irrespective of compositions, the shell always consists of a Bi-rich phase due to surface segregation. With decreasing the superheat degree above the highest critical point of Al-65.5 wt.% Bi alloy, the shell of particles changed from irregular, annular to crescent shapes under the actions of Marangoni motion and gravity. The simulation suggests that the superheating and particle size affect markedly the temperature gradient and cooling rate of droplets, and thus influence the Marangoni and Stokes motions. At a superheat degree of 100 K, a perfect core-shell microstructure of Al-65.5 wt.% Bi particles with a diameter of 0.9 mm was successfully obtained. The dimensional relationship between the core and whole particle could be described by a function of D_core = 0.9137 D_particle − 0.0312.     

轻质高导电镀银复合粒子的制备研究

采用分散聚合工艺,以聚乙烯吡咯烷酮为分散剂,偶氟二异丁腈为引发剂,无水乙醇为分散介质,制备出粒径2.0μm、表面光滑、分散均匀的聚苯乙烯微球.将其进行表面磺化处理后运用化学镀工艺制备出了具有轻质高导电特性的聚苯乙烯/银复合粒子.对所制备的复合粒子进行了扫描电镜、红外光谱以及体积电阻率的测试.结果表明:所制备的复合粒子包覆均匀、导电性能良好;表面修饰提高了PS微球表面的电负性和亲水性并引入了磺酸基团,对PS微球表面镀银起到了重要作用;另外,随着PdCl2浓度和AgNO3/PS质量比的增加,复合粒子包覆完整性和导电性能都随之增加,最佳体积电阻率为1.61×10 -4Ω·cm.