层层自组装制备PANI/CuTsPc复合薄膜及其性能研究

运用层层自组装技术制备了聚苯胺/磺化酞菁铜(PANI/CuTsPc)超分子复合薄膜,并通过紫外-可见-近红外吸收光谱、红外光谱、电导率测试仪与热分析仪对复合薄膜进行了分析表征以及导电性、光吸收与热稳定性能的研究.紫外-可见-近红外光谱表明,PANI与CuTsPc具有良好的层层自组装特性,沉积过程具有均匀性与重复性,复合薄膜在可见光区和近红外区均具有平而且宽的强吸收谱带;红外光谱表明,PANI和CuTsPc通过静电力的作用成功组装成膜,复合薄膜的共轭体系得到加强;电导率测试结果表明复合薄膜具有较高的电导率,达到了0.3S/cm;热分析结果表明CuTsPc组分的加入使复合薄膜具有良好的热稳定性.     

Fabrication of graphene thin films based on layer-by-layer self-assembly of functionalized graphene nanosheets

In this study, we present a facile means of fabricating graphene thin films via layer-by-layer (LbL) assembly of charged graphene nanosheets (GS) based on electrostatic interactions. To this end, graphite oxide (GO) obtained from graphite powder using Hummers method is chemically reduced to carboxylic acid-functionalized GS and amine-functionalized GS to perform an alternate LbL deposition between oppositely charged GSs. Specifically, for successful preparation of positively charged GS, GOs are treated with an intermediate acyl-chlorination reaction by thionyl chloride and a subsequent amidation reaction in pyridine, whereby a stable GO dispersibility can be maintained within the polar reaction solvent. As a result, without the aid of additional hybridization with charged nanomaterials or polyelectrolytes, the oppositely charged graphene nanosheets can be electrostatically assembled to form graphene thin films in an aqueous environment, while obtaining controllability over film thickness and transparency. Finally, the electrical property of the assembled graphene thin films can be enhanced through a thermal treatment process. Notably, the introduction of chloride functions during the acyl-chlorination reaction provides the p-doping effect for the assembled graphene thin films, yielding a sheet resistance of 1.4 kΩ/sq with a light transmittance of 80% after thermal treatment. Since the proposed method allows for large-scale production as well as elaborate manipulation of the physical properties of the graphene thin films, it can be potentially utilized in various applications, such as transparent electrodes, flexible displays and highly sensitive biosensors.     

聚苯胺/磺化酞菁铜自组装复合薄膜的制备与表征

运用层层自组装的技术制备了聚苯胺/磺化酞菁铜(PANI/CuTsPc)超分子复合薄膜,并通过紫外-可见-近红外吸收光谱、傅立叶红外光谱、X射线衍射仪与原子力显微镜对薄膜进行了表征与分析.紫外-可见-近红外吸收光谱表明,PANI和CuTsPe具有良好的层层自组装特性,沉积过程具有均匀性与重复性;傅立叶红外光谱表明,复合薄膜是由PANI和CuTsPc组成的,PANI和cuTsPc通过静电力的作用组装成膜;X射线衍射结果表明,复合薄膜是非晶态的;原子力显微镜观察到薄膜表面是比较均匀和致密的,但有一定的粗糙度.     

Immobilization of ibuprofen-containing nanospheres in layer-by-layer films

Liposomes have been applied to many fields as nanocarriers, especially in drug delivery as active molecules may be entrapped either in their aqueous interior or onto the hydrophobic surface. In this paper we describe the fabrication of layer-by-layer (LbL) films made with liposomes incorporating the anti-inflammatory ibuprofen. The liposomes were made with dipalmitoyl phosphatidyl choline (DPPC), dipalmitoyl phosphatidyl glycerol (DPPG) and palmitoyl oleoyl phosphatidyl glycerol (POPG). LbL films were assembled via alternate adsorption of the polyamidoamine dendrimer (PAMAM), generation 4, and liposomes containing ibuprofen. According to dynamic light scattering measurements, the incorporation of ibuprofen caused DPPC and DPPG liposomes to become more stable, with a decrease in diameter from 140 to 74 nm and 132 to 63 nm, respectively. In contrast, liposomes from POPG became less stable, with an increase in size from 110 to 160 nm after ibuprofen incorporation. These results were confirmed by atomic force microscopy images of LbL films, which showed a large tendency to rupture for POPG liposomes. Film growth was monitored using nanogravimetry and UV-Vis spectroscopy, indicating that growth stops after 10 bilayers. The release of ibuprofen obtained with fluorescence measurements was slower for the liposomes, with decay times of 9.2 and 8.5 h for DPPG and POPG liposomes, respectively, than for the free drug with a decay time of 5.2 h. Ibuprofen could also be released from the LbL films made with DPPG and POPG liposomes, which is promising for further uses in patches.     

C/Co/C纳米颗粒膜的制备及特性

应用对靶磁控溅射法在玻璃基底上制备了类三明治结构C/Co/C纳米颗粒膜,并进行了原位退火.发现磁性层厚度对C/Co/C颗粒膜的微结构和磁特性有明显影响.在400℃退火的样品具有很好的六角密堆积结构,磁矩很好的排列在膜面内.随着磁性层Co层厚度的增加,矫顽力Hc先增大然后减小,粒径和磁畴簇略微增大,样品的表面粗糙度Ra也减小到了0.5 nm左右.     

Fabrication of luminescent SrWO4 thin films by a novel electrochemical method

Highly crystallized SrWO₄ thin films with single scheelite structure were prepared within 60 min by a cell electrochemical method. X-ray diffraction analysis shows that SrWO₄ thin films have a tetragonal structure. Scanning electron microscopy examinations reveal that SrWO₄ grains grow well in tetragonal tapers and grains like flowers or bunches, which can usually form by using the electrolysis electrochemical method, have disappeared under cell electrochemical conditions. X-ray photoelectron spectra and energy dispersive X-ray microanalysis examinations demonstrate that the composition of the film is consistent with its stoichiometry. These SrWO₄ films show a single blue emission peak (located at 460 nm) using an excitation wave of 230 nm. The speed of cell electrochemical method can be controlled by changing temperature. The optimum treatment temperature is about 50-60 °C.     

Fabrication of layered double hydroxide/photoresponsive dendron nanocomposite multilayer film by electrostatic layer-by-layer assembly

A novel inorganic–organic nanoscopic multilayer film consisting of exfoliated MgAl-type layered double hydroxide (LDH) nanosheets and anthryl dendrons [i.e., poly(amidoamine) dendrons with an anthracene chromophore group at the focal point] was fabricated using an electrostatic layer-by-layer (LbL) assembly. UV–vis spectroscopy and X-ray diffraction analysis indicated the successful LbL growth of dendron/LDH multilayer films. Furthermore, fluorescence spectroscopic analysis indicated that the dendrons are present as a monolayer between LDH nanosheets in the film.     

Modifying PTAA/Perovskite Interface via 4-Butanediol Ammonium Bromide for Efficient and Stable Inverted Perovskite Solar Cells

Inverted perovskite solar cells (IPSCs) have witnessed an impressive development in recent years. However, their efficiency is still significantly behind theoretical limits, and device instabilities hinder their commercialization. Two main obstacles to further enhancing their performance via one-step deposition are: 1) the unsatisfactory film quality of perovskite and 2) the poor surface contact. To address the above issues, 4-butanediol ammonium Bromide (BD) is utilized to passivate Pb²⁺ defects by forming Pb N bonds and fill vacancies of formamidinium ions at the buried surface of perovskite. The wettability of poly [bis (4-phenyl) (2,4,6-triMethylphenyl) amine] films is also improved due to the formation of hydrogen bonds between PTAA and BD molecules, resulting in better surface contacts and enhanced perovskite crystallinity. As a result, BD-modified perovskite thin films show a significant increase in the mean grain size, as well as a dramatic enhancement in the PL decay lifetime. The BD-treated device exhibits an efficiency of up to 21.26%, considerably higher than the control device. Moreover, the modified devices show dramatically enhanced thermal and ambient stability compared to the control ones. This methodology paves the way to obtain high-quality perovskite films for fabricating high-performance IPSCs.     

Fabrication of mesoporous titanium oxide nanotubes based on layer-by-layer assembly

Titanium oxide (TiO2)/polyacrylic acid (PAA) composite nanotubes were firstly fabricated through the sol-gel process of titanium alkoxide in the inner pores of alumina template followed layer-by-layer assembly with polyacrylic acid (PAA). Mesoporous TiO2 nanotubes could be obtained after the removal of PAA component by calcination and etching of the template with concentrated sodium hydroxide aqueous solution. The surface area of as-prepared porous TiO2 nanotubes was measured as twice larger than that of the conventional TiO2 nanotubes and the pore diameter in the wall of the tubes is several nanometers. Such assembled mesoporous nanotubes can serve as carriers for catalysis release and biomolecules.     

碳纳米管和壳聚糖的层层静电自组装多层膜(英文)

将多壁碳纳米管(MWCNT)置于混酸(硝酸∶硫酸=1∶3)中,利用超声波振荡截短碳纳米管、并使其与羧基链接,而后基于阳离子聚合电解质壳聚糖(CS)和阴离子短切碳纳米管之间的静电作用,在玻璃衬底上通过层层的模式均匀稳定地自组装形成复合壳聚糖多层膜。UV-vis光谱显示:组装过程呈现均匀而连续的生长。AFM和SEM观察表明:CS/MWCNT多层膜具有良好的光学特性,在生物传感器方面具有潜在的应用前景。     

Fracture toughness of exponential layer-by-layer polyurethane/poly(acrylic acid) nanocomposite films

This paper characterizes the fracture toughness of layer-by-layer (LBL) manufactured thin films with elastic polyurethane, a tough polymer, and poly(acrylic acid) as a stiffening agent. A single-edge-notch tension (SENT) specimen is used to study mode I crack propagation as a function of applied loading. Experimental results for the full-field time histories of the strain maps in the fracturing film have been analyzed to obtain R-curve parameters for the nanocomposite. In particular, by using the strain maps, details of the traction law are measured. A validated finite strain phenomenological visco-plastic constitutive model is used to characterize the nanocomposite film while a discrete cohesive zone model (DCZM) is implemented to model the fracture behavior. The LBL manufactured nanocomposite is found to display a higher fracture toughness than the unstiffened base polymer.     

Fabrication and characterization of Fe3O4 thin films deposited by reactive magnetron sputtering

Fe-O thin films with different atomic ratio of iron to oxygen were deposited on glass and thermally oxidized silicon substrates at temperatures of 300, 473 and 593 K, by reactive magnetron sputtering in Ar+O₂ atmosphere. The composition and structure of the thin films were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and electrical resistivity. It was found from XRD that with increasing the oxygen partial pressure in the working gas, the crystalline structure of the Fe-O films deposited at the substrate temperature of 473 K gradually changed from α-Fe, amorphous Fe-O, Fe₃O₄, γ-Fe₂O₃ to Fe_21.34O₃₂. The structure and chemical valence of the Fe₃O₄ films were analyzed by electron microscopy and XPS, respectively.     

Fabrication and characterization of Cu2ZnSnS4 thin films deposited by spray pyrolysis technique

We have investigated synthesis conditions and some properties of sprayed Cu₂ZnSnS₄ (CZTS) thin films in order to determine the best preparation conditions for the realization of CZTS based photovoltaic solar cells. The thin films are made by means of spraying of aqueous solutions containing copper chloride, zinc chloride, tin chloride and thiourea on heated glass substrates at various temperatures. In order to optimize the synthesis conditions of the CZTS films, two series of experiments are performed. In the first series the sprayed duration was fixed at 30 min and in the second it is fixed at 60 min. In each series, the substrate temperature was changed from 553°K to 633°K. The X-ray diffraction shows, on one hand, that the best crystallinity was obtained for 613°K as substrate temperature and 60 min as sprayed duration. On the other hand, these CZTS films exhibit the kesterite structure with preferential orientation along the [112] direction. Atomical Force Microscopy was used to determine the grain sizes and the roughness of these CZTS thin film. After the annealing treatment, we estimated the optical band-gap energy of the CZTS thin film exhibiting the best crystallinity as 1.5 eV which is quite close to the optimum value for a solar cell.     

纳米石墨负载功能化石墨烯纳米带/EVA复合材料薄膜的性能及表征

采用十二烷基硫酸钠改善纳米石墨(CNPs)在水溶液中的分散性,使其均匀负载至功能化石墨烯纳米带(EGNRs)上,制得功能化石墨烯纳米带-纳米石墨复合体(EGNRs_(75%)-CNPs),随后利用溶液涂覆成膜工艺在涂膜机上制得EGNRs_(75%)-CNPs/乙烯-醋酸乙烯共聚物(EVA)复合材料薄膜。采用FTIR、XRD、XPS、TEM、FESEM、氧气透过仪、高阻计对不同EGNRs_(75%)-CNPs含量的EGNRs_(75%)-CNPs/EVA复合材料薄膜进行了结构和性能表征。研究表明:EGNRs_(75%)-CNPs以3D网络形式存在,能够抑制纳米带团聚,说明其与EVA基体相容性好。当EGNRs_(75%)-CNPs质量分数为1%时,EGNRs_(75%)-CNPs/EVA复合材料薄膜的氧气透过率降低了67.6%,阻隔性能提高明显;当质量分数为0.8%时,CNPs负载到EGNRs构建3D导电网络,协同发挥增强作用,EGNRs_(75%)-CNPs/EVA复合材料薄膜导电性能提升了约8个数量级,表现出了优良的室温导电性能。     

Fabrication and characterization of silk fibroin/bioactive glass composite films

Composite films of silk fibroin (SF) with nano bioactive glass (NBG) were prepared by the solvent casting method, and the structures and properties of the composite films were characterized. Fourier transform infrared (FT-IR) spectroscopy analysis shows that the random coil and β-sheet structure co-exist in the SF films. Results of field emission scanning electron microscope (FESEM) indicate that the NBG particles are uniformly dispersed in the SF films. The measurements of the water contact angles suggest that the incorporation of NBG into SF can improve the hydrophilicity of the composites. The bioactivity of the composite films was evaluated by soaking in 1.5 times simulated body fluid (1.5 × SBF), and formation of a hydroxycarbonate apatite (HCA) layer was determined by XRD and FESEM. The results show that the SF/NBG composite film is bioactive as it induces the formation of HCA on the surface of the composite film after soaking in 1.5 × SBF for 7 days. In vitro osteoblasts attachment and proliferation tests show that the composite film is a good matrix for the growth of osteoblasts. Consequently, the incorporation of NBG into the SF film can enhance both the bioactivity and biocompatibility of the film, which suggests that the SF/NBG composite film may be a potential biomaterial for bone tissue engineering.     

纤维素/木质素微球抗紫外薄膜制备与性能研究

随着包装工业的快速发展和人类社会对环保要求的提高,功能性且可生物降解的包装膜材料越来越受到人们的重视.然而,目前市场上的可降解包装膜材料由于成本较高、力学性能差以及耐水性低而限制了其发展.采用自组装方法制备木质素微球,并将其沉积在纤维素膜表面,制备出一种新型纤维素基抗紫外薄膜材料.通过扫描电子显微镜(SEM)、红外光谱(FTIR)和激光共聚焦电子显微镜对薄膜的表面性能进行研究.利用抗张实验和紫外透光率测试对纤维素基功能薄膜的力学性能和抗紫外性能进行表征.结果表明:自沉积木质素微球在纤维素膜表面分布均匀,尺寸为1～2μm;纤维素薄膜疏水改性后有助于木质素微球的沉积,且沉积量随着木质素质量浓度的增加而增大.由于木质素微球的引入,纤维素复合膜的抗张强度比对照样增加22％,同时其对UVB屏蔽效果可达94％.     

Immobilization of liposomes in nanostructured layer-by-layer films containing dendrimers

Artificial vesicles or liposomes composed of lipid bilayers have been widely exploited as building blocks for artificial membranes, in attempts to mimic membrane interaction with drugs and proteins and to investigate drug delivery processes. In this study we report on the immobilization of liposomes of 1,2-dipalmitoyl-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (Sodium Salt) (DPPG) in layer-by-layer (LbL) films, alternated with poly(amidoamine) G4 (PAMAM) dendrimer layers. The average size of the liposomes in solution was 120 nm as determined by dynamic light scattering, with their spherical shape being inferred from scanning electron microscopy (SEM) in cast films. LbL films containing up to 20 PAMAM/DPPG bilayers were assembled onto glass and/or silicon wafer substrates. The growth of the multilayers was achieved by alternately immersing the substrates into the PAMAM and DPPG solutions for 5 and 10 min, respectively. The formation of PAMAM/DPPG liposome multilayers and its ability to interact with BSA were confirmed by Fourier transform infrared spectroscopy (FTIR). The structural features and film thickness were obtained using X-ray diffraction and surface plasmon resonance (SPR).     

Fabrication and properties of Fe/Fe oxide and Co/Co oxide films

Evaporation of Fe and Co at a residual O2pressure of 10^-5to 10^-4Torr yielded magnetic films of high coercivities up to 500 Oe and magnetizations of about 1000 EMU/cm³. While the Co films were continuously deposited in the O2atmosphere, a sandwich structure of Fe and Fe2O3was formed by intermittently altering the evaporation conditions. Both kinds of films were produced in the same geometrical arrangement. The Fe/Fe2O3films showed shape anisotropy caused by the oblique incidence deposition, while no uniaxial anisotropy was observed on the Co films. For both, Co films and Fe/Fe2O3sandwich films, it was possible to adjust the magnetic properties within a certain range. In both cases the coercivity increased considerably by annealing at 200°C.