聚丙烯酰胺修饰Fe_3O_4磁性纳米粒子的制备与表征

首先通过化学处理在Fe3O4磁性纳米粒子表面引入Si—H键,然后通过选择性的硅氢加成反应制备了一个端基带溴的磁性引发剂,并利用原子转移自由基聚合(ATRP)技术,在该磁性引发剂表面接枝了聚丙烯酰胺高分子,该聚丙烯酰胺高分子展现出分子量高度可控性和窄的分子量分布.经聚丙烯酰胺修饰后Fe3O4磁性纳米粒子的比饱和磁化强度为58.5 emu.g-1,与未修饰纳米Fe3O4相比下降约20%.     

原位聚合法制备具有温敏PNIPAM壳的核-壳结构聚合物纳米微球的研究

结合大分子自组装和原位自由基聚合方法,采用油溶性引发剂偶氮二异丁腈(AIBN),在聚(ε-已内酯)(PCL)纳米粒子表面引发聚合单体N-异丙基丙烯酰胺(NIPAM)和交联剂亚甲基双(丙烯酰胺)(MBA),制备得到了核-壳结构的PCL/PNIPAM聚合物纳米微球.系统研究了单体和交联剂用量、壳层目标交联度、初始PCL/DMF溶液的浓度及引发剂AIBN含量4个反应参数对核-壳结构PCL/PNIPAM纳米微球的PNIPAM壳层得率、微球尺寸、温敏性能及电镜形貌的影响.结果表明,在制备核-壳结构PCL/PNIPAM纳米微球的反应过程中,PCL粒子表面的聚合和水中的聚合二者之间相互竞争.适当增加引发剂AIBN的添加量,有利于制备得到核/壳比例可控的PCL/PNIPAM纳米微球;交联剂MBA较高的反应活性导致形成了非均匀交联的PNIPAM壳层.     

聚(苯乙烯-马来酸酐)/Fe3O4纳米杂化材料的制备与表征

采用2,2,6,6-四甲基-1-哌啶氧化物(TEMPO)的溴盐对化学共沉淀法制备的Fe3O4纳米粒子进行表面修饰,以该粒子为过氧引发剂,苯乙烯(St)、马来酸酐(MA)为单体,采用"活性"/可控自由基聚合技术在粒子表面原位引发聚合,制备了聚(苯乙烯-马来酸酐)/Fe3O4纳米杂化材料,并对纳米Fe3O4及杂化材料进行了FT-IR、XRD、TGA、TEM和GPC表征。结果表明,所制备的纳米杂化材料的平均粒径约为70 nm,磁性粒子表面的聚合物分子链随着聚合时间的增长而增长。振动样品磁强计测试结果显示,在室温、外加磁场下,该纳米杂化材料呈现超顺磁性,饱和磁化强度随着包覆聚合物量的增加而降低。     

聚丙烯酰胺/蒙脱土纳米复合物-聚乙烯醇共混膜的制备及其渗透汽化性能

用原位聚合法制备聚丙烯酰胺/蒙脱土(PAM/MMT)纳米复合材料, 通过透射电镜研究了蒙脱土在聚丙烯酰胺基体中的形貌和分布. 结果表明, 蒙脱土以片层结构分布在聚合物基体中. 用超声波分散聚乙烯醇和聚丙烯酰胺-蒙脱土共混铸膜液制得共混膜, 用红外吸收光谱和扫描电镜研究了两者的相互作用和形貌. 考察了共混膜在异丙醇-水混合溶液中的溶胀吸附性能及共混比和蒙脱土含量对膜分离性能的影响, 结果显示, 聚乙烯醇膜中添加适量的蒙脱土纳米粒子可以大大改善膜的分离选择性.     

聚谷氨酸基双重响应性纳米胶束的制备及药物控释性能

首先制备端氨基聚(N-异丙基丙烯酰胺-co-聚乙二醇)大分子引发剂,再通过端氨基引发L-谷氨酸-γ-苄酯-N-羧酸酐开环聚合,制备了聚(N-异丙基丙烯酰胺-co-聚乙二醇)与聚(L-谷氨酸-γ-苄酯)的嵌段共聚物,将其中的γ-苄酯基团转化为酰肼基团后与阿霉素(DOX)共价结合,最后在水溶液中自组装成纳米胶束,制备了温度和pH值双重响应性纳米胶束。胶束外层由亲水性聚(N-异丙基丙烯酰胺-co-聚乙二醇)组成,具有温敏性,低临界溶液温度为38℃;胶束内层由聚(L-谷氨酸-γ-酰肼-阿霉素)组成。该胶束对于药物的释放具有温度和pH双重敏感性。     

反向胶束法制备聚3,4-乙烯二氧噻吩纳米粒子的光电性能和热稳定性

采用聚合和掺杂同时进行的反向胶束体系制备了粒径分散较小的聚3,4-乙烯二氧噻吩(PEDOT)纳米粒子, 利用紫外-可见光光谱(UV-Vis)、X射线衍射(XRD)和扫描电子显微镜(SEM)等分析方法对纳米粒子进行了表征. 实验结果发现, 氧化剂用量、超声处理、聚合温度及掺杂程度对PEDOT纳米粒子的形貌、电性能及热稳定性有不同程度的影响. 根据实验结果对反向胶束法制备PEDOT纳米粒子过程进行优化发现, 在PEDOT纳米粒子聚合过程中, 甲基苯磺酸有效掺杂浓度约为0.17 mol/L时, PEDOT链的取向最规则, 在6.7°, 12.7°, 25°出现衍射峰, 掺杂剂的有效掺杂使得纳米粒子中分子链的取向不同, 并可以获得较高的电导率(>100 S/cm)的PEDOT纳米粒子, 当粒子的尺寸小于20 nm后电导率降低; 热失重法(TG)分析结果表明, PEDOT纳米粒子的热稳定性比普通块材好, 掺杂剂浓度对纳米粒子的热稳定性有一定影响.     

三元无规接枝共聚物的合成及其自组装性能的研究

通过甲基丙烯酸羟乙酯(HEMA)引发ε-己内酯(ε-CL)开环聚合得到带有双键的大分子预聚体甲基丙烯酸羟乙酯-聚己内酯(HEMA-PCL), 该预聚体与N-异丙基丙烯酰胺(NIPAAm)及丙烯酸(AAc)自由基聚合得到一系列含有不同比例组分的三元无规接枝共聚物. 研究了该聚合物的自组装性能. 通过1H NMR, FTIR, 凝胶渗透色谱(GPC)对聚合物进行结构和分子量的表征. 通过TEM, DLS与表面张力等方法表征其纳米粒子情况.     

P(St-NIPAm)核-壳纳米粒子的制备及其光子晶体薄膜

以过硫酸铵为引发剂,固定反应单体物质的量之比,采用一步无皂乳液聚合法,制备粒径不同的聚(苯乙烯-N-异丙基丙烯酰胺)纳米粒子,研究了反应单体用量对纳米粒子粒径的影响;然后利用简单的垂直沉积法,在载玻片上自组装光子晶体薄膜。结果表明:制备的纳米粒子具有较高的单分散性并呈明显的核-壳结构,其粒径与反应单体用量呈线性关系;薄膜中纳米粒子呈面心立方紧密堆积,薄膜厚度约8μm;薄膜光子禁带的实验测量值与理论计算值基本一致,且禁带与纳米粒子粒径呈线性关系;当反应单体的总物质的量分别为20,25,30,35mmol时,自组装成的光子晶体薄膜的颜色分别呈蓝紫、蓝绿、黄绿和橘红色。     

两亲性三嵌段共聚物PHB-PEG-PHB的合成及其纳米粒子的制备与表征

基于聚(β-丁内酯)(PHB)和聚乙二醇(PEG)的两亲性三嵌段共聚物聚(β-丁内酯)-聚乙二醇-聚(β-丁内酯)(PHB-PEG-PHB)可在聚乙二醇钾盐大分子引发剂的作用下、以四氢呋喃为溶剂,通过β-丁内酯(BL)的阴离子开环聚合进行制备,调节BL与聚乙二醇钾盐的配比,可制备分子量不同的共聚物.产物可通过1H-NMR、13C-NMR、FTIR、DSC、GPC等测试进行表征,DSC结果表明无定形的PHB阻碍了PEG的结晶,且随着PHB链段长度的增加,阻碍作用更加明显.PHB-PEG-PHB可在水中通过沉淀/溶剂蒸发技术进行自组装形成具有核壳结构的纳米粒子,并通过SEM、DLS手段对其表征,发现粒子尺寸在纳米级,形态为球形或方形.聚合物的初始浓度对纳米粒子的形态和尺寸有明显影响,随着聚合物初始浓度的降低,纳米粒子的尺寸降低.     

基于不对称星形聚合物制备Janus杂化金纳米粒子

利用原子转移自由基聚合(ATRP)和叠氮-炔基点击化学反应,对β-环糊精(β-CD)进行不对称改性,在其宽截面一侧聚合得到14条亲水性聚(N-异丙基丙烯酰胺)(PNIPAM)链,在其窄截面一侧偶联7个硫辛酸(LA)基元,得到不对称星形聚合物(LA)7-CD-(PNIPAM46)14,采用配体交换法以此聚合物对金纳米粒子进行表面修饰,得到表面具有不对称化学组成和亲疏水性的Janus杂化金纳米粒子(Au3.1-CD-(PNIPAM46)14),该两亲性Janus杂化金纳米粒子可以在选择性溶剂水中组装形成类似于胶束结构的球状组装体。     

Controlled placement of polystyrene-grafted CdSe nanoparticles in self-assembled block copolymers

Surface functionalization of semiconductor CdSe nanoparticles has been achieved with polystyrene (PS) brushes by “grafting from” technique for further addition to a polystyrene-b-polybutadiene-b-polystyrene (SBS) block copolymer in order to obtain self-assembled composites. For modification of nanoparticle surface 3-glycidoxypropyltrimethoxysilane (GPS) was used at first for the later attachment of the 4,4′-azobis(4-cyanopentanoic acid) azo initiator. Fourier-transform infrared spectroscopy confirmed the presence of GPS and PS on the surface of nanoparticles. Atomic force microscopy was used for morphological characterization of SBS/CdSe nanocomposites. Modification of nanoparticles with PS brushes by radical polymerization improved their affinity with PS block and the dispersion of nanoparticles avoiding agglomeration. CdSe nanoparticle size was measured to be around 2 nm by the use of X-ray diffraction and UV–Vis techniques. Optical properties were characterized using fluorescence measurements.     

Origin of dc and ac electric transport phenomena in carbon/manganese oxide nanocomposite

Hybrid organic/inorganic nanocomposites based on manganese oxide nanoparticles enriched pyrogallol-formaldehyde matrix (PF/MnO) were synthesized by sol-gel technique. After a drying step, the samples were heated during 2 h at different pyrolysis temperatures between 600 and 1000 °C in tubular furnace under open nitrogen atmosphere. The obtained nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and electrical technics in the measurement temperature range between 80 and 300 K. The XRD spectra show that PF/MnO nanocomposites are crystallized with the appearance of different phases: the graphite (C), the manganese oxide (MnO), the metallic manganese (Mn) and the manganese dioxide (MnO₂) with proportions depending on pyrolysis temperature. The measurement temperature dependence conductivity can be explained by Godet-Variable Range Hopping (3D-GVRH) conduction model in all samples with the presence of an exponential distribution of localized states. The voltage-current V(I) characteristics show the presence of negative differential resistance (NDR) in some samples. The ac conductance exhibits the dominance of hopping conduction mechanism and the Small Polaron Hopping (SPH) model. The Nyquist plots for the PF/MnO-650 °C nanocomposite obey at Cole-Cole model. The impedance spectra were fitted by an equivalent circuit involving two contributions attributed to grains and grain boundaries.     

Alignment of nanoparticles in polymer matrices

This paper briefly summarizes the state of the art in the field of designing composites containing semiconductor nanoparticles distributed in a polymer matrix. Special attention is focused on (i) nanocomposites based on block copolymers and (ii) LC polymer matrices capable of controlling the localization and alignment of nanoparticles.     

Microwave-assisted solution synthesis and photocatalytic activity of Ag nanoparticles supported on ZnO nanostructure flowers

Ag nanoparticles supported on the surface of three-dimensional (3D) flower-like ZnO nanostructure were synthesized by a microwave-assisted solution method. The obtained products were characterized by X-ray diffraction analysis, field-emission scanning electron microscopy, Fourier-transform infrared spectroscopy, Raman spectrophotometry, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy. The analytical results confirmed homogeneously distributed Ag nanoparticles supported on the surface of flower-like ZnO nanostructure. The photocatalytic effect of the heterostructure Ag/ZnO nanocomposites was investigated using photodegradation under ultraviolet (UV) light of methylene blue as model dye. The heterostructure Ag/ZnO nanocomposites exhibited much higher photocatalytic activity than pure ZnO flowers. The improved photocatalytic properties are attributed to formation of a Schottky barrier at the metal–semiconductor interface of the Ag/ZnO nanocomposites.     

Conducting polyaniline-rutile TiO2 nanocomposites for the development of high-k dielectric materials

Inorganic dielectrics encapsulated in an organic matrix are showing excellent promise as novel dielectric materials. In this work, firstly highly organized crystalline nanoparticles of rutile TiO₂ were synthesized by acid hydrolysis of titanium isopropoxide at room temperature. Then we developed a novel dielectric material consisting of highly organized rutile TiO₂/polyaniline (PAni) nanocomposites by in-situ chemical oxidative polymerization. The structural, morphological, conducting, and dielectric properties of the rutile TiO₂/PAni nanoparticles have been evaluated by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution-transmission emission microscopy (HR-TEM), four-point probe technique, CV (Capacitance versus Voltage), and Impedance analyzer. The nanocomposites show 70 times higher permittivity compared to rutile nanoparticles and much higher compared to anatase/PAni (ES) nanocomposites at 10 MHz. Large interfacial polarizations, nanostructure, and dopant levels are the key factors for the large dielectric constant of the nanocomposites. The rutile/PAni (ES) nanocomposites might see potential uses in super-capacitors, gate dielectric in transistors, and capacitive-type gas sensors.     

TiO2浓度对核-壳结构Ag/TiO2纳米复合粒子结构以及三阶非线性光学性质的影响

采用光还原方法制备了核-壳结构的Ag/TiO2纳米复合粒子, 通过TEM、UV-Vis光谱和XRD表征了不同TiO2浓度下Ag/TiO2纳米复合粒子的结构和光学性质. UV-Vis光谱证明了银颗粒的存在, 且复合粒子中的银粒径随着TiO2含量的增加而增加, 同时随着TiO2浓度的增加, 银的吸收峰出现明显的增强和展宽；从TEM照片 发现, Ag/TiO2纳米复合粒子是一种以Ag为核, 外面包覆一层TiO2的核-壳结构, TiO2浓度和Ag+浓度的增加, 使得复合粒子的银颗粒粒径增大. 用Z-扫描技术, 以锁模Ti:sapphire飞秒激光器发出的脉宽为130 fs激光做光源, 在790 nm波长的光作用下, 研究了0.5%(w)Ag+含量, 不同TiO2浓度的Ag/TiO2纳米复合粒子的非线性光学特性. 结果发现, 在790 nm激光作用下, 0.25%(w)TiO2样品膜有双光子吸收和自聚焦非线性折射现象; 而当TiO2浓度为0.70%(w)时, 样品膜的非线性吸收由反饱和吸收转变为饱和吸收.     

Effects of inorganic nanofillers on the thermal degradation and UV-absorbance properties of polyvinyl acetate

The effects of calcium carbonate (CaCO₃) and calcium sulfate (CaSO₄) nanoparticles on the thermal and UV-absorbing properties of polyvinyl acetate (PVAc) were analyzed in this study. Nanoparticles of CaCO₃ and CaSO₄ were synthesized by in situ deposition technique. The size and shape of nanoparticles were recognized by X-ray diffraction and scanning electron microscope (SEM) analyses which confirmed that the particle was having a diameter of 25–33 nm. In this technique, the surface modification of nanoparticles was done by non-ionic polymeric surfactant. PVAc/CaCO₃ and PVAc/CaSO₄ nanocomposites film samples with an average thickness of 30 µm and in the mass ratio of nanoparticles (0–4% (w/w)) were prepared by solution mixing technique. Chemical, structural, and elemental characterizations of nanocomposites were done by, fourier transform infrared, SEM, and energy dispersive X-ray spectroscopy analyses, respectively. Thermal properties of pure polymer and nanocomposites were characterized through differential scanning calorimetric, thermogravimetric, and differential thermogravimetry techniques. The glass transition temperature of nanocomposites increases with increase in content of nanoparticles. It may be due to the interaction between inorganic and organic components. The thermogravimetric analysis results indicate that the thermal degradation temperatures of nanocomposites were enhanced upon the addition of nanosized inorganic fillers. The thermal results show that PVAc/CaSO₄ nanocomposites were more thermally stable than PVAc/CaCO₃ nanocomposites. The addition of nanoparticles affects degradation mechanism and consequently improves thermal stability of PVAc. The reduction of polymer chain mobility and the tendency of nanoparticles to eliminate free radicals were the principal effects responsible for these enhancements. The ultraviolet–visible (UV–Vis) absorbance spectra of PVAc and its nanocomposites films show that the intensity of absorbance increases with increasing filling content, suggesting that nanocomposites films have greater UV-shielding property.     

Transparent poly(bisphenol A carbonate)-based nanocomposites with high refractive index nanoparticles

Transparent organic-inorganic nanocomposites were successfully synthesized from sulfonic acid-modified poly(bisphenol A carbonate) (SPC) and TiO₂ or ZrO₂ nanoparticles. The dispersibility of nanoparticles was significantly improved by both the surface treatment of nanoparticles with phosphoric acid 2-ethylhexyl esters (PAEH) and the introduction of a sulfonic acid moiety into the PC chain. It was found that in some cases, crystallization of the matrix caused a reduction in transparency. Efficient dispersion of nanoparticles and the absence of crystallization resulted in highly transparent nanocomposites with up to 42 wt% TiO₂ and 50 wt% ZrO₂ nanoparticles. The refractive indices of the nanocomposites based on SPC increased with the increasing amount of nanoparticles. Theoretical equation based on Maxwell-Garnett effective medium theory provided reasonably close estimation of the refractive indices to the experimentally observed values. The prepared nanocomposites had lower thermal stability than the host matrix polymers.     

An Unconventional Route to Monodisperse and Intimately Contacted Semiconducting Organic–Inorganic Nanocomposites

We developed an unconventional route to produce uniform and intimately contacted semiconducting organic–inorganic nanocomposites for potential applications in thermoelectrics. By utilizing amphiphilic star‐like PAA‐b‐PEDOT diblock copolymer as template, monodisperse PEDOT‐functionalized lead telluride (PbTe) nanoparticles were crafted via the strong coordination interaction between PAA blocks of star‐like PAA‐b‐PEDOT and the metal moieties of precursors (i.e., forming PEDOT–PbTe nanocomposites). As the inner PAA blocks are covalently connected to the outer PEDOT blocks, the PEDOT chains are intimately and permanently tethered on the PbTe nanoparticle surface, thereby affording a well‐defined PEDOT/PbTe interface, which prevents the PbTe nanoparticles from aggregation, and more importantly promotes the long‐term stability of PEDOT–PbTe nanocomposites. We envision that the template strategy is general and robust, and offers easy access to other conjugated polymer–inorganic semiconductor nanocomposites for use in a variety of applications.     

Al2O3/SnO2 Co-Nanoparticle Modified Grafted Collagen for Improving Thermal Stability and Infrared Emissivity

Al2O3/SnO2 co-nanoparticles were prepared with a modified sol-gel technique followed by a thermal treatment process. With these co-nanoparticles the grafted collagen-Al2O3/SnO2 nanocomposites were obtained using a supersonic dispersion method. X-ray diffraction, FT-IR analysis, transmission electron microscopy, TGA/DTA and infrared emissivity test were performed to characterize the resulting nanoparticles and nanocomposites, respectively. The Al2O3/SnO2 co-nanoparticles showed a narrow distribution of size between 20-40 nm and could be uniformly absorbed on the tri-helix scaffolds of the grafted collagen without any aggregation. The nanocomposites possessed better thermal stability and substantially lower infrared emissivity than the grafted collagen and Al2O3/SnO2 co-nanoparticles with an increase of degradation temperature from 39 to 210 ℃ and a decrease of infrared emissivity from 0.850 of the grafted collagen and 0.708 of the Al2O3/SnO2 co-nanoparticles to 0.424, which provided a potential application of the nanocomposites to areas such as photoelectronics.