以葡聚糖-乙二胺聚合物为载体制备纳米银

以葡聚糖-乙二胺聚合物为载体制备纳米银.首先合成葡聚糖-乙二胺聚合物,并用紫外光谱红外光谱对聚合物进行表征;该聚合物与硝酸银反应生成葡聚糖-乙二胺聚合物-银配合物,再通过化学还原或光化学还原法使配合物中的银离子转变成单质银纳米粒,以透射电子显微镜激光纳米测定仪对制备的纳米银进行测定.结果表明制备出了粒径为23.1nm的纳米单质银.以葡聚糖-乙二胺聚合物为载体制备纳米银的方法是可行的.     

聚合物存在下纳米银复合材料的制备与表征

以聚丙烯腈聚乙二醇嵌段共聚物PAN-b-PEG-b-PAN为稳定剂, 在超声辐照下成功地制备了分散性较好、尺寸均匀的纳米银颗粒. 用X射线衍射(XRD)、红外光谱(FTIR)、透射电镜(TEM)、紫外-可见吸收光谱(UV-Vis)和热分析(TGA)等对制备的纳米银复合材料进行了表征. 红外结果表明超声辐照并没有破坏聚合物的链结构. 聚合物的引入, 对纳米银颗粒起到了很好的分散保护作用. 用低浓度的硝酸银溶液, 得到粒径较小的纳米银颗粒; 随着硝酸银浓度增大, 纳米银颗粒粒径也增大. 而聚合物的浓度增大时, 所得银纳米颗粒粒径减小. 对银纳米颗粒的形成机理进行了讨论.     

银/碳纳米管纳米复合物制备及性质研究

基于苯环与碳纳米管之间较强的π-π共轭效应和醛基对银氨溶液的还原作用,利用吸附在碳纳米管上的香草醛分子原位还原[Ag(NH3)2]+,成功获得了纳米银/碳纳米管(Ag-NPs/CNTs)复合纳米材料。紫外-可见吸收光谱和荧光光谱结果表明,碳纳米管对香草醛分子有较强的吸附作用及银纳米粒子的形成。透射电镜结果表明,碳纳米管表面形成了大小约5.0 nm银纳米颗粒。所制备的纳米复合材料表现出较明显的荧光特性,且对浓度为1.0×10-7～6.0×10-7 mol/L的H2O2表现出较好的电催化还原能力。     

超支化聚胺-酯改性聚硅氧烷及纳米银导电胶的制备与性能

利用端羟基超支化聚胺-酯(HBP3-OH)与马来酸酐的酯化反应,合成了含双键的超支化聚胺-酯(HBP3-MA),并用红外光谱和核磁共振光谱对HBP3-MA进行了表征.将HBP3-MA作为改性剂,液体硅橡胶为基体,镀银铜粉为导电填料,制备了改性硅橡胶导电复合材料.HBP3-MA参与到液体硅橡胶的固化,采用示差扫描量热仪(DSC)对复合体系的固化条件进行了研究.采用原位还原法在复合体系中生成纳米银,利用透射电子显微镜(TEM)、扫描电子显微镜(SEM)对银纳米粒子的形貌和复合体系的结构进行了表征,探讨了纳米粒子增强复合物体系导电性的机理,即银纳米粒子具有低温烧结的特性,固化时可在镀银铜粉表面烧结,降低了镀银铜粉之间的接触电阻.最后,对导电复合材料的导电性能和粘结性能进行了研究.研究发现,当醋酸银用量为4.4份时,导电复合材料的体积电阻率和剪切强度均达到最佳值,分别为3.6×10-3Ω·cm和0.32 MPa.     

镱的配合物及其复合材料的合成及性能研究

采用回流冷凝法合成了近红外发光的YbAA(TTA)2phen配合物,对配合物进行的荧光光谱分析结果表明:配合物中Yb3+的2F5/2→2F7/2电子跃迁被分成了3个峰。采用原位反应方法制备了键合型的YbAA(TTA)2phen/EVA复合材料,对复合材料进行的SEM,XRD分析结果表明:交联固化后配合物在复合材料中分散性增强,颗粒变小。对YbAA(TTA)2phen/EVA复合材料进行的荧光光谱分析结果表明:复合材料表现为Yb3+的特征发射,且相同配合物含量下交联固化后的复合材料的发光强度要强得多。对YbAA(TTA)2phen/EVA复合材料进行了拉伸性能和原子力显微镜表征,结果表明:交联固化后复合材料的拉伸强度和平整度得到了提高。     

超声引发无皂乳液聚合制备纳米银/PAAEM复合材料及其表征

在不使用气体保护及乳化剂的条件下,超声辐射引发无皂乳液聚合双原位合成纳米银/聚乙酰乙酸基甲基丙烯酸乙酯(PAAEM)复合材料。并通过XRD、FTIR、TEM、HRTEM、XPS和TG等分析方法对其进行表征。结果表明:纳米银粒子具有面心立方结构和球形或近球形形貌,且较均匀地分散在聚合物基体中;纳米银粒子与基体之间的相互作用是纳米银与基体中乙酰乙酸基的羰基氧原子配位所产生的;而且纳米银粒子对基体PAAEM的热学性能有很大影响。     

壳聚糖改性织物中原位合成银纳米粒子

采用壳聚糖改性棉和涤纶织物,通过织物表面的壳聚糖原位吸附、还原银离子制备了纳米银抗菌织物.用场发射扫描电子显微镜(SEM)、X射线能谱(EDA)、X射线粉末衍射仪(XRD)和反射光谱等对纳米银织物进行了表征,研究了银离子浓度和壳聚糖浓度对纳米银织物的影响,并检测了纳米银织物的抗菌性能.结果表明,在无需任何还原剂的条件下,壳聚糖改性的棉和涤纶织物表面可以均匀地形成银纳米粒子,晶粒大小为5~10 nm,所制备的纳米银织物均具有优异的抗菌性能.     

在线性壳聚糖膜内原位还原制备银纳米粒子及银单晶体

采用光还原方法，在线性壳聚糖膜内原位还原获得球形银粒子(粒径10～30 nm)和外观呈三角形、六边形的银单晶体(边长200～2000 nm)；采用电化学方法，在壳聚糖膜内制备了球形银纳米粒子，粒径为5～8 nm.用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、红外光谱(IR)和X射线衍射(XRD)等测试技术对壳聚糖/银复合物进行了表征，对光还原过程中银晶体结构由多晶到单晶的转变原因进行了初步的分析和探讨.     

新型氮杂环卡宾银(Ⅰ)配合物的合成及其晶体结构

以取代苄氯(1a~1c)为起始原料,与咪唑经氮烷基化反应制得苄基咪唑氯盐(2a~2c);2a~2c与氧化银经原位去质子化反应合成了3种新型的氮杂环卡宾银配合物——(NHC)AgCl[NHC:1,3-二(4-甲氧基苄基)咪唑-2-亚基(3a),1,3-二(3-甲氧基苄基)咪唑-2-亚基(3b)]和[(NHC)AgCl]_2[NHC=1,3-二(4-氯苄基)咪唑-2-亚基(3c)],其结构经~1H NMR,~(13)C NMR,IR,元素分析和X-射线单晶衍射表征。3a~3c单晶结构均属单斜晶系,3a为P21/n空间群,3b和3c为P21/c空间群,3a和3b为单核银配合物,3c为双核银配合物。     

单颗粒-电感耦合等离子体质谱法表征纳米抗菌商品中纳米银颗粒粒径分布

建立了单颗粒-电感耦合等离子体质谱法(Single particle ICP-MS,SP-ICP-MS)测定纳米抗菌商品中纳米银颗粒(Silver nanoparticles,AgNPs)粒度分布的方法。首先采用微波消解-ICP-MS法测定了纳米抗菌商品中的总银含量,确定样品稀释倍数。然后在SP-ICP-MS模式下,测定3种AgNPs标准样品(30、50和80nm)的粒径,所得结果与供应商提供的TEM值接近,说明SP-ICP-MS法能够准确表征水溶液中AgNPs的粒径分布,同时采用SP-ICP-MS测定了纳米抗菌商品中纳米银颗粒粒径分布。方法简单快速、灵敏度高,能够为纳米抗菌材料中AgNPs表征提供准确的表征方法。     

Mechanical properties of epoxy composites based on silver nanoparticles formed in situ

The mechanical and thermomechanical properties of metal-containing epoxy composite films based on silver nanoparticles synthesized in situ are investigated. There is a nonmonotonic dependence of the mechanical properties on the concentration of silver myristate used as a precursor. It is found for the first time that the breaking strength and elastic modulus increase by a factor of 1.8–1.5 relative to those of the unmodified matrix at a small concentration of precursor nanoparticles (on the order of 0.1 wt %). DSC and thermomechanical studies reveal that the glass-transition temperature decreases slightly (by 5–6°C) as the precursor concentration is increased to 0.5 wt %, thereby suggesting a weak plasticization of the modified epoxy matrix. On the basis of the spectrophotometry data measured in the region of surface plasmon resonance of silver nanoparticles (420–425 nm) and SEM data, it is inferred that the in situ strengthening of an epoxy nanocomposite based on epoxy resin ED-20, triethylamine, and silver myristate is attained because silver nanoparticles smaller than 20 nm in size and having a narrow particle-size distribution are formed during curing.     

Study on improving the toughness of rapidly curing epoxy resin composite materials with a biobased microcrystalline cellulose

Rapid solidification molding is one of the main low-cost forming methods for composite materials, and the reasonable selection of the solidification molding process is the key to achieving material performance. The curing system used in this paper is the widely used, inexpensive, and readily available epoxy resin (WSR618) and the transparent, colorless, and less toxic 593 curing agent, which cures at room temperature. Through the study of various temperature formulations, a rapid curing system was determined that has a 10-min cure at 80°C. The results showed that when the mass ratio of epoxy (EP) resin to curing agent was 5:1, the curing system was selected at 80°C for 10 min, and the bending strength could reach 100.19 MPa, and the impact strength could reach 12.82 kJ/m². However, the difficulty caused by quick solidification was a reduction in mechanical characteristics, which required modification. Microcrystalline cellulose is cheap and readily available and widely available, so microcrystalline cellulose (MCC) was chosen for modification in this study. The experimental results showed that the addition of MCC reduced the fracture brittleness of EP composite materials. When 0.75% MCC was added, the bending and tensile strengths reached 116.88 and 52.53 MPa, respectively, which were 16.66% and 18.74% higher than unmodified EP. The elongation at break reached 11.57%, which is 14.13% higher than unmodified.     

Synthesis of raspberry-like monodisperse magnetic hollow hybrid nanospheres by coating polystyrene template with Fe(3)O(4)@SiO(2) particles

A new inorganic/organic hybrid material containing silsesquioxane was prepared by the reaction of caged octa (aminopropyl silsesquioxane) (POSS-NH(2)) with n-butyl glycidyl ether (nBGE) and 1,4-butanediol diglycidyl ether (BDGE). The copolymers of POSS, nBGE, and BDGE could be obtained with varied feed ratio of POSS-NH(2), nBGE, and BDGE in the preparation. The hybrid material was added into an epoxy resin (E51) for enhancing the toughening and thermal properties of the epoxy resin. The results showed that the toughening and the thermal properties of the cured epoxy resin were greatly improved by the addition of the hybrid. The enhancement was ascribed to nano-scale effect of the POSS structure and the formation of anchor structure in the cured network. The investigation of kinetics for the curing process of the hybrid-modified epoxy resin revealed that two kinds of curing reactions occurred in different temperature ranges. They were attributed to the reactions between amino groups of the curing agent with epoxy groups of E51 and with residue epoxy groups in the hybrid. The reacting activation energies were calculated based on Kissinger's and Flynn-Wall-Ozawa's methods, respectively.     

Anisotropy in optical transmittance and molecular chain orientation of silver- dispersed uniaxially drawn polyimide films

The anisotropy in optical transmittance in the visible and near-infrared region observed for uniaxially drawn and silver-dispersed polyimide (PI) films was investigated. The films were prepared in a one-step operation that consists of thermal curing and simultaneous uniaxial drawing of poly(amic acid) (PAA) films dissolving 5.7 ∼ 20 mol% of silver nitrate. The PAA was converted to PI by heating, and the PI chains were orientated along the drawing direction during curing. Silver nanoparticles were precipitated in the films when they were cured in air and under nitrogen. In particular, silver nanoparticles aggregated along drawing direction and spheroidal nanoparticles (size of longer axis: 10–25 nm, aspect ratio: ca. 1.5) were observed in the films cured in air, and distinct anisotropy in optical transmittance was observed. The maximum optical anisotropy was obtained with a specific holding time at the final curing temperature (320 °C). In addition, the anisotropy can be controlled by polymer chain orientation when films are cured with the optimal holding time. In optimized preparing conditions, anisotropies in transmittance larger than 500 : 1 were obtained at the wavelengths between 700 and 900 nm, and its optical properties were retained after annealing at 150 °C for 1 hr. The PI films thus obtained can be used as thermally stable thin-film polarizers. Copyright © 2003 John Wiley & Sons, Ltd.     

Kinetics studies on the accelerated curing of liquid crystalline epoxy resin/multiwalled carbon nanotube nanocomposites

A new class of nanocomposite has been fabricated from liquid crystalline (LC) epoxy resin of 4,4′‐bis(2,3‐epoxypropoxy) biphenyl (BP), 4,4′‐diamino‐diphenyl sulfone (DDS), and multiwalled carbon nanotubes (CNTs). The surface of the CNTs was functionalized by LC epoxy resin (ef‐CNT). The ef‐CNT can be blended well with the BP that is further cured with an equivalent of DDS to form nanocomposite. We have studied the curing kinetics of this nanocomposite using isothermal and nonisothermal differential scanning calorimetry (DSC). The dependence of the conversion on time can fit into the autocatalytic model before the vitrification, and then it becomes diffusion control process. The reaction rate increases and the activation energy decreases with increasing concentration of the ef‐CNT. At 10 wt % of ef‐CNT, the activation energy of nanocomposite curing is lowered by about 20% when compared with the neat BP/DDS resin. If the ef‐CNT was replaced by thermal‐insulating TiO₂ nanorods on the same weight basis, the decrease of activation energy was not observed. The result indicates the accelerating effect on the nanocomposite was raised from the high‐thermal conductivity of CNT and aligned LC epoxy resin. However, at ef‐CNT concentration higher than 2 wt %, the accelerating effect of ef‐CNTs also antedates the vitrification and turns the reaction to diffusion control driven. As the molecular motions are limited, the degree of cure is lowered. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

插层聚合制备粘土/环氧树脂纳米复合材料过程中粘土剥离行为的研究

用ＸＲＤ、ＤＳＣ 等手段研究了有机蒙脱土在环氧树脂中的插层与剥离行为,证明环氧树脂容易插层到粘土片层间,形成稳定的插层混合物,加入胺固化剂固化后,粘土被剥离而得到剥离型纳米复合材料,剥离程度与所采用的固化温度关系不大,主要取决于固化程度,全部剥离的时间与环氧树脂凝胶的时间接近．     

Kinetics of curing and thermal degradation of hyperbranched epoxy (HTDE)/diglycidyl ether of bisphenol-A epoxy hybrid resin

Hyperbranched epoxy resin (HTDE) has relatively low viscosity and high molecular mass and holds great promise as a functional additive for enhancing the strength and toughness of thermosetting resins. In this work, the curing and thermal degradation kinetics of HTDE/diglycidyl ether of bisphenol-A epoxy (DGEBA) hybrid resin were studied in detail using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG) techniques by Coats–Redfern model. The effect of molecular mass or generation and content of HTME on the activation energy, reaction order, and curing time were discussed; the results indicated that HTDE could accelerate the curing speed and reduce the activation energy and reaction order of the curing reaction.     

Improving Thermal and Flame Retardant Properties of Epoxy Resin with Organic NiFe‐Layered Double Hydroxide‐Carbon Nanotubes Hybrids

To improve the dispersion of carbon nanotubes (CNTs) and flame retardancy of layered double hydroxide (LDH) in epoxy resin (EP), organic nickel‐iron layered double hydroxide (ONiFe‐LDH‐CNTs) hybrids were assembled through co‐precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe‐LDH‐CNTs nanocomposites containing 4 wt% of ONiFe‐LDH‐CNTs with different ratios of ONiFe‐LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy (TEM). The results revealed a coexistence of exfoliated and intercalated ONiFe‐LDH‐ CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe‐LDH‐CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe‐LDH and synergistic effect between ONiFe‐LDH and CNTs.     

The curing kinetics and mechanical properties of epoxy resin composites reinforced by PEEK microparticles

In this paper, a polyether-ether-ketone (PEEK)/epoxy composite was prepared by using PEEK microparticles as the reinforcement. The nonisothermal differential scanning calorimetry (DSC) test was used to evaluate the curing reaction of PEEK/epoxy resin system. The curing kinetics of this system were examined utilizing nonisothermal kinetic analyses (Kissinger and Ozawa), isoconversional methods (Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose) and an autocatalytic reaction model. During these analyses, the kinetic parameters and models were obtained, the curing behavior of PEEK/epoxy resin system under dynamic conditions was predicted. The results show that isoconversional methods can adequately interpret the curing behavior of PEEK/epoxy resin system and that the theoretical DSC curves calculated by the autocatalytic reaction model are in good agreement with experimental data. Furthermore, the tensile elongation at break, tensile strength, flexural strength, compression strength and compression modulus increased by 81.6%, 33.66%, 36.53%, 10.98% and 15.14%, respectively, when PEEK microparticles were added in epoxy resin composites.     

Epoxy/amine‐functionalized short‐length vapor‐grown carbon nanofiber composites

Short length vapor‐grown carbon nanofibers (VGCNFs) were functionalized with 4‐aminobenzoic acid in polyphosphoric acid/phosphorous phentoxide medium via “direct” Friedel‐Crafts acylation reaction to afford aminobenzoyl‐functionalized VGCNFs (AF‐VGCNFs). The AF‐VGCNFs as a cocuring agent were mixed with epoxy resin by simple mechanical stirring in methanol which was added to help efficient mixing. After evaporation of methanol, 4,4′‐methylenedianiline as a curing agent was added to the mixture, which was then cured at elevated temperatures. The resultant composites displayed uniform dispersion of AF‐VGCNFs into cured epoxy matrix. During curing process, the amine functionalities on AF‐VGCNF together with 4,4′‐methylenedianiline were expected to be involved in covalent attachment to the epoxy resin. As a result, both tensile modulus and strength of the composites were improved when compared with those of pure epoxy resin. Thus, the AF‐VGCNFs play a role as an outstanding functional additive, which could resolve both dispersion and interfacial adhesion issues at the same time by functionalization of VGCNFs and covalent bonding between the additive and matrix, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7473–7482, 2008