SiO2/聚氨酯纳米复合物的在位合成及其在环氧树脂中分散行为的研究

以水性阳离子聚氨酯纳米粒子为纳米微囊,利用原位水解法使正硅酸乙酯(TEOS)在囊内水解、聚合生成二氧化硅(SiO2)纳米粒子,从而合成出SiO2/聚氨酯纳米复合物的稳定水基乳液,实现纳米复合物中SiO2纳米粒子的均匀分散和良好的界面结合。并以此作为已表面改性的纳米粒子实现SiO2纳米粒子在环氧树脂的均匀分散。通过能谱扫描、透射电镜和乳液粒子粒径与分布等测试方式对含有环氧树脂的水性SiO2/聚氨酯纳米复合物进行测试。结果表明,SiO2/聚氨酯纳米复合物可以在环氧树脂中均匀分散且不团聚,同时也可促进环氧树脂在水中的分散。     

纳米SiO2粒子静电吸附引发剂及引发甲基丙烯酸甲酯乳液聚合

对纳米SiO2粒子静电吸附2,2′-偶氮(2-脒基丙烷)二氯化氢(AIBA)引发剂,进而在其表面引发甲基丙烯酸甲酯乳液聚合而制备聚甲基丙烯酸甲酯(PMMA)/纳米SiO2复合粒子进行了研究.发现当介质pH值高于SiO2粒子等电势点时,纳米SiO2能与AIBA发生静电吸附而锚固上引发剂.使用高速离心分离/紫外分光光度计分析,证明引发剂吸附存在一个稳定上限,在pH=10时为0.067g·(g·SiO2)-1.随着纳米SiO2粒子锚固AIBA量的增加,聚合速率增加,PMMA/纳米SiO2复合粒子的平均粒径变小;乳化剂OP-10用量过大时,复合粒子的胶体稳定性降低.原位乳液聚合得到的PMMA/纳米SiO2复合粒子的典型形态为"草莓"型核壳结构.     

硬质聚氨酯/二氧化硅纳米粒子复合材料泡沫形貌和性能研究

利用2种不同粒径的球形二氧化硅（SiO2）纳米粒子作为填料,制备了硬质聚氨酯（PU-R）/SiO2纳米粒子复合材料泡沫。利用扫描电子显微镜考察复合材料的形貌,通过压缩试验、尺寸稳定性测试和热导率测试表征复合材料的力学性能、尺寸稳定性和热导率。结果表明,球形SiO2纳米粒子对复合材料的泡孔结构有明显的细化作用（孔径从纯PU-R泡沫的303 μm降低到170 μm）,可以有效提高复合材料的压缩性能（与纯PU-R泡沫相比,比强度和比模量分别提高了8.3 %和12.5 %）,降低了其线膨胀系数,并使热导率略微下降,而对尺寸稳定性无明显影响。与粒径为400 nm的SiO2纳米粒子相比,粒径为700 nm的SiO2纳米粒子较易均匀分散,对PU-R泡沫力学性能的改善效果更为明显。     

细乳液聚合制备聚丙烯腈/纳米SiO2复合粒子

由含甲基丙烯酸-3-三甲氧基硅烷(MPS)改性纳米SiO2的丙烯腈细乳液聚合制备聚丙烯腈/纳米SiO2复合粒子.研究了纳米SiO2的改性及含量、十二烷基硫酸钠(SDS)乳化剂和十六烷(HD)助乳化剂浓度对细乳化液滴粒径的影响.结果表明,直接采用未改性纳米SiO2,细乳化后出现双峰分布,纳米SiO2粒子未有效进入单体液滴;用10%MPS改性纳米SiO2后,细乳化液滴呈单峰分布.随着纳米SiO2粒子含量的增加,细乳化液滴的平均粒径增大,分布变宽.含纳米SiO2粒子的细乳化液滴体的平均粒径随SDS浓度和HD浓度增大而减小.透射电镜观察发现,细乳液聚合产物的连续相中无纳米SiO2粒子分布,复合粒子呈非规整结构,纳米SiO2>粒子在聚丙烯腈基体中基本呈初级粒子分布.     

Ag/Co/Au三金属纳米粒子的合成及表征

反胶束是指由介于油和水界面的表面活性剂分子来稳定的,且均匀分散于连续油介质中的微液滴,由于微液滴的尺寸限制和其在油介质中的良好分散性,它可以作为"微反应器"合成纳米材料。以AOT为阴离子表面活性剂,采用反胶束法合成了Ag/Co/Au纳米粒子。采用紫外-可见(UV-Vis)吸收光谱、傅立叶红外光谱(FT-IR)对产物进行表征。研究结果表明,反胶束法合成Ag/Co/Au纳米粒子粒径均匀,分散性好、稳定性好。     

二氧化硅球的制备及其功能化

以正硅酸四乙酯为硅源,分别在碱性和酸性条件下制备了二氧化硅(SiO2)球状粒子;在碱性条件下制备了具有荧光功能的SiO2-FITC复合纳米球;以Sn2+作为敏化剂,在SiO2球表面沉积Ag纳米颗粒,制备了SiO2/Ag核-壳结构纳米粒子。通过透射电子显微镜(TEM)、紫外-可见近红外(UV-vis-NIR)分光光度计,荧光分光光度计对SiO2球,SiO2-FITC荧光纳米球,SiO2/Ag核-壳结构纳米粒子的形貌和光学吸收、荧光发射特性进行了表征。结果表明,碱性环境下制备的SiO2球粒径大小为纳米级,酸性环境下制备的SiO2球粒径大小为微米级,酸性环境下制备的SiO2球比碱性环境下制备的硅球致密。掺入FITC的SiO2球具有荧光发射特性,且发光强度可以控制。Ag纳米颗粒修饰的SiO2/Ag核-壳结构纳米粒子具有等表面等离子体共振吸收特性。     

水性聚氨酯/纳米SiO_2杂化材料的制备及性能研究

首先合成内交联的WPU预聚体,以KH550为偶联剂,加入亲水性的纳米SiO2(A200),通过溶胶-凝胶过程合成了一种水性聚氨酯/纳米SiO2杂化材料(WPUNS)。通过FTIR、TG、DSC、物理机械性能测试对WPUNS的结构和膜性能进行了研究,用动态激光光散射法测试了杂化乳液的粒径和粒径分布,并用TEM对乳液形貌进行了观察。红外分析表明,WPU大分子和A200之间形成了化学键,粒径和乳液形貌观察显示了PU大分子包裹A200粒子形成了复合粒子结构。当w(A200)由0增大到2%时,粒径由79.9 nm增至139.9 nm,膜的拉伸强度由6.32 MPa增加到20.46 MPa,吸水率由28.3%降低到6.3%,硬度亦相应提高。TG分析表明,A200的加入可以提高材料的耐热性。DSC表明,A200的加入使硬段Tg向高温扩展。     

反胶束法纳米TiO_2的UV-vis和TEM研究

用石油醚为溶剂的反胶束体系溶胶-凝胶法合成了纳米TiO2,采用UV-vis光谱跟踪纳米TiO2粒子粒径的变化,研究了影响纳米TiO2溶胶粒子大小的因素,采用TEM表征了纳米TiO2的粒子大小及其粒径分布。结果表明,合成的反胶束纳米TiO2的UV-vis光谱吸收边λonset为344.8~363.2 nm,与锐钛型纳米TiO2的吸收边λonset=385 nm相比,紫外可见光谱发生“蓝移”,反胶束纳米TiO2粒子的半径为5~6.5 nm;TEM表明,纳米TiO2粒子的粒径为15~55 nm,粒径分布较窄,粒径分布指数SD I为1.19~1.29;FTIR谱图表明,TiO2粒子为表面具有一定数量钛羟基的水合TiO2。     

表面引发活性聚合SiO2/PMMA核壳复合纳米粒子的制备及表征

在乙醇介质中,通过在窄粒径分布SiO2胶体粒子表面上接枝的α-溴代物引发甲基丙烯酸甲酯的原子转移自由基聚合,制备了具有核壳结构的SiO2/PMMA复合纳米粒子.采用FTIR、TGA和Acoustosizer等表征了该核壳结构粒子的结构与性能、粒径和粒径分布.结果表明:PMMA已经成功接枝到SiO2表面,并且其链长约为8...     

SiO2纳米粒子改性填充PC的力学与流变性能

采用SiO2纳米粒子填充改性聚碳酸酯(PC),为使无机纳米粒子在基体PC中分散均匀,经硅烷偶联剂KH-550对SiO2纳米粒子进行表面处理,分析了改性SiO2纳米粒子对复合材料机械与加工性能的影响,并对复合材料进行了分析表征,探讨了无机刚性纳米粒子填充改性典型工程塑料PC的特点并探索其增强增韧的机理,研究了复合物的粘流变性能. 结果表明,改性SiO2纳米粒为球形,在PC基体中分散均匀,湿法改性制备的PC/SiO2纳米粒子复合材料的力学拉伸性能和流变性能最好.     

In situ polymerization of polyamide 66 nanocomposites utilizing interfacial polycondensation. III. Co‐synthesis of silica nanocomposites via sol–gel chemistry

In situ co‐synthesis of nylon 66 (PA66)‐silica nanocomposites can be accomplished through sol–gel chemistry conducted simultaneously with the nylon polymerization. Unfunctionalized silica nanocomposites and bonded silica nanocomposites wherein the inorganic silica phase chemically couples to the nylon polymer through a functionalized silane are generated via the simultaneous initiation of synthesis reactions in the inorganic and organic species. The effects of agitation and water‐to‐silane molar ratio on the courses of the inorganic and organic reactions and the generated silica morphology in the resulting nanocomposites are investigated using the tools of Brookfield Viscometer, Fourier transform infrared spectroscopy, and transmission electron microscopy. Dynamic mechanical analysis confirms the mechanical reinforcement of the various nanocomposites in relation to their silica content and network morphology. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Effect of storage time on the characteristics of a waterborne polyurethane/tetraethoxysilane mixture and the properties of prepared films

Waterborne polyurethane (WPU) is one of the most important resins. The properties of WPU can be modified by introducing inorganic components. Tetraethoxysilane (TEOS) is a precursor for preparing inorganic polymers and can be used to prepare WPU/silica hybrids. In this study, WPU dispersion was synthesized by reacting polytetramethylene ether glycol and dimethylolpropionic acid with isophorone diisocyanate, followed by chain extension with ethylenediamine. After mixing WPU with TEOS, the mixture was sealed and stored at room temperature for different lengths of times. The influence of time on the characteristics of the WPU/TEOS mixture and the properties of films were investigated. The results showed that the viscosity, surface tension and average particle size of the mixture increased with prolonged storage time. ²⁹Si-NMR analysis indicated that the structure of silica exists in the WPU film. DSC, DMA and TGA results showed that WPU/silica films made from the mixture have less thermal activity, higher storage modulus, lower damping peak heights and better heat resistance after relatively long storage times.     

有机聚合物／无机化合物纳米复合阻燃材料研究进展

综述了有机聚合物／无机化合物纳米复合阻燃材料的研究和应用现状。阐述的纳米复合阻燃材料包括有机聚合物／层状硅酸盐纳米复合材料、有机聚合物／碳纳米管纳米复合材料、有机聚合物／二氧化硅纳米复合材料、有机聚合物／石墨纳米复合材料等。与传统无机阻燃剂填充阻燃材料相比,这类新型纳米复合阻燃材料的填料与基体的亲合性、基体的物理力学性能和阻燃性能等均得到改善。     

Effects of Silica,Vinyl-Terminated Polydimethylsiloxane (VPDMS) and PMHS-Grafted-POSS (PH) Nanocomposites: Morphology,Thermal Behavior and Mechanical Property

Nanocomposites with different cross-linking agents (PH and PMHS) and silica were prepared. Morphology, thermal and mechanical properties of nanocomposites respectively studied by means of SEM, TGA and universal tensile testing machine. The results revealed that the thermal stabilities and mechanical properties were significantly enhanced by using PH compared with PMHS when silica was added. From the obtained results, it was found that “synergistic” effect of PH on thermal stability and mechanical property of nanocomposites existed. The striking “synergistic” effect of PH on thermal and mechanical properties of nanocomposites was mainly attributed to the organic/inorganic hybrid cross-linking agent of PH.     

纳米二氧化硅水溶胶改性UWPU的研究

通过丙酮法合成光固化水性聚氨酯丙烯酸酯预聚体,用三乙胺中和后在乳化过程中原位引入纳米二氧化硅水溶胶(Wv33、R900、R301)制备二氧化硅/光固化水性聚氨酯(SiO2/UWPU)纳米复合乳液,并进一步通过紫外光固化制备了SiO2/UWPU复合膜。通过电子扫描显微镜(SEM)和电子拉力机研究了不同纳米二氧化硅水溶胶对UWPU/SiO2复合膜的微观结构和力学性能的影响。SEM分析表明表面有机改性的pH值接近中性的硅溶胶(Wv33)较pH为酸性或碱性的硅溶胶在聚氨酯基体中有较好的分散性;应力-应变曲线分析表明Wv33能有效实现对复合膜的增强,即提高了复合膜的储存模量、拉伸强度和邵A硬度。     

Analyzing the influence of different synthetic talcs in waterborne polyurethane nanocomposites obtainment

Waterborne polyurethane (WPU) nanocomposites were produced utilizing synthetic talc in gel form in order to improve its physical–chemical properties. Synthetic talc manufactured in nano‐gel form are interesting because their interaction with water occurs through hydrogen bonding favoring fillers dispersion within the WPU matrix. WPUs are environmental friendly materials because no organic solvents are used in its production. The nanocomposites obtained with the three synthetic talc nano‐gel fillers presented a good dispersion even when higher amounts of fillers were added, as seen by X‐ray diffraction, transmission electron microscopy, field emission scanning electron microscopy, and atomic force microscopy analyses. The addition of synthetic talcs improved WPU nanocomposites mechanical properties. Storage and loss modulus results proved fillers incorporation into the WPU matrix corroborating with Fourier transform infrared spectroscopy results. Results demonstrated that synthetic talcs in nano‐gel form are interesting to obtain WPU nanocomposites with superior mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46107.     

Elaboration and mechanical characterization of nanocomposites thin films: Part II. Correlation between structure and mechanical properties of SiO2-PMMA hybrid materials

Mechanical properties of hybrid thin films based on SiO₂-PMMA materials were investigated through nanoindentation tests. We demonstrated in the part I of this paper, that nanoindentation is an appropriate technique to characterize hybrid organic–inorganic thin films. Specific procedures of analysis and the use of appropriate models allows to determine reproductive indentation modulus and hardness of the hybrid layers. The mechanical responses of nanocomposites are not only governed by the composition of the layers but also by the nature and the extent of the hybrid interface. Different layers have been studied, constituted by an inorganic and an organic phase that just be physically mixed or covalently connected. The weak (H bonds) or strong (covalent bonds) interactions generated by the hybrid interface lead to nanocomposites which exhibit different mechanical behaviours. Moreover, comparison between layers obtained by in situ inorganic polymerization in PMMA and layers obtained with preformed silica nano-particles have been also investigated to correlate the morphology of the nanocomposites with the mechanical responses.     

Preparation of novel hydrophobic magnetic Fe3O4/waterborne polyurethane nanocomposites

Magnetic Fe₃O₄/waterborne polyurethane nanocomposites were synthesized based on waterborne polyurethane (WPU) and amino-functionalized Fe₃O₄ by in situ polymerization. The Fe₃O₄ nanoparticle was found to be uniformly distributed in Fe₃O₄/WPU nanocomposites with linear or crosslinked structure. In addition, the formation mechanism and magnetic conduction mechanism of stable inorganic–organic nanocomposites were discussed. The experimental results showed that the thermal stability, magnetic, and mechanical properties of magnetic Fe₃O₄/waterborne polyurethane nanocomposites were improved by amino functionalized Fe₃O₄. Furthermore, the defoaming property of the emulsion and the hydrophobic property of magnetic Fe₃O₄/waterborne polyurethane nanocomposites were improved by the 1-hexadecanol-terminated prepolymer. What more, polycaprolactone (PCL)-based Fe₃O₄/WPU nanocomposites have excellent mechanical properties (The tensile strength is over 30 MPa, the elongation rate is above 300%.) and magnetic properties. Magnetic Fe₃O₄/waterborne polyurethane nanocomposites will be used in the field of hydrophobic and microwave absorbent materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48546.     

Self-healing waterborne polyurethane coating by pH-dependent triggered-release mechanism

In this study, effect of high-loaded silica capsules with corrosion inhibitor on thermal degradation and self-healing properties of waterborne polyurethane (WPU) was investigated. Silica capsules were synthesized using an oil in water (O/W) microemulsion and WPU was prepared via the prepolymer method. Assembled capsules demonstrated pH dependent release of their core. Incorporating silica capsule as an inorganic component resulted to improve thermal and barrier properties of WPU coatings. WPU coating with 1% silica capsules demonstrated better barrier quality in corrosive media and adding more than that resulted a rapid deterioration in barrier properties. Furthermore, such coatings possess an excellent adhesive strength with steel substrate. Electrochemical impedance spectroscopy was used in corrosion monitoring and healing procedure. Moreover, capsule morphology and thermal degradation of the WPU coating has been investigated separately by scanning electron microscopy and thermal gravimetric analysis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47082.     

An experimental study on improving the atomic oxygen resistance of epoxy resin/silica nanocomposites

To improve the atomic oxygen (AO) resistance of the spacecraft resin matrix material, inorganic silica nanoparticles were filled into the epoxy resin. Samples of the epoxy/silica nanocomposites were prepared and AO exposure experiments were conducted in a ground-based AO effects simulation facility. The samples exhibited significantly less mass loss and erosion yield than the corresponding pristine epoxy resin. Analysis of the surface morphology, composition and chemical structures showed that some organic structures still resides on the nanocomposites surface after the AO exposure experiment. The silica nanoparticles and the organic structures could serve as a barrier to resist further erosion. POLYM. ENG. SCI., 47:1156–1162, 2007. © 2007 Society of Plastics Engineers