纳米二氧化硅表面改性及其补强天然胶乳研究

简述了纳米二氧化硅的表面结构、表面改性机理及方法。介绍国内外对纳米二氧化硅表面化学改性及纳米二氧化硅改性天然橡胶复合材料的制备工艺进行详述,最后对纳米二氧化硅改性天然胶乳存在的问题和发展方向进行了展望。     

鞣酸改性纳米二氧化硅对UV固化涂料性能的影响

通过在纳米二氧化硅-乙醇悬浮液中加入一定量鞣酸的方法,在纳米二氧化硅表面引入羟基等活性基团对纳米二氧化硅进行表面改性,并用SEM、FTIR和TG等手段对鞣酸表面改性纳米二氧化硅的改性机理进行研究。利用交流阻抗图谱(EIS)研究包覆后二氧化硅对UV固化涂料的防腐蚀性能。结果表明:鞣酸是以化学键合的方式接枝到纳米二氧化硅表面,改性后的纳米二氧化硅分散良好,鞣酸改性纳米SiO2能极大提高UV固化涂层防腐蚀效果。     

纳米二氧化硅表面改性及增强聚氨酯密封胶

采用不同硅烷偶联剂对纳米二氧化硅表面进行改性,探讨了不同纳米二氧化硅含量对聚氨酯密封胶力学性能的影响。研究结果表明:使用γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷对二氧化硅表面改性,可得到分散均匀的球形纳米二氧化硅粒子;将改性后的纳米二氧化硅加入聚氨酯密封胶中,产品的力学性能有明显提高。     

纳米二氧化硅的表面改性及其应用进展

综述了国内外纳米二氧化硅的表面改性方法，并分类介绍了粉体纳米二氧化硅和胶体纳米二氧化硅的表面改性方法及其对材料性能的影响，分析讨论了纳米二氧化硅与有机聚合物的反应机理及其在聚合物基复合材料中的应用，展望了其发展前景。     

纳米二氧化硅在润滑剂中的应用

介绍了纳米二氧化硅的表面结构特点,简述了纳米二氧化硅作为无机稠化剂的特点及其研究现状,综述了表面改性前后的纳米二氧化硅作为减磨添加剂的研究进展,分析了纳米二氧化硅的润滑减磨作用机理。     

纳米二氧化硅在润滑剂中的应用

介绍了纳米二氧化硅的表面结构特点,简述了纳米二氧化硅作为无机稠化剂的特点及其研究现状,综述了表面改性前后的纳米二氧化硅作为减磨添加剂的研究进展,分析了纳米二氧化硅的润滑减磨作用机理.     

氟烷基改性的二氧化硅纳米球的制备与应用研究

以浓氨水为催化剂、正硅酸乙酯(TEOS)为原料,通过种子生长法制得二氧化硅纳米球;进一步以十三氟辛基三乙氧基硅烷(F-8261)对二氧化硅纳米球的表面进行改性,得到氟烷基改性二氧化硅纳米球.利用IR、UV、TEM等手段对氟烷基改性纳米球进行了表征.结果表明,改性单体F-8261通过化学键结合在二氧化硅纳米球表面;通过改变催化剂的用量,可制得平均粒径分别为35 nm和86 nm的纳米球.用含氟烷基改性二氧化硅纳米球的乙醇溶液处理玻璃、基准混凝土,其表面与水的的静态接触角分别从32°和0°提高到104°和141°,表明处理过的基材表面具有良好的防水和防污性能.     

纳米二氧化硅粉体的表面改性研究进展

简介了纳米二氧化硅的表面改性方法；重点介绍了国内外纳米二氧化硅的表面改性方法及其对材料性能的影响；指出了纳米二氧化硅在聚合物基复合材料中的应用；展望了其发展前景。     

改性二氧化硅/NR纳米复合材料结构与性能研究

采用聚二甲基二烯丙基氯化铵(PDDA)对二氧化硅进行表面改性,制备改性二氧化硅/NR纳米复合材料,并对其微观结构和物理性能进行研究.结果表明,改性二氧化硅均匀分散在天然胶乳基体中;扫描电子显微镜分析显示复合材料呈界面模糊的海岛结构;改性二氧化硅/NR纳米复合材料的物理性能较NR胶料大幅提高;随着改性二氧化硅用量的增大,改性二氧化硅/NR纳米复合材料的物理性能先提高后降低;当改性二氧化硅的用量为5.3份时,纳米复合材料的综合物理性能较好.     

苯基三甲氧基硅烷改性纳米二氧化硅的制备及其应用

采用偶联剂苯基三甲氧基硅烷(PTMS)对纳米二氧化硅进行改性,研究反应温度、反应体系pH值、反应时间及偶联剂PTMS用量对改性纳米二氧化硅活化度和表面羟基数的影响,采用X射线衍射分析、热重分析、傅里叶变换红外光谱分析和透射电子显微镜分析等对改性前后纳米二氧化硅结构进行表征,考察改性纳米二氧化硅对丁苯橡胶(SBR)的补强效果。结果表明:当反应温度为80℃、反应体系pH值为3.5、反应时间为90 min、偶联剂PTMS用量为纳米二氧化硅用量的6.85%时,改性纳米二氧化硅的活化度达到100%,表面羟基数最小,为0.99个·nm~(-2);与使用未改性纳米二氧化硅补强的SBR胶料相比,使用改性纳米二氧化硅(优化工艺条件下改性)补强的SBR胶料的门尼粘度明显下降,t90明显缩短,拉伸强度提高4.5%,拉断伸长率提高9%,DIN磨耗量降低21%。     

纳米二氧化硅的结构及表面改性对橡胶复合材料性能影响的研究进展

分析了纳米SiO_2结构及表面改性对其填充橡胶复合材料性能的影响,对比了不同表面改性方法对SiO_2增强效果的影响,指出基于良好分散性的适度结构化和高效功能化表面改性是提高SiO_2增强橡胶复合材料性能的重要因素.简要介绍了纳米SiO_2在橡胶复合材料中的应用研究现状.     

Effects of alkyl/vinyl-modified nanosilicas on negative or positive high voltage direct current breakdown strength and tensile properties in silicone rubber nanocomposites

To develop silicone/nanosilica insulation materials for high voltage direct current (HVDC), hydrophilic surface of fumed nanosilica was changed to hydrophobic by modifying with various ratios of alkylsilane and alkylsilane/vinylsilane coupling agents and the effects of the modified nanosilicas on the HVDC breakdown strength under negative or positive polarities were studied. Dielectric and tensile properties were also studied. The surface modification was confirmed by Fourier-transform infrared spectroscopy (FT-IR) analysis and the weights of the alkyl and alkyl/vinyl groups on the modified nanosilicas were measured by thermogravimetric analysis (TGA). Silicone rubber nanocomposites were prepared by mixing a liquid silicone rubber (LSR) and the modified nanosilicas, in which the mixing ratio of the LSR to the nanosilicas was fixed to be 20 wt%. Transmission electron microscopy (TEM) was used to observe the even dispersion of the nanosilica particles in the LSR matrix, and it was found that the surface-modified nanosilicas were well dispersed in the form of nano-clusters with 20–60 nm in size. Electrical properties (±HVDC breakdown strength and dielectric properties) and mechanical properties (tensile strength and elongation-at-break) were estimated, and it was found that ±HVDC breakdown strength and tensile strength were maximal when the surface modification ratio of alkyl: alkyl/vinyl groups was 50: 50 wt%.     

Unique behavior of in-situ generated nanosilica particles on physico-mechanical properties of fluoroelastomer

Fluoroelastomer (FKM) rubber containing different weight percentage of in-situ generated nanosilica particles have been prepared by sol-gel method using tetraethoxysilane (TEOS) as precursor and n-butyl amine as catalyst. FKM rubber with precipitated silica particles have also been prepared to compare the effect of in-situ generated nanosilica particles and precipitated silica particles on the physico-mechanical properties of FKM rubber. It is interesting to note that the FKM rubber containing in-situ generated nanosilica particles display excellent tensile stress-strain properties, rheological properties and thermal properties in comparison to the FKM rubber containing precipitated silica particles. The better performance of the in-situ generated nanosilica particles has been attributed to the good dispersion of in-situ generated nanosilica particles in FKM rubber matrix when compared to the precipitated silica particles. The fourier transform infrared (FTIR) spectroscopy clearly confirms the existence of chemical interaction between the FKM rubber chains and the in-situ generated nanosilica particles which leads to the good dispersion of the nanosilica particles in the rubber matrix. Strain sweep studies confirm the presence of more rubber-filler interaction in FKM rubber filled with in-situ generated nanosilica particles. On the other hand, strain sweep studies confirm the presence of more filler-filler aggregation in FKM rubber filled with precipitated silica particles. The dispersion of the in-situ generated nanosilica particles and precipitated silica particles in the surface and bulk of FKM rubber has been studied by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Selected samples have been cured to understand the effect of curing on the efficiency of in-situ generated nanosilica particles and precipitated silica particles on the physico-mechanical properties of FKM rubber.     

Synthesis of new superhydrophobic nanosilica and investigation of their performance in reinforcement of polysiloxane

We reported a new facile method to synthesize superhydrophobic nanosilica using glycidoxypropyltrimethoxysilane and dodecylamine as treatment agents. Also, we systemically investigate their performance in reinforcement of poly(dimethylsiloxane) (PDMS) rubber. Fourier transform infrared spectrum, contact angle (CA) and thermogravimetric analysis (TGA) measurements were used to characterize the modified nanosilica. Results show that the inherent hydrophilicity of parent nanosilica surface can be greatly altered through this modification method. The CA of as‐prepared superhydrophobic nanosilica can reach 160.2°. The properties of as‐prepared modified nanosilica‐filled PDMS composites were systemically investigated by dynamic rheological test, scanning electron microscopy, TGA, dynamic mechanical analysis. These as‐prepared superhydrophobic nanosilica exhibit uniform dispersion in the PDMS matrix, and their composites also show good mechanical properties and distinct advantage on thermal stability compared with those of the pure silica‐filled PDMS composites. Also described is the probable mechanism for the reinforcement of as‐prepared superhydrophobic nanosilica‐filled PDMS. POLYM. COMPOS., 31:1628–1636, 2010. © 2009 Society of Plastics Engineers     

Vulcanization accelerator functionalized nanosilica: Effect on the reinforcement behavior of SSBR/BR

The application of nanosilica in high performance tire highly depends on its uniform dispersion in rubber matrix. A series of dispersible nanosilica (denoted as DNS) modified by diphenyl guanidine (denoted as DPG, a vulcanization accelerator) were synthesized by liquid phase in situ surface chemical modification. The structure of the as‐obtained DNS‐DPG fillers was investigated in relation to Fourier transform infrared spectrometric analysis, thermogravimetric analysis, dynamic light scattering test, and transmission electron microscopic observation. It was found that the rubber vulcanization accelerator DPG was successfully grafted onto the surface of nanosilica, thereby effectively preventing the silica nanoparticles from agglomeration and significantly reducing the average particle size. The reinforcing effect of the DPG‐modified DNS nano‐fillers for the solution polymerized styrene butadiene rubber/butadiene rubber (denoted as SSBR/BR) was dependent on the fraction of the modifier DPG; in particular, when the amount of modifier DPG is 135.25 mmol/kg (denoted as DNS‐DPG‐3), silica exhibited very homogeneous dispersion in the SSBR/BR matrix, which contributed to significantly enhancing the filler‐rubber compatibility. As a result, SSBR/BR/DNS‐DPG‐3 nanocomposite exhibited the best mechanical properties, integrated high abrasion resistance and low rolling resistance. The modified silica not only possessed the effect of accelerating the crosslinking reaction, but also showed the reinforcing effect. This could make it feasible for SSBR/BR/DNS‐DPG nanocomposite to find promising application in green tire tread. POLYM. ENG. SCI., 59:1270–1278 2019. © 2019 Society of Plastics Engineers     

Surface modification of nanosilica with 3-mercaptopropyl trimethoxysilane and investigation of its effect on the properties of UV curable coatings

This paper describes surface modification of commercial nanosilica with 3-mercaptopropyl trimethoxysilane (MPTMS) and its effect on the properties of UV curable coatings. The mercapto groups were grafted onto nanosilica surface by a condensation of the surface Si–OH with the hydrolysized Si–OH of MPTMS. Fourier transform infrared spectroscopy, thermal gravimetric analysis, and particle size distribution were employed to characterize nanosilica and modified nanosilica. It was demonstrated that the mercapto groups were successfully grafted onto the nanosilica surface with the grafting ratio of 16.8% and the mercapto groups content of 0.9 mmol/g. The dispersion and self-aggregation of nanosilica in UV curable coatings were improved significantly. The photopolymerization kinetics of UV curable coatings, containing various amounts of nanosilica and modified nanosilica, were evaluated by the photo differential scanning calorimetry technique. This indicated that nanosilica both before and after modification decreased UV curing speed and ultimate percentage conversion; however, in comparison with the coatings containing unmodified nanosilica, the coatings containing modified nanosilica exhibited higher curing speeds and conversion ratios. It can be ascribed that the mercapto groups on the nanosilica surface reduced oxygen inhibition during the UV curing process via the thiol–ene click reaction. The mechanical properties of UV curable coatings were also compared.     

纳米SiO2对石灰基材料性能影响研究进展

作为一种应用广泛的无机纳米材料,纳米SiO2颗粒尺寸小、比表面积大、表面吸附性强,在改性石灰早期强度低和耐久性方面效果显著.综述了纳米SiO2对石灰基材料力学性能、耐久性以及改性机理等方面的研究进展,并基于上述综述提出了纳米SiO2改性石灰基材料当前存在的问题,结合纳米SiO2改性石灰的应用情况,展望了该类材料未来的发展方向.     

Grafting hydroxy‐terminated polybutadiene onto nanosilica surface for styrene butadiene rubber compounds

Hydroxy teminated polybutadiene (HTPB) was grafted onto the surface of nanosilica particles via toluene di‐isocyanate (TDI) bridging to reduce filler–filler interactions and improve dispersion of nanosilica in rubber. Also, this prepolymer as modifier contains double bonds which participate in sulfur curing of styrene butadiene rubber (SBR) matrix to enhance filler/polymer interaction and reinforcement effects of silica. The reactions were characterized by titration and Fourier transforms infrared spectroscopy. Thermogravimetric analysis was utilized to evaluate the weight percentage of grafted TDI and HTPB. About 60% of the hydroxyl sites of silica were reacted with excess TDI in the first reaction. In the second reaction, HTPB as desired reactive coating was grafted on the functionalized nanosilica to constitute about 24 wt % of the final modified silica. The sedimentation experiments showed good suspension stability for the modified nanosilica in the organic media. Scanning electron microscopy revealed nanoscale dispersion of modified silica aggregates in the SBR matrix at concentration of about 14 phr. Also, vulcanization characteristics and mechanical properties of compounds demonstrated that HTPB grafting improved dispersion of nanosilica as well as its interaction to the rubber matrix as an efficient reinforcement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011