Properties of PMMA/Carbon nanotubes nanocomposites prepared by “grafting through” method

A number of batch polymerizations were performed to study the effect of multi‐walled carbon nanotubes (MWCNTs) on the properties of PMMA/MWCNTs nanocomposites. To improve the dispersion of nanotubes in PMMA matrix, MWCNTs were functionalized with methacrylate groups via a four‐step modification process and the modified nanoparticles were used to synthesize the nanocomposites. The prepared samples were characterized by Raman spectroscopy, thermogravimetric analysis, dynamic mechanical thermal analysis, differential scanning calorimetry, gel permeation chromatography, UV–visible, and TEM techniques. According to the results, modified nanotubes improved thermal and mechanical properties better than the pristine MWCNTs. The main improvement in the mechanical and thermophysical properties was achieved for the nanocomposite containing 0.5 wt% of MWCNTs. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Synthesis of poly(methyl methacrylate)-silica nanocomposites using methacrylate-functionalized silica nanoparticles and RAFT polymerization

Well-defined poly(methyl methacrylate)-silica nanocomposites were produced by “grafting through” using reversible addition-fragmentation chain transfer (RAFT) polymerization. The surface of silica nanoparticle was modified covalently by attaching methacryl group to the surface using 3-methacryloxypropyldimethylchlorosilane. Polymerization of methyl methacrylate (MMA) using the 4-cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid RAFT agent, produced the PMMA-SiO₂ nanocomposites. Characterization of these well-defined nanocomposites included FT-IR, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), transmission electron microscopy (TEM) and dynamic mechanical analysis. These results show that the T_g values are higher and the mechanical strength of the PMMA-SiO₂ nanocomposites is slightly improved when compared to bulk PMMA. Further, the molecular weight of the PMMA (up to M_n = 100,000) is controlled and the SiO₂ are well dispersed in the PMMA matrix.     

Surface‐modified silica nanoparticles for reinforcement of PMMA

Polymethyl methacrylate (PMMA) was introduced onto the surface of silica nanoparticles by particle pretreatment using silane coupling agent (γ‐methacryloxypropyl trimethoxy silane, KH570) followed by solution polymerization. The modified silica nanoparticles were characterized by Fourier‐transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). Sedimentation tests and lipophilic degree (LD) measurements were also performed to observe the compatibility between the modified silica nanoparticles and organic solvents. Thereafter, the PMMA slices reinforced by silica‐nanoparticle were prepared by in situ bulk polymerization using modified silica nanoparticles accompanied with an initiator. The resultant polymers were characterized by UV–vis, Sclerometer, differential scanning calorimetry (DSC). The mechanical properties of the hybrid materials were measured. The results showed that the glass transition temperature, surface hardness, flexural strength as well as impact strength of the silica‐nanoparticle reinforced PMMA slices were improved. Moreover, the tensile properties of PMMA films doped with silica nanoparticles via solution blending were enhanced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and properties of polyimide/silica hybrid nanocomposites

In this study, a commercially available nano‐sized silica (SiO₂) was surface‐modified via esterification with oleic acid (OA), a relatively inexpensive and hydrophobic modifier. The surface‐modified silica (SiO₂‐OA) nanoparticles were used to disperse in the poly(amic acid) solutions of a commercial polyimide (PI), used for two‐layer film, and thermally imidized to form a series of PI/silica nanocomposites. The effects of the addition of SiO₂‐OA nanoparticles on the properties of the as‐prepared PI/silica nanocomposites were studied. The results indicated that the as‐prepared PI/silica nanocomposites exhibited improvements in the dynamic mechanical property, thermal stability, water resistance, and thermal expansion. POLYM. COMPOS. 28:575–581, 2007. © 2007 Society of Plastics Engineers     

“胶乳共混法”制备天然橡胶／二氧化硅纳米复合材料及其性能

采用γ-甲基丙烯酰氧基丙基三甲氧基硅烷（KH570）改性纳米二氧化硅（SiO2）,然后通过乳液聚合接枝上聚甲基丙烯酸甲酯（PMMA）,再将其与甲基丙烯酸甲酯（MMA）改性的天然胶乳,通过胶乳共混法制备天然橡胶／二氧化硅纳米复合材料,结果显示,纳米二氧化硅表面接枝上了PMMA,二氧化硅在橡胶基体中分散良好,粒径在60～100nm之间,得到的胶膜力学性能有很大的提高。     

Synthesis and characterization of PMMA/SiO2 organic–inorganic hybrid materials via RAFT‐mediated miniemulsion polymerization

In this article, we first carried out the surface modification of SiO₂ using silane coupling agent KH570, and then prepared PMMA/SiO₂ organic–inorganic hybrid materials by conventional free radical polymerization and RAFT polymerization in miniemulsion, respectively. The kinetics comparisons of these two polymerizations were studied. PMMA/SiO₂ hybrid materials were characterized by gel permeation chromatography, differential scanning calorimetry and thermogravimetric analysis. Experimental results indicated that the polymerization behavior of MMA in miniemulsion showed controlled/living radical polymerization characteristics under the control of RAFT agent. Incorporation of RAFT agent and SiO₂ nanoparticles improved the thermal properties of polymers, the thermal stability of polymers increased with increasing content of SiO₂ nanoparticles. The structures and morphologies of SiO₂, modified SiO₂, and PMMA/SiO₂ hybrid materials were characterized by FT‐IR and TEM. TEM results showed that the addition of modified SiO₂ nanoparticles to miniemulsion polymerization system obtained different morphology latex particles. Most of modified SiO₂ nanoparticles were wrapped by polymer matrix after polymerization. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Poly(methyl methacrylate)/montmorillonite nanocomposites prepared by bulk polymerization and melt compounding

This article focuses on structural, thermal, and mechanical properties of nanocomposites in dependence of preparation method and poly(methyl mathacrylate) (PMMA)/organically modified montmorillonite (OMMT) ratio. PMMA/OMMT nanocomposites were prepared by bulk polymerization and by melt compounding. Properties of nanocomposites of the same composition prepared by the two methods were compared. It was observed that nanocomposites prepared via melt compounding at 200°C had a highly oriented structure with lower interlayer spacing values than nanocomposites prepared via bulk polymerization. Two reasons for the observed smaller interlayer spacing obtained by melt compounding were identified. The first is enhanced PMMA penetration and/or formation between layers in the case of bulk polymerization, which was confirmed by determination of stronger interactions between OMMT and PMMA by Soxhlet extraction, infrared spectroscopy, and differential dynamic calorimery. The second reason for smaller interlayer spacing for nanocomposites prepared by melt compounding is organic modifier degradation during melt compounding process, which was confirmed by thermogravimetric analysis. Both reasons lead to the fracture of melt compounded nanocomposites on the OMMT‐polymer interface, which was observed by scanning electron microscopy. For nanocomposites with disoriented structure and larger interlayer spacing prepared via bulk polymerization the fracture occurred in the polymer matrix. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Synthesis and characterization of polyimide–silica nanocomposites using novel fluorine‐modified silica nanoparticles

Polyimide–silica nanocomposites were synthesized with 4,4′‐oxydianiline, 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), and fluorine‐modified silica nanoparticles. Fluorinated precursors such as 4″,4?‐(hexafluoroisopropylidene)bis(4‐phenoxyaniline) (6FBPA) and 4,4′‐(hexafluoroisopropylindene)diphenol (BISAF) were employed to modify the surface of the silica nanoparticles. The microstructures and thermal, mechanical, and dielectric properties of the polyimide–silica nanocomposites were investigated. An improvement in the thermal stability and storage modulus of the polyimide nanocomposites due to the addition of the modified silica nanoparticles was observed. The microstructures of the polyimide–silica nanocomposites containing 6FBPA‐modified silica exhibited more uniformity than those of the nanocomposites containing BISAF‐modified silica. The dielectric constants of the polyimide were considerably reduced by the incorporation of pristine silica or 6FBPA‐modified silica but not BISAF‐modified silica. The addition of a modifier with higher fluorine contents did not ensure a lower dielectric constant. The uniformity of the silica distribution, manipulated by the reactivity of the modifier, played an important role in the reduction of the dielectric constant. Using 6FBPA‐modified silica nanoparticles demonstrated an effective way of synthesizing low‐dielectric‐constant polyimide–silica nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 882–890, 2007     

Production and characterization of UHMWPE/fumed silica nanocomposites

Ultrahigh‐molecular‐weight polyethylene (UHMWPE)/fumed silica nanocomposites were prepared via in situ polymerization using a bi‐supported Ziegler‐Natta catalytic system. Nanocomposites with different nanoparticle weight fractions were produced in order to investigate the effect of fumed silica on thermal and mechanical properties of UHMWPE/fumed silica nanocomposites. The viscosity average molecular weight (M ) of all samples including pure UHMWPE as the reference sample and nanocomposites were measured. Scanning electron microscope (SEM) images showed the homogenous dispersion of nanoparticles throughout the UHMWPE matrix while no nanoparticle cluster has been formed. Crystallization behavior of nanocomposites was investigated by differential scanning calorimetry (DSC), which showed a slight increase in melting temperature by enhancing the nanoparticle concentration while no significant change was observed in the crystallization temperature as the fumed silica concentration enhanced. The improvement in all thermal stability parameters was recorded by thermogravimetric analysis (TGA). Besides, via tensile testing, it was confirmed that addition of nanoparticles caused considerable improvement in such mechanical properties as Young's modulus, yield stress, and tensile strength of samples while the elongation at break declined by addition of more nanoparticles. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Synthesis and physicochemical investigation of imide-functionalized silica nanocomposites

The incorporation of inorganic nanoparticles into polymers have gained significant attention to improving functional properties. The ultimate nanocomposite behaviors are influenced by many parameters, such as microstructural distribution that are produced during the treatment process. Herein, a hybrid material integrating a modified network into a polyimide PI matrix was produced via the sol–gel method by the reaction of pyromellitic dianhydride, 4, 4-oxydianaline, and 1, 5-diaminonaphthalene to synthesize copolyimides nanocomposite. The modified polyimide and unmodified polyimide silica (SiO₂) nanoparticles were incorporated in the polyimide matrix to have polyimide silica nanocomposite. In modified silica nanoparticles, 3-aminopropyltriethosilane was introduced to have better compatibility among inorganic–organic hybrid with similar chemical contact due to their flexible alkyl group. The surface morphology or structure of silica and polyimide was affirmed by scanning electron microscopy, Fourier transforms infrared spectroscopy confirmed the synthesis of pure polyimide, unmodified polyimide, and modified polyimide silica via presence and absence of certain peaks. Thermogravimetric analysis (TGA) results showed high thermal stability of nanocomposites as silica content increases. In contrast to unmodified silica, the modified silica provides more thermal stability to the nanocomposites. Dynamic mechanical analysis was used to investigate the tensile stress of pure polyimide, unmodified, and modified silica nanocomposites. Thermal stability, storage modulus, and moisture absorption of these hybrid materials were improved with silica nanoparticles. The TG mass spectrum confirms the successful synthesis of modified silica networks. The substituted silica nanoparticles show higher mechanical toughness and storage in modified compared to unmodified silica nanocomposite, which exhibits stronger binding attraction between silica nanoparticles and polyimide matrix.     

Preparation of Polyetherimide Nanocomposites with Improved Thermal, Mechanical and Dielectric Properties

Summary Thermoplastic polyetherimide (PEI)-SiO₂ nanocomposites were prepared from a soluble PEI, which was synthesized from m-phenylenediamine and bisphenol A dianhydride, in combination with tetraethoxysilane solution via a novel sol-gel process. A coupling agent was used to enhance the compatibility between PEI and silica. This approach was compared with PEI-clay nanocomposite in which montmorillonite was modified with ammonium salts of 12-aminododecanoic acid using an intercalation polymerization. The size and dispersion of the silica or clay in the PEI nanocomposites were analyzed by X-ray diffractometer and scanning electron microscopy. It was found that the sol-gel process offered a fine interconnected or co-continuous phase, whereas the clay remained dispersed in nanocomposites. Though the thermal properties of PEI-clay nanocomposites were improved over pristine PEI, physical testing showed that the films become brittle as the organoclay content increased to over 2%. The thermal stability and mechanical properties of the PEI/silica nanocomposites prepared by sol-gel process were improved with silica content up to 10%. The onset decomposition temperatures were 550–600 °C. The dielectric constant decreased with increasing amounts of silica. At higher silica contents, the mechanical properties were reduced as a result of the phase separation.     

纳米粒子种类对PMMA／纳米复合材料性能的影响

研究了胶体SiO2、粉体SiO2、有机改性蒙脱土OMMT等不同纳米粒子种类对纳米复合材料性能的影响,通过红外光谱、X射线衍射、热重分析和动态力学性能等测试手段对复合材料进行了分析表征。结果表明,OMMT和胶体SiO2与聚甲基丙烯酸甲酯（PMMA）的复合效果最好;OMMT的加入对复合材料的热性能有一定提高,而胶体和粉体SiO2的加入提高了复合材料的储能模量。     

PMMA/silica nanocomposite studies: Synthesis and properties

Polymethylmethacrylate (PMMA)/silica nanocomposites are prepared by solution polymerization in this project and the resulting materials are subjected to characterization to evaluate thermal, mechanical, and fire properties. IR results show that both (3‐acryloxypropyl)methydimethoxy‐silane (APMDMOS) and (3‐acryloxypropyl)trimethoxysilane (APTMOS) can serve as reagents for the surface modification of silica, while APTMOS performed better than APMDMOS for the modification of the silica surface. Mechanical properties of PMMA/silica nanocomposites prepared by solution blending showed decreased tensile strength and elongation at break, while materials from solution polymerization performed better than PMMA itself. Moreover, all prepared samples have shown improved thermal stabilities versus PMMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3844–3850, 2004     

Polyimide‐silica nanocomposites exhibiting low thermal expansion coefficient and water absorption from surface‐modified silica

In this study, a commercially available nano‐sized silica (SiO₂) was surface‐modified via esterification with oleic acid (OA), a relatively inexpensive and hydrophobic modifier, and characterized by FTIR, NMR, SEM, EDS, and TGA measurements. Various amounts of the surface‐modified silica nanoparticles (SiO₂‐OA) were dispersed in a poly(amic acid), which were then cyclized at high temperatures to form a series of PI/SiO₂‐OA nanocomposite films (PISA). The effect of the addition of the SiO₂‐OA nanoparticles on the properties of the as‐prepared polyimide nanocomposite was studied. The results indicated that, comparing with pure PI and PI/pristine‐SiO₂ composite film (PISI), the as‐prepared PISA films had enhanced dynamic mechanical properties and thermal stability, as well as reduced water absorption and thermal expansion. The as‐prepared PI/SiO₂‐OA nanocomposites have potential for applications in high performance microelectronic devices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 4096–4105, 2007     

The Effect of Surface Modification of TiO2 with Diblock Copolymers on the Properties of Epoxy Nanocomposites

The TiO₂ nanoparticles were modified by diblock copolymers, poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS), via reversible addition-fragmentation chain transfer (RAFT) polymerization, and the epoxy nanocomposites containing different TiO₂ and with different contents were prepared. Subsequently, the effects of TiO₂ content on the mechanical and thermal properties of nanocomposites were investigated. The results indicated that after grafting copolymers onto TiO₂, the dispersion of TiO₂ and interaction with epoxy matrix could be significantly increased, therefore, the mechanical properties of the nanocomposites were improved greatly. When the TiO₂-PMMA-b-PS content was 1 wt%, the impact strength and flexural strength reached their the best, and increased up to 96% and 43%, respectively. Furthermore, the thermal stability of the nanocomposites was also distinctly improved.     

悬浮聚合聚甲基丙烯酸甲酯／蒙脱土纳米复合材料的制备及表征

采用悬浮聚合法制备了聚甲基丙烯酸甲酯／蒙脱土（PMMA/MMT）纳米复合材料，利用X射线衍射仪、透射电子显微镜和傅里叶变换红外光谱等手段表征了复合材料的结构，研究了不同改性剂对复合材料结构的影响。通过热重分析考察了复合材料的热性能。结果表明，通过悬浮聚合可以成功制备剥离型纳米复合材料，PMMA基体与MMT可以产生较强的相互作用。MMT的加入可以显著提高复合材料的热稳定性。当MMT含量为10％（质量分数，下同）时，PMMA的最大分解温度提高了15℃。     

PMMA/o‐MMT nanocomposites obtained using thermally stable surfactants

In the preparation of polymer/montmorillonite (MMT) nanocomposites, the commonly used compatibilizers (cations of long carbon‐chain alkyl ammonium salts) present the drawback of a poor thermal stability. During bulk processing of nanocomposites elevated temperatures are usually required and, if processing temperature is close to decomposition temperature of the surfactant, decomposition will occur altering the interface between filler and polymer. To solve this problem, organically modified MMTs with thermally stable imidazolium surfactants have been prepared. A series of nanocomposites were obtained by dispersing o‐MMT in poly(methyl methacryate) (PMMA) matrix via an in situ free radical polymerization. The nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, gel permeation chromatography, thermogravimetric analysis, dynamic mechanical analysis, and nanoindentation measurements. The results showed that nanocomposite thermal stability depended on both the kind of used surfactant and degree of exfoliation. Under the same values of molecular weight, the nanocomposites containing imidazolium cations showed a better thermal stability with respect to the nanocomposite obtained using a standard alkylammonium surfactant. Dynamic mechanical and Nanoindentation measurements showed an improvement of mechanical properties, such as modulus and hardness, with respect to pure PMMA. Solution blending treatments on these nanocomposites led to obtaining of further improvement of the thermal performance. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41393.     

Synthesis and properties of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposites

PMMA/MMT nanocomposites were successfully synthesized via in situ intercalative polymerization, and characterized by means of wide‐angle X‐ray diffractometry, transmission electron microscopy, thermal gravimetric analysis, dynamic mechanical analysis and Fourier‐transform infrared analysis. The nanocomposites possess partially exfoliated and partially intercalated structure, in which the silicate layers are exfoliated into nanometre secondary particles with thickness of less than 20 nm and uniformly dispersed in the polymer matrix. In comparison with pure PMMA, the thermal stability, glass transition temperature, and mechanical properties of the polymer are notably improved by the presence of the nanometric silicate layers. It was found that part of the PMMA chains in the nanocomposites are well immobilized inside and/or onto the layered silicates and, therefore, the unique properties of the nanocomposites result from the strong interactions between the nanometric silicate layers and the polymer chains. Copyright © 2003 Society of Chemical Industry     

Rheological and mechanical properties of PVC/CaCO3 nanocomposites prepared by in situ polymerization

Poly(vinyl chloride) (PVC)/calcium carbonate (CaCO₃) nanocomposites were synthesized by in situ polymerization of vinyl chloride (VC) in the presence of CaCO₃ nanoparticles. Their thermal, rheological and mechanical properties were evaluated by dynamic mechanical analysis (DMA), thermogravimetry analysis (TGA), capillary rheometry, tensile and impact fracture tests. The results showed that CaCO₃ nanoparticles were uniformly distributed in the PVC matrix during in situ polymerization of VC with 5.0 wt% or less nanoparticles. The glass transition and thermal decomposition temperatures of PVC phase in PVC/CaCO₃ nanocomposites are shifted toward higher temperatures by the restriction of CaCO₃ nanoparticles on the segmental and long-range chain mobility of the PVC phase. The nanocomposites showed shear thinning and power law behaviors. The ‘ball bearing’ effect of the spherical nanoparticles decreased the apparent viscosity of the PVC/CaCO₃ nanocomposite melts, and the viscosity sensitivity on shear rate of the PVC/CaCO₃ nanocomposite is higher than that of pristine PVC. Moreover, CaCO₃ nanoparticles stiffen and toughen PVC simultaneously, and optimal properties were achieved at 5 wt% of CaCO₃ nanoparticles in Young's modulus, tensile yield strength, elongation at break and Charpy notched impact energy. Detailed examinations of micro-failure micromechanisms of impact and tensile specimens showed that the CaCO₃ nanoparticles acted as stress raisers leading to debonding/voiding and deformation of the matrix material around the nanoparticles. These mechanisms also lead to impact toughening of the nanocomposites.     

Preparation of highly emissive,thermally stable,UV‐cured polysilsesquioxane/ZnO nanoparticle composites

A high molecular weight polysilsesquioxane (LPMSQ)/ZnO nanocomposite was prepared by blending a methacryl‐substituted polysilsesquioxane and PMMA‐coated ZnO nanoparticle (NP) followed by UV‐curing process. These LPMSQ/ZnO nanocomposites gave high thermal and mechanical stabilities originated from the rigid ladder structured siloxane backbone of LPMSQ. The polysilsesquioxane and surface‐modified ZnO nanoparticles showed excellent compatibility between MMA groups in LPMSQ‐ and PMMA‐capped ZnO nanoparticles to give well‐dispersed LPMSQ/ZnO nanocomposites. Mechanically pliant and flexible free standing films were obtained, and the photo and optical properties of these hybrid nanocomposites were examined. The high photoluminescent properties were maintained even after severe thermal treatments exceeding 400°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42333.