Synthesis and thermal behavior of poly(methyl methacrylate)/Maghnia bentonite nanocomposite prepared at room temperature via in situ polymerization initiated by a new Ni(II)α‐benzoinoxime complex

Poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate)/clay nanocomposite (PMMA/OBT) were successfully prepared in dioxan at room temperature via in situ radical polymerization initiated by a new Ni(II)α‐ Benzoinoxime complex as a single component in presence of 3% by weight of an organically modified bentonite (OBT) (originated from Maghnia, Algeria) and characterized by FTIR, ¹H‐NMR and viscometry. Mainly intercalated and partially exfoliated PMMA/OBT nanocomposite was elaborated and evidenced by X‐Ray diffraction (XRD) and transmission electron microscopy (TEM). The intrinsic viscosity of PMMA/OBT nanocomposite is much higher than the one of pure PMMA prepared under the same conditions. Differential scanning calorimetry (DSC) displayed an increase of 10°C in the glass transition temperature of the elaborated PMMA/OBT nanocomposite relative to the one of pure PMMA. Moreover, the TGA analysis confirms a significant improvement of the thermal stability of PMMA/OBT nanocomposite compared to virgin PMMA: the onset degradation temperature of the nanocomposite, carried out under nitrogen atmosphere, increased by more than 45°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(methyl methacrylate) nanocomposite reinforced with graphene,graphene oxide,and graphite: a review

Poly(methyl methacrylate) (PMMA) is an important transparent thermoplastic polymer having appropriate strength, chemical, weathering, heat, and UV resistance. However, essential properties of this versatile polymer need to be enhanced for high-tech applications. Graphene has opened up a new vista for developing functional polymeric nanocomposite. Therefore, reinforcement of PMMA with graphene and related nanofiller has been focused in literature. This review basically highlights the fundamentals and characteristics of the significant classes of PMMA/graphene, PMMA/graphene oxide, and PMMA/graphite nanocomposite. Recent developments in the applications of PMMA/graphene-based nanofiller nanocomposite in biomedical, sensor, supercapacitor, flame retardant, and electromagnetic interference shielding materials were also comprehended.     

Preparation of cadmium sulfide/poly(methyl methacrylate) composites by precipitation with compressed CO2

Cadmium sulfide (CdS) nanoparticles and poly(methyl methacrylate) (PMMA) were first synthesized in methyl methacrylate (MMA)/sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) microemulsion, in which MMA acts as the solvent and monomer. Then compressed CO₂ was used as an antisolvent to precipitate the CdS and PMMA simultaneously. Using this method, a CdS/PMMA composite was successfully prepared. The CdS nanoparticles dispersed in the polymer matrices were characterized by transmission electron microscopy. The higher pressure is favorable to producing CdS nanoparticles of smaller size. The phase structure of the obtained composite was characterized by X‐ray diffraction, which reveals that cubic CdS particles were formed. The FTIR spectra of the composite showed that there is no chemical bonding or strong interaction between CdS and PMMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1643–1648, 2004     

Effect of tacticity of poly(methyl methacrylate) on interfacial region with silica in polymer nanocomposite

The effect of tacticity on the interfacial region between poly(methyl methacrylate) (PMMA) and silica in a PMMA/silica nanocomposite was investigated by differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). The glass transition temperature (T_g) values of the syndiotactic (st-) and atactic (at-) PMMA/silica nanocomposites are higher than those of the neat PMMA. Conversely, the T_g of the isotactic (it-) PMMA/silica nanocomposite is slightly higher than that of the neat it-PMMA. DSC and XRD results suggest that the restriction of the PMMA chain mobility in the silica nanoparticle interfacial region heightens as the syndiotactic content increases. FT-IR results show that this phenomenon is caused by the interaction between the carbonyl group of PMMA and the silanol group on the silicon dioxide surface. Therefore, it can be concluded that the syndiotactic-rich PMMA has a significantly different molecular mobility from that of the neat PMMA in the interfacial region with silica nanoparticle surface than isotactic-rich PMMA.     

Thermal‐Insulation,Electrical, and Mechanical Properties of Highly‐Expanded PMMA/MWCNT Nanocomposite Foams Fabricated by Supercritical CO2 Foaming

Foaming behavior of poly(methyl methacrylate) (PMMA)/multi‐walled carbon nanotubes (MWCNTs) nanocomposites and thermally‐insulating, electrical, and mechanical properties of the nanocomposite foams are investigated. PMMA/MWCNT nanocomposites containing various amounts of MWCNTs are first prepared by combining solution and melt blending methods, and then foamed using CO₂. The foaming temperature and MWCNT content are varied for regulating the structure of PMMA/MWCNT nanocomposite foams. The electrical conductivity measurement results show that MWCNTs have little effect on the electrical conductivity of foams with large expansion ratio. Thermal conductivities of both solid and foamed PMMA/MWCNT nanocomposites are measured to evaluate their thermally insulating properties. The gas conduction, solid conduction, and thermal radiation of the foams are calculated for clarifying the effects of cellular structure and MWCNT content on thermal insulation properties. The result demonstrates that MWCNTs endowed foams with enhanced thermal insulation performance by blocking thermal radiation. Moreover, the compressive testing shows that MWCNTs improve the compressive strength and rigidity of foams. This research is essential for optimizing environmentally friendly thermal insulation nanocomposite foams with enhanced thermal‐insulation and compressive mechanical properties.     

Preparation and performance of CdS-hyperbranched poly(arylene ether ketone) nanocomposite materials

A new kind of CdS-hyperbranched poly (arylene ether ketone) (HP-PAEK) nanocomposite was prepared in dimethylformamide solution by carboxylic-functionalised HP-PAEK as surface modifier without ligand exchange. The CdS/HP-PAEK nanocomposites were characterised through ultraviolet–visible and photoluminescence spectroscopy. The experimental results of photoluminescence measurement showed that the nanocomposites had obvious luminescence properties. The formation and size of CdS quantum dots were determined by Fourier transform infrared spectroscopy and transmission electron microscopy. The thermal properties of CdS/HP-PAEK nanocomposites were analysed by differential scanning calorimetry and thermogravimetric analysis. Owing to the introduction of CdS nanoparticles, the nanocomposites exhibited excellent heat resistance and higher fluorescent quantum efficiency.     

Investigation of the elastic properties of poly (methyl methacrylate) reinforced with graphene nanoplatelets

The technique for synthesis of poly (methyl methacrylate) (PMMA) by atom transfer radical polymerization has been strengthened by using graphene nanoplatelets (GNPs) to enhance the elastic properties of the polymer. In order to improve practical, economical and mechanical performance, the requirements for effective implementation of production control as a smart bulk polymer nanocomposite were determined for cost-effective bulk production. Three-dimensional inspection (using an ultrasound interrogation method for the whole volume under test) confirmed the synthesis of the nanocomposite to be free of agglomeration and bubbles. As a result of this elimination of defects, an enhancement in compressive strength of 42.7% was achieved and the Rockwell hardness was increased by 19.9% through the addition of GNPs at 2 wt% by mass. The deformation and mechanical failure properties have been characterized in the mechanical enhancement of the polymer nanocomposite. Elastic parameters determined using ultrasound testing identified that changes in the structural features following the addition of these GNPs were uniquely connected to the enhancements in these elastic parameters (such as Young's modulus, Poisson's ratio, shear modulus, and microhardness) of the PMMA/GNPs nanocomposite.     

Synthesis of Volcano‐Like CdS/Organic Nanocomposite

Cadmium sulfide/organic nanocomposites, which were based on long nanowires, were synthesized by a simple reaction between cadmium nitrate and thioglycolic acid (TGA) at room temperature. The products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected‐area electron diffraction (SAED), Fourier transform infrared (FTIR) spectra, and thermogravimetric analysis (TG). The CdS/organic nanocomposites was decomposed into pure wurtzite CdS nanorods through hydrothermal treatment at 190°C. Photoluminescence (PL) spectra were used to study the optical properties of CdS/organic composite and pure CdS. It is found that the emission maximum of the CdS/TGA nanocomposite is significantly blue‐shifted, and the intensity is highly enhanced as compared to the luminescence spectrum of the bare CdS nanorods.     

Synthesis of CdS nanoparticles dispersed within solutions and polymer films using amphiphilic urethane acrylate chains

In this study, a new process for preparation of CdS/polymer nanocomposite films using a new amphiphilic oligomer chain (Urethane Acrylate Nonionomer: UAN) is presented. UAN chains have hydrophilic polyethylene oxide segments and polypropylene oxide-based hydrophobic segments as part of the same backbone. In addition, these chains also have reactive vinyl groups at their hydrophobic segments. For the preparation of CdS nano-colloid solutions, UAN chains acted as a stabilizer for CdS nanoparticles dispersed in a solvent. For the fabrication of CdS/polymer nanocomposite films, UAN chains in CdS nano-colloid solutions were polymerized through reactions between their vinyl groups, resulting in the formation of CdS nanoparticle dispersed films swollen by the solvent. The nature of the solvent used strongly influenced the size of the CdS nanoparticles, which was confirmed by UV absorption spectra, PL emission spectra and TEM images. Smaller sized CdS nanoparticles were formed in higher polar solvents such as DMAc and methanol, which can be explained by the higher solubility of UAN chains and the more effective dissociation and stabilization of cadmium salts and CdS nanoparticles by UAN chains in the polar solvent.     

Facile Bulk Synthesis of Homogeneous and Transparent Nanocrystals Hybrids via In Situ Transformation of Ionomers into CdS Quantum-Dot-Polymer

We systemically report on a method for fabricating bulk CdS QD-polymer hybrids nanocomposites with tunable control photoluminescence (PL) by using as-prepared ionomers. Firstly, we rationally designed to synthesize well-dispersed PMMA/Cd(AA)₂ (cadmium acrylate) ionomers containing different concentrations of Cd²⁺ ion clusters via free-radical polymerization. And then, we introduced H₂S gas into the ionomer solutions to obtain transparent PMMA/CdS QD-polymers in situ. Subsequently, we employed PMMA/CdS QD-polymers to further produce claviform CdS/PMMA hybrid nanocomposites via in situ bulk polymerization. The properties of as-prepared QD-polymers and their hybrid nanocomposites were thoroughly investigated by Ultraviolet–visible (UV-vis), transmission electron microscope (TEM), Fourier transform infrared spectra (FT-IR), photoluminescence (PL), thermogravimetric analyses (TGA) measurements. We have found that these QD-polymers exhibit uniform dispersity, good optical property and an obvious advantage on thermal stability, along with facilely producing bulk nanocrystal/polymer hybrid nanocomposites with a large scale.     

Cure behavior of epoxy resin/CdS/2,4-EMI nanocomposites investigated by dynamic torsional vibration method (DTVM)

Summary Epoxy resin/CdS nanocomposite was prepared by a novel method and its cure behavior was investigated by the HLX-II Resin Curemeter based on the dynamic torsional vibration method (DTVM). The non-equilibrium thermodynamic fluctuation theory, the Avrami equation and the Flory’s gelation theory have been used to analysis the cure behavior of the composite systems with different CdS and cure agent loadings at various temperatures. The results show that the addition of CdS nanoparticles reduces the gel time t_g, but has little effect on the mechanism of the cure reaction. The theoretical prediction is in good agreement with the experimental results. The Avrami exponent of n decreases a little when the temperature increases.     

鞭毛辅助CdS/TiO_2纳米复合薄膜的制备以及显著增强的光电催化活性

采用鞭毛作为生物模板剂制备Cd S/TiO_2复合纳米结构薄膜,采用SEM、XRD、IR、紫外-可见漫反射和电化学工作站等对其结构和光电化学性质进行表征。结果表明,鞭毛的引入不但减小了CdS颗粒尺寸和增大了比表面积,而且改善了复合材料的带隙结构。该薄膜可见光光电催化活性比未加入鞭毛的空白样品高1.4倍。提供了一个利用生物模板剂控制半导体纳米结构单元生长与组装及改善光电性能的简单方法。     

ZrO2/聚甲基丙烯酸甲酯纳米复合物:制备及其在聚合物阵列中的分散（英文）

ZrO2/PMMA nanocomposite particles are synthesized through an in-situ free radical emulsion polymerization based on the silane coupling agent (Z-6030) modified ZrO2 nanoparticles, and the morphology, size and its distribution of nanocomposite particles are investigated. Scanning electron microscopy (SEM) images demonstrate that the methyl methacrylate (MMA) feeding rate has a significant effect on the particle size and morphology. When the MMA feeding rate decreases from 0.42ml·min-1 to 0.08ml·min-1 , large particles (about 200-550nm) will not form, and the size distribution become narrow (36-54nm). The average nanocomposite particles size increases from 34nm to 55nm, as the MMA/ZrO2 nanoparticles mass ratio increased from 4:1 to 16:1. Regular spherical ZrO2/PMMA nanocomposite particles are synthesized when the emulsifier OP-10 concentration is 2mg·ml-1. The nanocomposite particles could be mixed with VAc-VeoVa10 polymer matrix just by magnetic stirring to prepare the ZrO2 /PMMA/VAc-VeoVa10 hybrid coatings. SEM and atomic force microscopy (AFM) photos reveal that the distribution of the ZrO2 /PMMA nanocomposite particles in the VAc-VeoVa10 polymer matrix is homogenous and stable. Here, the grafted-PMMA polymer on ZrO2 nanoparticles plays as a bridge which effectively connects the ZrO2 nanoparticles and the VAc-VeoVa10 polymer matrix with improved comparability. In consequence, the hybrid coating with good dispersion stability is obtained.     

The disorderly exfoliated LDHs/PMMA nanocomposite synthesized by in situ bulk polymerization

A new nanocomposite—disorderly exfoliated layered double hydroxides/poly(methyl methacrylate) (LDHs/PMMA)—was prepared by a two-stage process with an in situ bulk polymerization of methyl methacrylate (MMA) in the presence of 10-undecenoate intercalated LDH (LDH-U). The LDH-U was prepared using the co-precipitation method. The structural and compositional details of the LDH-U were determined by X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FT-IR), ²⁷Al and ¹³C magic-angle spinning nuclear magnetic resonance (²⁷Al and ¹³C MAS NMR), elemental analysis (EA), inductively coupled plasma-mass (ICP) and transmission electron microscopy (TEM). During the preparation of LDHs/PMMA nanocomposite, XRD and TEM were also employed to monitor the formation of the exfoliated LDHs/PMMA nanocomposite and the dispersion behavior of the LDH layers, respectively. The pre-polymerization process exfoliates LDH layers within pre-polymer, according to the XRD and TEM results. Additionally, the LDHs/PMMA nanocomposite contained 5 wt% LDH-U, indicating that the LDH layers were well exfoliated and dispersed in the PMMA matrix in a disordered fashion.     

Improving the physical properties of PEA/PMMA blends by the uniform dispersion of clay platelets

Poly(ethyl acrylate) (PEA)/poly(methyl methacrylate) (PMMA) emulsion blends that were combined with unmodified montmorillionite (MMT) to improve the physical properties via nanocomposite formation. We prepared a cationic PEA/PMMA latex and used a heterocoagulation process to create a homogeneous dispersion of the clay platelets in the matrix. The cationic PEA/PMMA emulsion blends were prepared using a cationic initiator in the presence of free surfactant, cetyl trimethylammonium bromide (CTABr), followed by mixing with an aqueous slurry of MMT. The PEA/PMMA-MMT nanocomposites could be processed at low temperatures. Low temperature processing prevented the commonly observed discoloration associated with many thermoplastic nanocomposites. DSC, SAXS, TEM and AFM were used to study the dispersion of MMT and morphology of PEA/PMMA-MMT nanocomposites. Tensile stress, elongation at break and Young's modulus demonstrated a significant reinforcing effect of clay.     

In situ growth of well-dispersed CdS nanocrystals in semiconducting polymers

A straight synthetic route to fabricate hybrid nanocomposite films of well-dispersed CdS nanocrystals (NCs) in poly[2-methoxy-5-(2''-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) is reported. A soluble cadmium complex [Cd(SBz)₂]₂·MI, obtained by incorporating a Lewis base (1-methylimidazole, MI) on the cadmium bis(benzyl)thiol, is used as starting reagent in an in situ thermolytic process. CdS NCs with spherical shape nucleate and grow well below 200°C in a relatively short time (30 min). Photoluminescence spectroscopy measurements performed on CdS/MEH-PPV nanocomposites show that CdS photoluminescence peaks are totally quenched inside MEH-PPV, if compared to CdS/PMMA nanocomposites, as expected due to overlapping of the polymer absorption and CdS emission spectra. The CdS NCs are well-dispersed in size and homogeneously distributed within MEH-PPV matrix as proved by transmission electron microscopy. Nanocomposites with different precursor/polymer weight ratios were prepared in the range from 1:4 to 4:1. Highly dense materials, without NCs clustering, were obtained for a weight/weight ratio of 2:3 between precursor and polymer, making these nanocomposites particularly suitable for optoelectronic and solar energy conversion applications.     

溶胶-凝胶法制备TiO2/PMMA纳米复合材料的研究

通过溶胶-凝胶法制备了TiO2溶胶,与聚甲基丙烯酸甲酯(PMMA)进行杂化处理制得了TiO2/PMMA纳米复合材料.并将不同量的溶胶与几种不同摩尔质量的PMMA进行复合,得到多种样品.通过透射电镜(TEM)、红外光谱(FTIR)、紫外-可见光谱(UV-Vis)、热失重(TGA)分析研究了TiO2/PMMA纳米复合材料的结构和性能,从而由溶胶含量、PMMA摩尔质量等不同因素对复合材料性质产生的影响作出了解释.结果表明当溶胶含量为1％、PMMA的摩尔质量较低(37.3万g/mol)时,TiO2微粒在聚合物中的分散性较好,粒径较均一,TiO2的加入使得材料的抗紫外线性和热稳定性都有所提高.     

Optical and physical properties of zirconium dioxide reinforced poly(methyl methacrylate) nanocomposite films

The objective of this study was to investigate the fundamental aspects of acrylic resin and zirconia nanoparticle interaction to analyze the optical properties and subsequent changes in refractive index with incremental loading of nanoparticles. Poly(methyl methacrylate) (PMMA) reinforced with zirconia nanoparticles were prepared by dip coating, spin coating and solvent casting techniques. An overall understanding of the polymer nanocomposite film has been achieved using the spectroscopic and morphological studies. The vital aspect of this whole study is to derive a simple yet an efficient nanocomposite film capable of imparting extraordinary optical properties. Within the limitations of this research a very crucial property of the material has been revealed. The RI as well as the optical transparency of the nanocomposite film has been steadily maintained with a significant increase of RI by the magnitude of 0.06 and ~100% light transmittance on incorporation of pure zirconia nanoparticles into PMMA matrix has been achieved. The best technique found was spin coating as it could yield thin films and better transparency and higher refractive index.     

Synthesis and characteristics of poly(methyl methacrylate)/expanded graphite nanocomposites

In this work, we synthesized poly(methyl methacrylate) (PMMA)/expanded graphite (EG) nanocomposites by a new polymerization method. The volume electrical conductivity of the nanocomposite prepared by this way is very high (when the content of EG is about 8 wt %, the conductivity could reach 60 S/cm). The structure of the nanocomposite was investigated by SEM, TEM, IR, and XRD. And we found temperature and voltage were important parameters of governing the electrical conductivity of PMMA/EG nanocomposites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1427–1431, 2006     

Poly(methyl methacrylate)/clay nanocomposites by photoinitiated free radical polymerization using intercalated monomer

A series of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposite were prepared by successfully dispersing the inorganic nanolayers of MMT clay in an organic PMMA matrix via in situ photoinitiated free radical polymerization. Methyl methacrylate monomer was first intercalated into the interlayer regions of organophilic clay hosts by “click” chemistry followed by a typical photoinitiated free radical polymerization. The intercalated monomer was characterized by FT-IR spectroscopy, elemental analysis and thermogravimetric analysis methods. The intercalation ability of the modified monomer and exfoliated nanocomposite structure were confirmed by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Thermal stability of PMMA/MMT nanocomposites was also studied by both differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).