Characterization and properties of in situ emulsion polymerized poly(methyl methacrylate)/graphene nanocomposites

Poly(methyl methacrylate) (PMMA)/graphene nanocomposites were prepared by in situ emulsion polymerization. Raman and Fourier transform infrared spectra showed that PMMA polymer contained partially reduced graphite oxide. Dynamic mechanical analysis and differential scanning calorimetry analysis showed that graphene in the PMMA matrix acted as reinforcing filler; it enhanced the storage moduli and glass transition temperatures of the nanocomposites. Thermogravimetric analysis showed that the thermal stability of the nanocomposites increased by ca. 35 °C. The electrical conductivity of nanocomposite with 3 wt.% graphite oxide was 1.5 S m⁻¹ at room temperature.     

In situ thermal reduction of graphene oxide for high electrical conductivity and low percolation threshold in polyamide 6 nanocomposites

Electrically conductive and thermally stable polyamide 6 (PA 6) nanocomposites were prepared through one-step in situ polymerization of ε-caprolactam monomer in the presence of electrically insulating and thermally unstable graphene oxide (GO) nanosheets. These nanocomposites show a low percolation threshold of ∼0.41 vol.% and high electrical conductivity of ∼0.028 S/m with only ∼1.64 vol.% of GO. Thermogravimetric analysis and X-ray photoelectron spectroscopy results of GO before and after thermal treatment at the polymerization temperature indicate that GO was reduced in situ during the polymerization process. X-ray diffraction patterns and scanning electron microscopy observation confirm the exfoliation of the reduced graphene oxide (RGO) in the PA 6 matrix. The low percolation threshold and high electrical conductivity are attributed to the large aspect ratio, high specific surface area and uniform dispersion of the RGO nanosheets in the matrix. In addition, although GO has a poor thermal stability, its PA 6 nanocomposite is thermally stable with a satisfactory thermal stability similar to those of neat PA 6 and PA 6/graphene nanocomposite. Such a one-step in situ polymerization and thermal reduction method shows significant potential for the mass production of electrically conductive polymer/RGO nanocomposites.     

Analysis of the electrical and rheological behavior of different processed CNF/PMMA nanocomposites

Carbon nanofiber (CNF)/poly(methyl methacrylate) (PMMA) nanocomposites were prepared via melt-compounding, solvent casting and in situ polymerization. Mechanical properties, rheological behavior and electrical resistivity were investigated in specimens with varying CNF loadings. The three processing techniques were compared. Improved properties were obtained in the solvent processed and in situ polymerized composites. The rheological and electrical percolation of these nanocomposites appeared in the same concentration set (between 1 and 5 wt%). No changes were found in melt-compounding, even by the addition of 10 wt% of CNFs. Electrical resistivity of the samples prepared by solvent casting was measured before and after pressing in the hot plate press. It is remarkable that in the non-pressed samples the CNFs formed an efficient 3-D conductive network, yielding composites with percolation thresholds even six orders of magnitude lower than after pressing, where this 3-D network was destroyed.     

Shape memory and physical properties of poly(ethyl methacrylate)/Na-MMT nanocomposites prepared by macroazoinitiator intercalated in Na-MMT

A macroazoinitiator (MAI) containing a poly(ethylene glycol) (PEG) segment was intercalated in the gallery of sodium montmorillonite (Na-MMT) and this intercalated MAI was used in the preparation of Na-MMT/poly(ethyl methacrylate) (PEMA) nanocomposites via in situ radical polymerization of ethyl methacrylate. The X-ray diffraction pattern and the morphology observed with a transmission electron microscope showed that Na-MMT intercalated with a PEG segment was heterogeneously dispersed in the polymer matrix. Thus Na-MMT intercalated with a PEG segment effectively enhanced the mechanical properties of PEMA. Shape memory behavior and rheological properties showed that Na-MMT intercalated with a PEG segment performed its role as a physical crosslinker effectively even with 1.2 wt% of Na-MMT.     

Dielectric properties of montmorillonite clay filled poly(vinyl alcohol)/poly(ethylene oxide) blend nanocomposites

Organic–inorganic nanocomposites of poly(vinyl alcohol) (PVA)–poly(ethylene oxide) (PEO) blend filled with montmorillonite (MMT) nanoclay up to 10 wt.% concentration were synthesized by aqueous solution-cast technique. The complex dielectric function, electrical conductivity, electric modulus and impedance spectra of the nanocomposites were measured in the frequency range 20 Hz–1 MHz at ambient temperature. A direct correlation was observed between the real part of dielectric function and the mean relaxation time of the polymer chain segmental dynamics, with the exfoliated and intercalated MMT clay structures, and the extent of miscibility between PVA and PEO due to hydrogen bonded bridging through exfoliated MMT clay nanosheets. The large increase of dielectric relaxation time revealed that the dispersed exfoliated nanoscale MMT clay in the polymers blend matrix produces a large hindrance to the polymer chain dynamics. Results confirm that the real part of dielectric function of the nanocomposites can be tailored by varying amount of MMT clay filler for their use as nanodielectric materials in the microelectronic technology.     

Effects of modified Clay on the morphology and thermal stability of PMMA/clay nanocomposites

The potential to improve the mechanical, thermal, and optical properties of poly(methyl methacrylate) (PMMA)/clay nanocomposites prepared with clay containing an organic modifier was investigated. Pristine sodium montmorillonite clay was modified using cocoamphodipropionate, which absorbs UVB in the 280–320 nm range, via ion exchange to enhance the compatibility between the clay platelets and the methyl methacrylate polymer matrix. PMMA/clay nanocomposites were synthesized via in situ free-radical polymerization. Three types of clay with various cation-exchange capacities (CEC) were used as inorganic layered materials in these organic–inorganic hybrid nanocomposites: CL42, CL120, and CL88 with CEC values of 116, 168, and 200 meq/100 g of clay, respectively. We characterized the effects of the organoclay dispersion on UV resistance, effectiveness as an O₂ gas barrier, thermal stability, and mechanical properties of PMMA/clay nanocomposites. Gas permeability analysis demonstrated the excellent gas barrier properties of the nanocomposites, consistent with the intercalated or exfoliated morphologies observed. The optical properties were assessed using UV–Visible spectroscopy, which revealed that these materials have good optical clarity, UV resistance, and scratch resistance. The effect of the dispersion capability of organoclay on the thermal properties of PMMA/clay nanocomposites was investigated by thermogravimetric analysis and differential scanning calorimetry; these analyses revealed excellent thermal stability of some of the modified clay nanocomposites.     

Improved thermal properties of graphene oxide-incorporated poly(methyl methacrylate) microspheres

Graphene, a single layer of carbon atoms in a two-dimensional lattice, has attracted considerable attention owing to its unique physical, chemical and mechanical properties. In particular, because of its excellent thermal properties such as high thermal conductivity and good thermal stability, graphene has been regarded as a one of the promising candidates for the reinforcing fillers on the polymer composites field. In this study, we prepared the poly(methyl methacrylate) (PMMA)/graphene oxide (GO) nanocomposite by a simple solution mixing process, and examined the thermal reinforcing effects of GO on a PMMA matrix. Using thermogravimetric analysis, differential scanning calorimeter, and thermal conductivity meter, we investigated the effects of GO on the thermal properties of PMMA/GO nanocomposites. With 3 wt% of GO loading, the glass transition temperature (Tg) of the PMMA/GO nanocomposite were increased by more than 7 degrees C and the thermal conductivity of which also improved 1.8 times compared to pure PMMA.     

The preparation of high performance and conductive poly (vinyl alcohol)/graphene nanocomposite via reducing graphite oxide with sodium hydrosulfite

Sodium hydrosulfite is used to reduce graphite oxide in current study. The preparation of poly (vinyl alcohol) (PVA)/graphene nanocomposites is realized using two simple steps: the synthesis of PVA/graphite oxide (GO) nanocomposites film and immersion of such a film in the reducing agent aqueous solution. This method prohibits the agglomeration of GO during direct reduction in PVA/GO aqueous solution, and opens a new way to scale up the production of graphene nanocomposites using a simple reducing agent. A 40% increase in tensile strength and 70% improvement in elongation at break have been obtained with only the addition of 0.7 wt.% of reduced graphite oxide. Furthermore, a good level of conductivity and a variation in the surface property of the prepared films have been observed for the composites containing graphene.     

The intercalation of poly(methyl methacrylate)/aluminophosphate nanocomposites and the properties improvement

Poly(methyl methacrylate) (PMMA)/dodecylamine templated lamellar aluminophosphate (DDA-LAP) intercalated nanocomposites are prepared by in situ bulk polymerization of MMA. The intercalated structure is characterized. With the intercalation of DDA-LAP in PMMA matrix, the glass-transition temperatures of nanocomposites (T_g) are increased. The nanocomposites obtained keep relatively high transparency in optical property and have a significant improvement in mechanical properties and thermal stability. The mechanism for the properties enhancement is investigated. The strong interfacial interaction between the aluminophosphate layers and the PMMA chains, the homogeneously distribution and the graphitized char formation during heating are three key roles for the properties improvement.     

Morphology,thermal and mechanical properties of PVC/MMT nanocomposites prepared by solution blending and solution blending + melt compounding

Two types of montmorillonite (MMT), natural sodium montmorillonite (Na-MMT) and organically modified montmorillonite (OMMT), in different amounts of 1, 2, 5, 10 and 25 phr (parts per hundred resin), were dispersed in rigid poly (vinyl chloride) by two different methods: solution blending and solution blending + melt compounding. The effects on morphology, thermal and mechanical properties of the PVC/MMT nanocomposites were studied by varying the amount of Na-MMT and OMMT in both methods. SEM and XRD analysis revealed that possible intercalated and exfoliated structures were obtained in all of the PVC/MMT nanocomposites. Thermogravimetric analysis revealed that PVC/Na-MMT nanocomposites have better thermal stability than PVC/OMMT nanocomposites and PVC. In general, PVC/MMT nanocomposites prepared by solution blending + melt compounding revealed improved thermal properties compared to PVC/MMT nanocomposites prepared by solution blending. Vicat tests revealed a significant decrease in Vicat softening temperature of PVC/MMT nanocomposites prepared by solution blending + melt compounding compared to unfilled PVC.     

Optical and mechanical anisotropies of aligned electrospun nanofibers reinforced transparent PMMA nanocomposites

This study aims to assess the nanofiber directionality effects on optomechanical properties of a widely used transparent thermoplastic poly(methyl methacrylate) (PMMA). Aligned fiber-hybrid mats consisted of nylon-6 (PA-6) nanofibers and PMMA microfibers are prepared using a self-blending co-electrospinning method, followed by hot press molding to fabricate into transparent nanocomposites. Effects of nanofiber orientation degree in two orthogonal directions and loading fraction on the optomechanical behavior of the nanocomposites are examined. Optical transmittance differences parallel and perpendicular to the nanofibers’ orientation are found to vary in a range of 3.9–5.4% at 589 nm, and strong mechanical anisotropy is observed with the 1% PA-6/PMMA nanocomposites. A maximal of 3% PA-6 nanofiber loading maintains the nanocomposite high transmittance (>75%) with improved strength and toughness along the nanofiber axis. This study reveals evident anisotropic optomechanical properties of transparent nanocomposites, and highlights the great designability of transparent nanocomposites by using aligned nanofibers as the designing elements.     

聚甲基丙烯酸甲酯/膨胀石墨纳米导电复合材料的制备与表征

通过原位插层聚合制备了聚甲基丙烯酸甲酯/膨胀石墨纳米导电复合材料,其室温导电渗滤阈值约为3%(质量分数),当膨胀石墨的质量分数为8%时,室温电导率可高达60 S/cm。通过TEM、SEM观察了复合材料的形貌,用DSC测定其热力学性能并探讨了不同外加电压对PMM A/膨胀石墨纳米导电复合材料体积电导率的影响,同时研究了复合材料的拉伸强度。     

Highly conducting poly(methyl methacrylate)/carbon nanotubes composites: Investigation on their thermal, dynamic-mechanical, electrical and dielectric properties

Nanocomposites of poly(methyl methacrylate) (PMMA) containing various multi-walled carbon nanotubes (MWCNT) contents were prepared using melt mixing. Several techniques were employed to study the influence of the MWCNT addition on the thermal, mechanical, electrical and dielectric properties of the PMMA matrix. The electrical percolation threshold (p_c) was found to be 0.5 vol.% by performing AC and DC conductivity measurements. Significantly high conductivity levels (σ_dc) were achieved: σ_dc exceeds 10⁻² S/cm already at 1.1 vol.%, the criterion for EMI shielding (σ_dc > 10⁻¹ S/cm) is fulfilled at 2.9 vol.%, and the highest loaded sample (5.2 vol.%) gave a maximum value of 0.5 S/cm. Dielectric relaxation spectroscopy measurements in broad frequency (10⁻¹−10⁶ Hz) and temperature ranges (−150 to 170 °C) indicated weak polymer-filler interactions, in consistency with differential scanning calorimetry and dynamic-mechanical analysis findings. Weak polymer-filler interactions and absence of crystallinity facilitate the achievement of high conductivity levels in the nanocomposites.     

Exfoliated poly(methyl methacrylate)/MgFe-layered double hydroxide nanocomposites with small inorganic loading and enhanced properties

The novel exfoliated polymer nanocomposites (PMMA/MgFe(DS)-LDH) were synthesized by in situ polymerization based on poly(methyl methacrylate) (PMMA) and dodecyl sulfate-intercalated MgFe-layered double hydroxide (MgFe(DS)-LDH). The participation of Fe³⁺ ion is found to play an important role in the improvement of thermal stability of nanocomposites with small inorganic loading and well-dispersed inorganic components. The thermal degradation mechanism was discussed.     

Effect of interfacial interaction between graphene oxide derivatives and poly(vinyl chloride) upon the mechanical properties of their nanocomposites

In this work, graphene oxide (GO) and poly(methyl methacrylate) (PMMA) grafted GO reduced by dopamine (rGO@PDA-g-PMMA) were employed to determine the key factor responsible for the improved mechanical properties of poly(vinyl chloride) (PVC). Dopamine was utilized to reduce GO and simultaneous coating of polydopamine (PDA) on the GO surface. rGO@PDA-g-PMMA was prepared by a combination of mussel-inspired chemistry and surface-initiated atom transfer radical polymerization techniques. The resulting derivatives were characterized by thermogravimetric analysis, Fourier transforms infrared spectroscopy, X-ray diffraction, and Raman spectroscopy. PVC nanocomposites containing GO derivatives were prepared by solution blend and the nanocomposite films were obtained using a casting method. The mechanical properties of the nanocomposites were studied using both dynamic mechanical thermal analysis and tensile testing. The results revealed that the vital components responsible for the improved mechanical properties and thermal stability of rGO@PDA-g-PMMA/PVC nanocomposites compared to pure PVC are the interfacial interactions between the GO derivatives and the PVC matrix.     

添加剂对聚吡咯/氧化石墨纳米复合材料结构和性能的影响

采用单体原位聚合法制备了三种聚吡咯/氧化石墨纳米复合材料。通过XRD、FT-IR和TEM对产物进行结构表征,探讨了未加添加剂及分别以N aOH和十二烷基苯磺酸钠为添加剂制得的聚吡咯/氧化石墨纳米复合材料的结构与性能的差别。结果表明,未加添加剂和以N aOH为添加剂时产物为非晶态的剥离型聚吡咯/氧化石墨纳米复合材料;而以十二烷基苯磺酸钠为添加剂时可得到具有层状有序结构的插层型聚吡咯/氧化石墨纳米复合材料。插层型聚吡咯/氧化石墨纳米复合材料的导电和电化学性能优于剥离型聚吡咯/氧化石墨纳米复合材料,它们的提高归因于聚吡咯分子链共轭程度的增加。     

Structural characterization, thermal and mechanical properties of polyurethane/CoAl layered double hydroxide nanocomposites prepared via in situ polymerization

Dodecyl sulfate (DS), one kind of sulfate anion, was intercalated in the interlayer space between CoAl layered double hydroxide (CoAl-LDH) layers, and then polyurethane (PU) based nanocomposites were prepared by in situ intercalation polymerization with different amounts of the organo-modified CoAl-LDH. An exfoliated dispersion of CoAl-LDH layers in PU matrix was verified by the disappearance of the (0 0 3) reflection of the XRD results when the LDH loading was less than 2.0 wt%. Tensile testing indicated that excellent mechanical properties of PU/LDH nanocomposites were achieved. The weak alkaline catalysis of DS to polyurethane chains, combined with the dehydration and structural degradation of the LDH below 300 °C, accounted for the process of proceeded degradation as shown in TGA results. The real-time FTIR revealed that the as-prepared nanocomposites had a slower thermo-oxidative rate than neat PU from 160 °C to 340 °C, probably due to the barrier effect of LDH layers. These results suggested potential applications of CoAl-LDH as a promising flame retardant in PUs.     

Processing and functionalization effect in CNF/PMMA nanocomposites

We compare results for polymer nanocomposites of poly(methyl methacrylate) (PMMA) and carbon nanofibers (CNFs) prepared by three different processing techniques: melt-compounding, solvent casting and in situ polymerization. Moreover, CNFs were used as received and functionalized with oxygen and nitrogen groups. Mechanical properties and rheological behavior of the composites revealed a strong filler-polymer interface interaction in the in situ polymerized composites, even through covalent binding, while was noticed to be weaker in melt-compounding and solvent casting. In addition, in these two further cases, the addition of CNFs, pristine or functionalized, improved toughness of the PMMA.     

Preparation and luminescent properties of GdOF:Ce,Tb nanoparticles and their transparent PMMA nanocomposites

GdOF:Ce, Tb nanoparticles and their poly (methyl methacrylate) (PMMA) nanocomposites have been successfully prepared by a thermolysis route and thermal polymerization of methyl methacrylate (MMA) monomer, respectively. The obtained nanoparticles and nanocomposites are characterized by XRD, EDS, TEM, FTIR, TGA, UV–Vis and PL spectrum. The as-synthesized transparent GdOF:Ce, Tb/PMMA nanocomposites exhibit green photoluminescence under the irradiation of 254 nm UV lamp due to the incorporation of luminescent GdOF:Ce, Tb nanoparticles into the PMMA matrix. The present route would provide a general strategy to prepare other functional nanocomposites.     

Electrical and mechanical properties of PMMA/reduced graphene oxide nanocomposites prepared via in situ polymerization

We report the effect of filler incorporation techniques on the electrical and mechanical properties of reduced graphene oxide (RGO)-filled poly(methyl methacrylate) (PMMA) nanocomposites. Composites were prepared by three different techniques, viz. in situ polymerisation of MMA monomer in presence of RGO, bulk polymerization of MMA in presence of PMMA beads/RGO and by in situ polymerization of MMA in presence of RGO followed by sheet casting. In particular, the effect of incorporation of varying amounts (i.e. ranging from 0.1 to 2 % w/w) of RGO on the electrical, thermal, morphological and mechanical properties of PMMA was investigated. The electrical conductivity was found to be critically dependent on the amount of RGO as well as on the method of its incorporation. The electrical conductivity of 2 wt% RGO-loaded PMMA composite was increased by factor of 10⁷, when composites were prepared by in situ polymerization of MMA in the presence of RGO and PMMA beads, whereas, 10⁸ times increase in conductivity was observed at the same RGO content when composites were prepared by casting method. FTIR and Raman spectra suggested the presence of chemical interactions between RGO and PMMA matrix, whereas XRD patterns, SEM and HRTEM studies show that among three methods, the sheet-casting method gives better exfoliation and dispersion of RGO sheets within PMMA matrix. The superior thermal, mechanical and electrical properties of composites prepared by sheet-casting method provided a facile and logical route towards ultimate target of utilizing maximum fraction of intrinsic properties of graphene sheets.