Chemical modification of TiO2 nanoparticles as an effective way for encapsulation in polyacrylic shell via emulsion polymerization

Encapsulation of inorganic nanoparticles by polymers is one of the interesting research topics that lead to the synthesis of nanocomposites. These nanocomposite materials comprise the properties of both organic polymer and inorganic nanoparticles. Here, hybrid latex particles with core–shell nanostructure were prepared via semi-batch emulsion polymerization. Copolymers of (methyl methacrylate-butyl acrylate) and (dimethylaminoethyl methacrylate-butyl acrylate-acrylic acid) were formed as the inner and outer layers, respectively on the surface of modified TiO₂ nanoparticles as the core. In order to create compatibility between inorganic and polymeric phases, modification of TiO₂ nanoparticles was performed with glycidyl methacrylate with an optimized procedure for the first time and then emulsion polymerization was carried out. The products of each step were fully characterized. The results of dynamic light scattering, TEM and SEM analyses proved the formation of encapsulated hybrid latex particles. DLS and SEM data revealed that the sizes of nanocomposite particles vary between 85 and 120 nm for 0–5 wt% of the modified TiO₂ nanoparticles. Physico-mechanical properties of the obtained nanocomposite films were studied by DMTA. It was found that using only 3 wt% of modified TiO₂ improved those properties of resulting films remarkably.     

The effect of clay modification on the mechanical properties of poly(methyl methacrylate)/organomodified montmorillonite nanocomposites prepared by in situ suspension polymerization

Poly(methylmethacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were prepared by in situ suspension polymerization. MMT was previously organically modified by different modification agents [dioctadecyl dimethyl ammonium chloride (DODAC) and methacrylatoethyltrimethyl ammonium chloride (MTC)] and different modification method (cation‐exchange reaction and grafting reaction), ultimately giving rise to five kinds of organomodified MMT (OMMT). The structure of the OMMT was studied by Wide angle X‐ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). Meanwhile, the structure of the PMMA/MMT nanocomposites microspheres was also investigated by WAXD. The molecular weight of the polymers extracted from PMMA/MMT nanocomposites was measured by gel permeation chromatograph (GPC). Finally, the mechanical properties of these PMMA/MMT nanocomposites were studied in detail. It was found that large interlayer spacing (d₀₀₁) of OMMT could not entirely ensure an exfoliated structure of resultant PMMA/MMT nanocomposites, while OMMT with relative small d₀₀₁ could still yield exfoliated structure as long as the compatibility between OMMT and polymer matrix was favorable. In addition, the results of mechanical investigation indicated that the compatibility between OMMT and PMMA matrix turned out to be the dominant factor deciding the final mechanical properties of PMMA/MMT nanocomposites. POLYM. COMPOS., 37:1705–1714, 2016. © 2014 Society of Plastics Engineers     

The characterization of organic modified clay and clay‐filled PMMA nanocomposite

Recently, polymer–clay hybrid materials have received considerable attention from both a fundamental research and application point of view. 1 - 3 This organic–inorganic hybrid, which contains a nanoscale dispersion of the layered silicates, is a material with greatly improved physical and mechanical characteristics. These nanocomposites are synthesized through in situ polymerization or direct intercalation of the organically modified layered silicate (OLS) into the polymer matrix. Thus, understanding the relationship between the molecular structure and the thermal stability (decomposition temperature, rate, and the degradation products) of the OLS is critical. In this study, modern thermal analysis techniques combined with infrared spectroscopy and mass spectrometry (TGA‐FTIR‐MS) were used to obtain information on the thermal stability and degradation products of organic modified clay. Furthermore, the thermal and mechanical properties of clay‐filled PMMA nanocomposites were determined by using TGA and DSC. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1702–1710, 2002     

Ultrasound assisted in situ emulsion polymerization for polymer nanocomposite: A review

This review covers an ultrasound assisted synthesis of polymer nanocomposites using in situ emulsion polymerization. First of all, surface modification of core nanoparticles with a coupling agent and surfactant has been employed for the synthesis of core–shell polymer nanocomposites. In addition to application of ultrasound for the synthesis of core–shell polymer nanocomposites, due to its influential efficiency, sonochemistry has been extensively used not only as an aid of dispersion for inorganic nanoparticles and organo-clay, but also acts as an initiator to enhance polymerization rate for synthesis of polymer nanocomposites. In situ emulsion polymerization of hydrophobic monomers, such as methyl methacrylate, butyl acrylate, aniline, vinyl monomers and styrene, using surfactant and water soluble initiator were carried out for a synthesis of core–shell polymer nanocomposite. This technique assists in preparation of stable and finely dispersed polymer nanocomposite with the loading of inorganic particles up to 5 wt.%. Recent developments in the preparation of core–shell polymer nanocomposites using an ultrasound assisted method with their physical characteristics such as morphology, thermal, and rheological properties and their potential engineering applications have been discussed in this review.     

Advance polymeric carbon nanocomposite films with enhanced thermo‐mechanical properties

The homogenous nanocomposite films of UV/O₃ oxidized multiwall carbon nanotubes (MWCNTs) subsequently modified with aniline moiety were synthesized with polymethylmethacrylate (PMMA) through free radical polymerization. The phenylamine functional groups present on the surface of MWCNTs providing an anchoring sites for deposition of Ag metal nanoparticles (NP).The in situ free radical polymerization of MMA in the presence of these well dispersed nanotubes gave a new class of radiation resistant nanocomposite films. The synthesized materials were characterized by FT‐IR, TGA, TEM, EDX, TC, DMA, universal testing machine, and optical microscopy to ascertain their structural morphologies, thermal stability, and mechanical strength. The microscopic and structural properties reflect the homogenous mixing of modified MWCNTs in polymer matrix contributing in enhancement of thermal stability, thermo‐mechanical strength, glass transition temperatures, and thermal conductivity of nanocomposites even at 0.25 wt% addition of modified nanofiller. Thermal and thermo‐mechanical behavior of pre‐ and post‐UV/O₃ irradiated nanocomposite films have been compared with neat polymer. The results revealed that modified nanofiller network can effectively disperse the radiation and has a dramatic reinforcement effect on the nature of degradation of PMMA matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

α-MnO2 nanorods-polyaniline (PANI) nanocomposites synthesized by polymer coating and grafting approaches for screening EMI pollution

In this work, α-MnO₂ nanorods-polyaniline nanocomposites were synthesized using polymer coating and grafting approaches. The synthesized nanocomposites were characterized by XRD, FESEM, EDAX, TEM, TG-DTA and FT-IR techniques. The Electromagnetic properties of prepared samples were measured using vector network analyzer in the 8–18 GHz (X and Ku-Band) frequency region. The α-MnO₂-NH₂-PANI nanocomposite synthesized by grafting approach showed better electrical conductivity, excellent dielectric loss with superior microwave absorption ability. In comparison with pure MnO₂, the microwave absorption characteristics of α-MnO₂-NH₂-PANI nanocomposite display considerable improvements, with an effective absorption band at 10.8 GHz and 14.5 GHz under ?10 dB and minimum reflection loss (RL) of ?30.79 dB at 14.5 GHz. The α-MnO₂-NH₂-PANI sample also showed considerable shielding effectiveness (SE) i.e. ?20.85 dB in the 8–18 GHz frequency region. The observed value of RL and SE surpasses the required value for being utilized at a commercial level. These results are surely helpful to explore the microwave absorption study of different combinations of organic/inorganic nanocomposite materials particularly for shielding and microwave absorption applications.     

The effect of polyoxypropylene‐montmorillonite intercalates on polymethylmethacrylate

Polymethylmethacrylate (PMMA)‐layered silicate nanocomposites have been prepared by in situ polymerization of commercial type of methylmethacrylate monomer (MMA), for denture base material, into organoclay. Organoclay was prepared through an ion exchange process between sodium cations in montmorillonite and NH₃⁺ groups in polyethertriamine hydrochloride and polyoxypropylene triamine hydrochloride with different molecular weight (5000, 440). X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) have been used to investigate the structure of the resulting composites. Both intercalated and exfoliated nanocomposites were obtained depending on the type and amount of organoclay. The thermal decomposition temperatures of the nanocomposites were found to be higher than that of pristine polymer. PMMA was strongly fixed to inorganic surfaces, due to cooperative formation of electrostatic bonding between NH₃⁺ group and negatively charged surface of layered silicate and amide linkage between PMMA and polyethertriamine or polyoxypropylene triamine. The effect of the organoclay on the hardness, toughness, tensile stress, and elongation at break of the polymer was studied and was compared with pristine polymer. The hardness and Izod impact strength of PMMA‐organoclay nanocomposites were enhanced with the inclusion of clay. Tensile properties appear to be enhanced at certain organoclay content. However, the water absorption is slightly higher than the pristine PMMA. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Investigation of improved dielectric and thermal properties of ternary nanocomposite PMMA/MXene/ZnO fabricated by in-situ bulk polymerization

Electric power system applications demand for high-temperature dielectric materials. The improved performance of polymer nanocomposites requires improvement in their thermal conductivity & stability, dielectric stability and processing technique. However, they often lose their dielectric properties with a rise in temperature. Here, we offer a solution by incorporating electrically conducting material (MXene) and semiconducting inorganic nanoparticles (ZnO NPs) into an insulating PMMA polymer matrix to maintain high dielectric constant, both at the room and high temperature. Therefore, to achieve desirable thermal and dielectric properties is the main objective of the present study based on the homogeneous distribution of the nanofillers by in-situ bulk polymerization assisted by strong sonication in the corresponding polymer. The introduction of MXene and ZnO NPs into the PMMA not only acquires a substantial increment in the dielectric constant, to attain a value 437, with minimum energy loss of 0.36 at 25 Hz, but also improves the thermal conductivity of PMMA up to 14 times by causing the reduction of thermal resistance, which is actually responsible for the poor thermal conductivity of amorphous pure PMMA polymer. More importantly, hybrid PMMA/4:2 wt% MXene:ZnO nanocomposite leads to an excellent thermal stability. Moreover, further characterization of the synthesized nanocomposites by FTIR, SEM and XRD leads to the evaluation of strong interaction of ternary components with PMMA matrix.     

Water-Based PMMA-Nano-CaCO3 Nanocomposites by In Situ Polymerization Technique: Synthesis,Characterization and Mechanical Properties

Water-based nanocomposite was synthesized using in-situ polymerization of Methyl Methacrylate. Nano-CaCO₃ was added during polymerization along with aqueous solution of surfactant. Quantity of nano-CaCO₃ was varied as 0, 2 and 4% of monomer quantity. XRD gram shows the presence of nano-CaCO₃, which causes the crystalline nature to nanocomposites. TEM images of nano-CaCO₃ show cubic structure. Synthesis of nanocomposite follows pseudo–first-order kinetics polymerization. PMMA-4% CaCO₃ nanocomposite showed significant improvement in UV absorbance and in mechanical properties like adhesion, scratch resistance as compared to neat PMMA and 2% CaCO₃ nanocomposite.     

Exceptionally good,transparent and flexible FeS2/poly(vinyl pyrrolidone) and FeS2/poly(vinyl alcohol) nanocomposite thin films with excellent UV‐shielding properties

Composites of nanocrystalline iron disulfide (FeS₂) coated with poly(vinyl pyrrolidone) (PVP) or poly(vinyl alcohol) (PVA) have been successfully synthesized using a solvothermal process, in which PVP and PVA serve as soft templates. Transparent, flexible thin films of these nanocomposites were prepared from homogeneous solution using a solution‐casting approach. X‐ray diffraction and thermogravimetric analysis and energy‐dispersive X‐ray, Fourier transform infrared and UV‐visible absorption spectroscopic techniques were employed to study the structural and optical properties of these nanocomposite films. UV‐visible spectra in transmission mode reveal the UV‐shielding efficiency of these nanocomposite films and the films are found to be exceptionally good for UV‐shielding applications in the wavelength range 200 to 400 nm. The present work aims at developing transparent and flexible UV‐shielding materials and colour filters using cost‐effective and non‐toxic inorganic–polymer nanocomposites. © 2012 Society of Chemical Industry     

Investigation of the crystalline structure of PVDF in PVDF/PMMA/graphene polymer blend nanocomposites

In this work, we report the preparation of poly(vinylidene fluoride)/poly methylmethacrylate (PVDF/PMMA)/graphene polymer blend nanocomposites via synthesis of PMMA/graphene as a masterbatch through in situ polymerization. The PMMA/graphene masterbatch compounded with PVDF by solution mixing in different ratios. The compounding was followed by solution casting to form polymer blend nanocomposites. Solution cast films were subjected to thermal treatments at three different temperatures. The crystalline structure of thermally treated samples was studied with X‐ray diffraction spectroscopy and Differential Scanning Calorimetric (DSC) analysis. Results indicated PMMA chains persuade the β crystalline form in PVDF but cannot stabilize them in elevated temperature; however, graphene sheets due to restricting effect on TT conformation chains are able to stabilize them. DSC data revealed the graphene sheets can increase the crystallinity of PVDF and also act as nucleating agents. Transmission Electron Microscopy demonstrated coexistence of the different stacking orders of graphene sheets in both masterbatch and polymer blend nanocomposite. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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     

Nanocomposite particles with core–shell morphology III: preparation and characterization of nano Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–poly(styrene–methyl methacrylate) particles via miniemulsion polymerization

Encapsulation of inorganic nanoparticles (as a core) by polymers (as a shell) is one of the interesting research subjects that lead to the synthesis of nanocomposite. These materials include properties of not only the organic polymer (e.g. optical properties, toughness, processability, flexibility, etc.) but also the inorganic nanoparticles (e.g. mechanical strength, thermal stability, etc.). Some of the applied preparative methods are dry-spray, dispersion, suspension, emulsion and miniemulsion polymerization techniques. Here, miniemulsion polymerization technique was used in order to obtain white-color nanocomposite latex particles containing nano-alumina (40–47 nm) encapsulated by copoly [styrene (St)–methyl methacrylate (MMA)] under high-shear ultrasonic irradiation. At first, bare nano-alumina was encapsulated with the copolymer to obtain latex particles. In another attempt and in order to investigate the effect of compatiblizing system, alumina nanoparticles were coated with oleic acid in order to form modified alumina core. Then miniemulsion polymerization was performed in the minidroplets including modified alumina, St and MMA for obtaining core/shell nanocomposite particles. The progress of encapsulation polymerization was followed by different instrumental techniques such as FT-IR spectra, thermal gravimetric analysis, dynamic light scattering, induced-coupled plasma, TEM and SEM.     

Polymers and nanocomposites: synthesis and metal ion pollutant uptake

This paper is an overview of the versatile polymer materials containing different functional groups at the main or side chain to remove hazardous inorganic species. These materials include water‐insoluble, nanocomposite and water‐soluble polymers. Water‐insoluble polymers and nanocomposites are used in adsorption and ion exchange processes, whereas water‐soluble polymers are employed with ultrafiltration membranes in the liquid‐phase polymer‐based retention technique. © 2015 Society of Chemical Industry     

Mechanical properties of Al2O3/polymethylmethacrylate nanocomposites

Alumina/polymethylmethacrylate (PMMA) nanocomposites were produced by incorporating alumina nanoparticles, synthesized using the forced gas condensation method, into methylmethacrylate. The particles were dispersed using sonication and the composites were polymerized using free radical polymerization. At an optimum weight percent, the resulting nanocomposites showed, on average, a 600% increase in the strain-to-failure and the appearance of a well-defined yield point when tested in uniaxial tension. Concurrently, the glass transition temperature (T_g) of the nanocomposites dropped by as much as 25°C, while the ultimate strength and the Young's modulus decreased by 20% and 15%, respectively. For comparison, composites containing micron size alumina particles were synthesized and displayed neither phenomenon. Solid-state deuterium NMR results showed enhanced chain mobility at room temperature in the nanocomposites and corroborate the observed T_g depression indicating considerable main chain motion at temperatures well below those observed in the neat polymer. A hypothesis is presented to relate the thermal and mechanical behavior observed in the composites to the higher chain mobility and T_g depression seen in recent ultrathin polymer film research.     

Friction spot welding of PMMA with PMMA/silica and PMMA/silica-g-PMMA nanocomposites functionalized via ATRP

In the present study, the feasibility of Friction Spot Welding (FSpW) of a commercial-grade poly(methyl methacrylate) (PMMA) (PMMA GS) and PMMA 6N/functionalized silica (SiO₂) nanocomposites was investigated. The silica nanoparticles were functionalized via atom transfer radical polymerization (ATRP) with PMMA chains to achieve a uniform dispersion in the polymer matrix. The successful functionalization of silica nanoparticles with PMMA chains via ATRP was evaluated by ATR-FT-IR and TGA measurements. Rheological investigations of the silica nanocomposites showed a plateau of the storage modulus G′ at low frequencies (0.01–0.03 rad/s) as a result of elastic particle–particle interactions. Overlap friction spot welds consisting of PMMA GS and a 2 wt% SiO₂-g-PMMA nanocomposite were successfully prepared and compared to spot joints of PMMA GS welded with PMMA 6N and PMMA 6N/silica nanocomposite with 2 wt% unfunctionalized silica nanoparticles. Raman mappings of selected areas of cross-sectional plastographic specimens revealed an increased mixing behavior between the two polymer plates in the case of PMMA GS/2 wt% SiO₂-g-PMMA joints. Although the joints welded with PMMA 6N/silica nanocomposites showed a reduction of 22% in lap shear strength and 21% displacement at peak load compared with the neat PMMA spot welds, they can compete with other state-of-the-art PMMA welding techniques such as thermal bonding and ultrasonic welding, which indicates the potential of friction spot welding as an alternative fabrication technology for joining future nanocomposite engineering parts.     

Synthetic method of polyethylene-poly(methylmethacrylate) (PE-PMMA) polymer hybrid via reversible addition-fragmentation chain transfer (RAFT) polymerization with functionalized polyethylene

Summary Polyethylene-poly(methylmethacrylate) (PE-PMMA) polymer hybrid was synthesized via RAFT polymerization of MMA with PE chain transfer agent (PE-CTA) for the first time. The structure of PE-CTA produced by sequential functionalization of terminally hydroxylated PE was confirmed by ¹H NMR and FT-IR analyses. The results of GPC after MMA polymerization revealed that the molecular weight (M_w) of the resulting polymers increased compared with the one of the PE-CTA. ¹H NMR analysis of resulting polymers confirmed that the amounts of PMMA segments were in a range of 7.8 and 23 wt %. TEM images indicated the nanometer level microphase-separation morphology between the PE segment and PMMA segment.     

Designing of fullers‐earth‐containing poly(vinyl alcohol)‐g‐poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) nanocomposites: Swelling and deswelling behaviors

In this study, polymer–clay nanocomposites (PCNs) composed of poly(vinyl alcohol)s (PVAs), poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid), and fullers earth were prepared by the effective dispersal of inorganic nanoclays in the organic PVA matrix via in situ free‐radical polymerization with potassium persulfate as an initiator and N,N‐methylene bisacrylamide as a crosslinker. The monomer, 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid, was grafted onto the PVA backbone, and at the same time, fullers earth layers were intercalated and exfoliated into the grafted copolymer, especially at a low or moderate loading of the fullers earth. The synthesized PCN materials were characterized by Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction techniques. The morphological features of the synthesized materials were studied by scanning electron microscopy; this revealed that the swelling ratio of this nanocomposite increased with increasing fullers earth content. The X‐ray diffraction results indicated that the fullers earth was exfoliated in the nanocomposite matrix, and its introduction into the polymer matrix enhanced the percentage crystallinity of the polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of polyurethane/titanium dioxide nanocomposites obtained by in situ polymerization

The development of new polymeric and polymeric based materials is fundamental to meet the market demands. This work aims the synthesis and characterization of polyurethane/titanium dioxide nanocomposite, using low cost commercial raw materials. Nanocomposites were synthesized by in situ polymerization reactions in which titanium dioxide were added in the following proportions, by weight, in relation to the mass obtained from the pure polymer: 0.5, 1.0, 2.0, 3.0, 5.0, 7.0, and 10.0 %. These reactions were based in poli (ε-caprolactone) and 1,6-diisocyanatohexane. The materials were characterized by infrared spectroscopy Fourier transform, scanning electron microscopy, differential scanning calorimetry analysis, thermogravimetric analysis, dynamic mechanical thermal analysis, and UV–Vis spectroscopy. Based on the obtained results it was concluded that the nanocomposites synthesized by in situ polymerization presented, in general, thermal properties (degradation temperature) and mechanical properties higher than the pure polymer.     

Preparation,structural characterization,and properties of poly(methyl methacrylate)/montmorillonite nanocomposites by bulk polymerization

Poly(methyl methacrylate) (PMMA)/montmorillonite (MMT) nanocomposites were synthesized by a simple technique of a monomer casting method, bulk polymerization. The products were purified by hot acetone extraction and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), examination of their mechanical properties, and light transmittance testing. Although XRD data did not show any apparent order of the MMT layers in the nanocomposites, TEM revealed parallel MMT layers with interlamellar spacings of an average of 9.8 nm and the presence of remnant multiplets of nonexfoliated layers. Therefore, PMMA chains were intercalated in the galleries of MMT. DSC and TGA traces also corroborated the confinement of the polymer in the inorganic layer by exhibiting the increase of glass‐transition temperatures and mass loss temperatures in the thermogram. Both the thermal stability and the mechanical properties of the products appeared to be substantially enhanced, although the light transmittances were not lost. Also, the materials had excellent mechanical properties. Measurement of the tensile properties of the PMMA/MMT nanocomposites indicated that the tensile modulus increased up to 1013 MPa with the addition of 0.6 wt % MMT, which was about 39% higher than that of the corresponding PMMA; the tensile strength and Charpy notched impact strength increased to 88 MPa and 12.9 kJ/m², respectively. As shown by the aforementioned results, PMMA/MMT nanocomposites may offer new technology and business opportunities. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 348–357, 2005