Preparation and characterization of hydrophilic and antibacterial silver decorated silica-grafted-poly(vinylpyrrolidone) (Ag-SiO2-PVP) nanoparticles for polymeric nanocomposites

Hydrophilic antibacterial silver decorated silica-grafted-poly(vinylpyrrolidone) (Ag-SiO₂-PVP) nanoparticles were successfully synthesized in multiple steps. In this regard, silanization of the silica nanoparticles was performed with different concentrations of vinyltrimethoxysilane (VTS) to generate vinyl groups onto the nanoparticles surface. Obtained results showed that by increasing the VTS concentration the amount of vinyl groups on the surface of the silica nanoparticles increased while nanoparticles agglomeration did not occur. Then, poly(vinylpyrrolidone) PVP brushes were grafted onto the silanized silica nanoparticles (SiO₂-VTS) via grafting-through polymerization method to obtain PVP-grafted silica nanoparticles (SiO₂-PVP). Fourier transform infrared spectroscopy, thermal gravimetric analysis, and dynamic light scattering confirmed the successful generation of the vinyl groups and PVP brushes onto the silica nanoparticles. Finally, Ag-SiO₂-PVP nanoparticles were prepared by synthesizing silver nanoparticles onto the SiO₂-PVP nanoparticles to render them antibacterial. Energy dispersive X-ray spectroscopy showed that highest grafting of silver nanoparticles onto the SiO₂-PVP nanoparticles was obtained for the nanoparticles with highest content of vinyl groups. X-ray photoelectron spectroscopy was used to identify the elements and their chemical structure for the synthesized nanoparticles. Plate colony counting method was applied to assess the antibacterial effects of the Ag-SiO₂-PVP nanoparticles which revealed outstanding bactericidal properties of them.     

Synthesis of poly(styrene-co-acrylonitrile) copolymer brushes on silica nanoparticles through surface-initiated polymerization

In the present investigation, silica nanoparticles have been coated with poly(styrene-co-acrylonitrile) (SAN) copolymer brushes synthesized via surface-initiated atom transfer radical polymerization (ATRP). In the initial step, silica nanoparticles were functionalized with triethoxysilane-based ATR initiator, 6-(2-bromo-2-methyl) propionyloxy hexyl triethoxysilane. Successful formation of the covalent linkages between ATRP initiator and silica nanoparticles is further corroborated using thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The surface initiated ATRP of the styrene and the acrylonitrile mediated by a copper complex was carried out using the initiator fixed silica nanoparticles in the presence of a sacrificial (free) initiator. The polymerization is preceded in a living manner in all examined cases, producing nanoparticles coated with well-defined poly(styrene-co-acrylonitrile) (SAN) brushes with molecular weight in the range of 12–22 kDa. SAN-grafted silica nanoparticles were characterized using TGA which showed significant weight loss in the temperature range of 340–420 °C confirming the formation of the polymer brushes on the surface with graft densities in the range of 0.109–0.190 chains/nm². Successful formation of the SAN copolymer brushes are further characterized by FTIR and proton nuclear magnetic resonance spectroscopy techniques. Differential scanning calorimetric studies revealed that the SAN copolymer grafted onto silica nanoparticles exhibits higher glass transition temperatures than free SAN copolymers. Transmission electron microscopy and dynamic light scattering studies revealed that the SAN copolymer-grafted silica nanoparticles showed relatively fine dispersion in organic solvents such as tetrahydrofuran, when compared to bare silica nanoparticles.     

Syntheses of an azo‐group‐bound silica initiator and silica–polystyrene composites

In this article, we present a facile method for the synthesis of an azo‐group‐bound silica (SiO₂–azo) initiator. The azo groups were introduced onto the surface of silica (SiO₂) nanoparticles via facile condensation between 4,4′‐azobis‐4‐cyanopentanoic acid and the alkyl–hydroxyl groups ‐ immobilized on the SiO₂ nanoparticle surface under ambient conditions. The polystyrene (PS) chains were grafted onto the SiO₂ nanoparticle surface by in situ polymerization with the resulting SiO₂–azo as an initiator, and then, the SiO₂–PS composite was prepared. The syntheses and properties of the SiO₂–azo initiator and the composite were characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, thermogravimetric analysis, gel permeation chromatography, and differential scanning calorimetry techniques. The results confirm that the SiO₂–azo initiator and the composite were synthesized successfully. Styrene was polymerized with the initiation of SiO₂–azo, and the resulting PS domain accounted for 48.6% of the total amount of composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Investigation of silica nanoparticles grafted with sulphonated polymer for enhanced oil recovery at high temperature and high salt

Nano-fluids' application for enhanced oil recovery (EOR) has attracted noticeable attention and formed a new research area in recent years. Currently, the greatest challenge in this area is to formulate stable nano-fluids for oil reservoirs with high temperatures and salinity. To overcome the limitations of its application in high-temperature drilling, polymer-coated nanoparticles (SiO₂-PAMPS NPs) were prepared via solution polymerization of 2-acrylamide-2-methyl-1-propane sulphonic acid (AMPS) from the surface of aminopropyl-functionalized silica nanoparticles. The SiO₂-PAMPS NPs were characterized by Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and dynamic light scattering (DLS). The results indicated that the AMPS was successfully grafted onto the surface of silica nanoparticles, and the average diameter of SiO₂-PAMPS NPs was about 16 nm. The nano-fluids showed noticeable stability in American Petroleum Institute (API) brine (2 wt.% CaCl₂ and 8 wt.% NaCl) at 90°C beyond 46 days. When amphipathic nanoparticles were introduced to brine at 90°C, the potential of the nano-fluids in recovering oil was evaluated by investigating the interfacial tension with kerosene oil and the oil contact angle in the nano-fluids. The contact angle of the glass sheet surface before treatment was about 144°, while after SiO₂-PAMPS NPs treatment for 72 h, it became about 92°. Meanwhile, the nano-fluids showed an excellent enhancing emulsibility property, which plays a vital role in promoting the development of EOR in high-temperature and high-salt environments.     

TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> composite nanoparticles containing hindered amine light stabilizers encapsulated by MMA–PMPM copolymers

TiO₂–SiO₂ composite nanoparticles containing hindered amine light stabilizers (HALSs) were prepared by encapsulation of commercially available TiO₂–SiO₂ nanoparticles using methyl methacrylate (MMA) and 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (PMPM) copolymers through mini-emulsion polymerization. The Fourier transform infrared spectral analysis (FTIR) showed that the hindered amine light stabilizer PMPM was incorporated into the TiO₂–SiO₂/P(MMA-co-PMPM) composite nanoparticles. The X-ray photoelectron spectroscopy analysis (XPS) showed that the surface of TiO₂–SiO₂ nanoparticles was enriched with HALS moieties. The formation of P(MMA-co-PMPM) random copolymers on the surface of TiO₂–SiO₂ nanoparticles was determined by differential scanning calorimetry (DSC), and the percentage of the chemically grafted P(MMA-co-PMPM) coverage on the TiO₂–SiO₂ nanoparticles surface was 40.9 wt% determined by thermogravimetric analysis (TGA), which revealed that the TiO₂–SiO₂ nanoparticles were successfully encapsulated by MMA–PMPM copolymers. Scanning electron microscopy analysis indicated that the TiO₂–SiO₂/P(MMA-co-PMPM) composite nanoparticles were mainly homogeneous spherical shape particles, with an average size of about 90 nm. Rhodamine B (Rh.B) photocatalytic degradation study revealed UV-shielding characteristics for TiO₂–SiO₂/P(MMA-co-PMPM) composite nanoparticles and showed a remarkable decrease in photocatalytic activity of TiO₂–SiO₂ nanoparticles. These results indicated that TiO₂–SiO₂/P(MMA-co-PMPM) composite nanoparticles may be promising light stabilizers with covalent functionalization of polymeric HALS, which has little photocatalytic activity, and can be introduced into the weathering-resistant polymer materials to improve their application properties.     

New fluorinated hybrid organic/inorganic water soluble polymeric network

This work presents the elaboration of nanoparticle networks from HASE (hydrophobically alkali-soluble emulsion) thickeners grafted with silica nanoparticles. Three HASE were realized by copolymerization in emulsion of methacrylic acid and ethyl acrylate or trifluoroethyl methacrylate and a hydrocarbon or fluorocarbon macromonomer. The macromonomer contains a hydrophobic pendant group separated from the backbone by a polyethylene glycol spacer chain. The free acid functions of the copolymer were coupled with amine functionalized silica nanoparticles. In basic aqueous solutions, the suspensions containing 1 wt.% of this polymer/SiO₂ nanocomposite characterized by DLS (size analysis) and Cryo-SEM are stable, translucent, and gel-like at pH = 7.5. Rheological measurements demonstrated that the grafting of silica nanoparticles did not affect the thickening effect of precursor co-polymers. Coating of glass plates was realized with these hybrid networks and characterized by AFM, indicating that the silica nanoparticles were more homogeneously dispersed when a fluorocarbon co-polymer was used.     

Catalytic graphene formation in coal tar pitch- derived carbon structure in the presence of SiO2 nanoparticles

A simple and effective way to manufacture graphene from a coal tar pitch (CTP) is demonstrated. Silica (SiO₂) nanoparticles were used to modify the CTP as carbon precursor. A silica nanofiller introduced into the CTP matrix underwent carboreduction during heat treatment to 2000 °C, resulting in the formation of silicon carbide. Surfaces of SiC grains were sites for graphene formation. The influence of SiO₂ on the structure and microstructure of CTP- based carbon matrix, after annealing up to 2800 °C, was studied. Carbon samples were analyzed using X- ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and Raman Spectroscopy. Crystallite sizes (L_a, L_c) and interplanar distance (d₀₀₂) were determined. The presence of SiO₂ in CTP carbon precursor favored the crystallites’ growth in the ‘a′ crystallographic graphite direction, and inhibited their growth on the ‘c′ axis. The crystallites composing of graphene layers, were characterized by an elongated dimension in the ‘a′ axis direction. Above 2000 °C silicon carbide decomposed, followed by the sublimation of silicon from the carbon matrix.     

Silica/polystyrene and silica/polystyrene‐b‐polymethacryloxypropyltrimethoxysilane hybrid nanoparticles via surface‐initiated ATRP and comparison of their wettabilities

Both silica/polystyrene (SiO₂/PS) and silica/polystyrene‐b‐polymethacryloxypropyltrimethoxysilane (SiO₂/PS‐b‐PMPTS) hybrid nanoparticles were synthesized via surface‐initiated atom transfer radical polymerization (SI‐ATRP) from SiO₂ nanoparticles. The growths of all polymers via ATRP from the SiO₂ surfaces were well controlled as demonstrated by the macromolecular characteristics of the grafted chains. Their wettabilities were measured and compared by water contact angle (WCA) and surface roughness. The results show that the nanoparticles possess hydrophobic surface properties. The static WCA of SiO₂/PS‐b‐PMPTS hybrid nanoparticles is smaller than that of SiO₂/PS hybrid nanoparticles, meanwhile, the surface roughness of SiO₂/PS‐b‐PMPTS hybrid nanoparticles is yet slightly rougher than that of SiO₂/PS hybrid nanoparticles, which shows that the combination and competition of surface chemistry and roughness of a solid material can finally determine its wettability. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Enhanced interfacial strength and mechanical properties of carbon fiber composites by introducing functionalized silica nanoparticles into the interface

Introducing nanoparticles onto the surface of carbon fibers (CFs) is a useful method for enhancing the quality of fiber-matrix interface. In this work, a liquid sizing agent containing functionalized silica nanoparticles (SiO₂) was well prepared to improve interfacial strength and mechanical properties of composites. In order to enhance the dispersion of SiO₂ nanoparticles in sizing agent, SiO₂ nanoparticles were chemically grafted with 3-aminopropyltriethoxysilane (APS), and then silanized silica (SiO₂-APS) was introduced into the interphase by a conventional sizing process as well. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) confirmed the successful preparation of SiO₂-APS. Scanning electron microscopy (SEM) showed that a uniform distribution of SiO₂-APS on the fiber surface and the increased surface roughness. The sized fibers (CF/SiO₂-APS) exhibited a high surface free energy and good wettability based on a dynamic contact angle testing. Interfacial microstructure and mechanical properties of untreated and sized CFs composites were investigated. Simultaneous enhancements of interlaminar shear strength (ILSS) and impact toughness of CF/SiO₂-APS composites were achieved, increasing 44.79% in ILSS and 31.53% in impact toughness compared to those of untreated composites. Moreover, flexural strength and modulus of composites increased by 32.22 and 50.0% according to flexural test. In addition, the hydrothermal aging resistance of CF/SiO₂-APS composites has been improved significantly owing to the introduced Si-O-Si bonds at the interface.     

Preparation and Characterization of Novel Polyimide/SiO2 Nano-hybrid Films by In Situ Polymerization

A silicon-based aromatic polyimide (PI) containing pendent aryl rings was synthesized by solution polycondensation of a silicon-containing diamine with 4,4′-(hexafluoroisopropylidene)diphthalic anhydride. Its nano-hybrids with different colloidal SiO₂ concentrations were synthesized by in situ polymerization. The reactions were carried out in presence of 3-aminopropyltriethoxysilane as a coupling agent. The inclusion of the coupling agent in the polymer chain and its co-condensation with SiO₂ nanoparticles afforded a silica network that was interconnected chemically with the PI matrix. The chemical structure of the hybrid materials was analyzed by Fourier transform infrared spectroscopy and energy dispersive X-ray spectroscopy. The morphology of the hybrid films and the surface roughness were characterized by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The results indicated that nanometer-scale inorganic particles were homogeneously dispersed throughout the PI matrix with 50–70 nm size range. The best results and favorable miscibility between polymer and silica phases in the nano-hybrids were obtained when up to 40 wt% nanoparticles were introduced into the backbone of PI matrix.     

Realization of reinforcing and toughening poly (phenylene sulfide) with rigid silica nanoparticles

Reinforcing and toughening poly (phenylene sulfide) (PPS) with rigid SiO₂ nano-particles was realized simultaneously under the suitable thermodynamic state of PPS, and the key issue about the effect of matrix/filler interaction was also demonstrated. The strong matrix/filler interaction realized by grafting reactive groups onto nanoparticles was beneficial for stress transfer and thus in favor of the increase in tensile strength of PPS. Meanwhile, this interaction provided nanoparticles with certain mobility to move with molecular chains and align along the tensile direction when T > T_g of PPS, thus the nanoparticles could significantly improve the tensile toughness of PPS according to the energy dissipation mechanism. Consequently, the tensile strength and elongation to break values of PPS increased to 59.0 MPa and 112.1 % from the initial values of 48.0 MPa and 78.5 % by adding 1 wt% grafted SiO₂ nano-particles. The work provided a promising method to reinforce and toughen rigid-chain polymer simultaneously and prepare high-performance PPS nanocomposites.     

Inorganic silica functionalized with PLLA chains via grafting methods to enhance the melt strength of PLLA/silica nanocomposites

The low melt strength greatly limits the application of PLA as biodegradable package materials produced by film blowing method. Modified silica nanoparticles are introduced into PLA matrix to solve this problem in this study. To build Poly (l-lactide) nanocomposites successfully, two kinds of convenient and efficient methods are conducted to synthesize well-defined topological PLLA grafted SiO₂ nanoparticle. One is the ring-opening of l-lactide (Grafting from), and another is nucleophilic addition reaction (Grafting to). The structure, molecular weight of grafted PLLA chains, grafting density, and the thermal decomposition behavior of the nanoparticles prepared by different methods are characterized. By varying the contents of the initiator SiO₂ and the molecular weight of the reacted PLA chains, high density-low molecular weight PLLA grafted SiO₂ are obtained in “grafting from” while high molecular weight-low grafting density PLLA grafted SiO₂ are synthesized in “grafting to”. It is exactly in good agreement with the theoretic model. The spatial distribution of nanoparticles as well as the interaction force between nanoparticles and matrix is critical important to structuring bionanocomposites with desirable properties. So the two kinds of synthesized nanoparticles are introduced into PLA matrix in our contribution to evaluate these two factors, respectively. The TEM and SEM results both reveal the uniform dispersion of nanoparticles after modified. While the extension and shear rheology results show that the long grafted chains covalently connected on the surface of the silica via “grafting to” contribute more to enhance the melt strength of PLA. Meanwhile, stabilized PLA nanocomposites films with modified silica via “grafting to” method are successfully blown base on these researches. The research in this work constitutes a robust way to design melt-strengthen PLA/SiO₂ nanocomposites.     

Preparation of poly(ethylene glycol)-grafted silica nanoparticles using a facile esterification condensation method

Organic–inorganic hybrid nanoparticles have been prepared by the direct facile esterification condensation under extremely mild conditions as ambient temperature, moisture and atmospheric pressure, and the resulting composite particles are characterized by ESCA, FTIR, TEM, DLS, TGA, DSC, and XRD techniques. Results show that this facile graft method has high graft efficiency and the grafted poly(ethylene glycol) (PEG) accounts for about 55 wt% of the total silica composites. The resulting silica nanoparticles have core-shell structure with PEG on the outside and SiO₂ in the core. As a result, the dispersion behavior of nanoparticles and the thermal stability of the grafted PEG are improved by the formation of covalent ester bonds between PEG and the reactive silica nanoparticles. The PEG phase, however, is disturbed by the proximity of the oxide phase of SiO₂. Consequently, less crystal or faulty crystal of PEG is resulted when PEG is grafted onto the surfaces of silica nanoparticles.     

PES/SiO2 nanocomposite by in situ polymerization: Synthesis,structure, properties,and new applications

SiO₂ nanoparticles of a quantum size (15 nm or less) were prepared via sol–gel method using tetraethylorthosilicate as a precursor. SiO₂ nanoparticles were characterized by X‐ray diffraction (XRD) and field‐emission scanning electron microscopy (FESEM) analyses. Polyethersulfone/silica (PES/SiO₂) crystal structure nanocomposite was prepared by in situ polymerization using silica nanoparticles as reinforcement filler. The polymerization reaction was done at 160°C in paraffin bath in the presence of diphenolic monomers. XRD and FESEM analyses were used to study the morphology of the synthesized nanocomposite. The purity and thermal property of the PES/SiO₂ nanocomposite were studied by energy dispersion of X‐ray analysis and differential scanning calorimetry, respectively. The effect of silica particles on the hydrophilicity of PES/SiO₂ nanocomposite was also investigated. It was showed that the PES/SiO₂ nanocomposite had a higher swelling degree when compared with the pure PES. The synthesized PES/SiO₂ powder was used to remove Cu(II) ions from its aqueous solution. The effect of experimental conditions such as pH, shaking time, and sorbent mass on adsorption capacity of PES/SiO₂ nanocomposite were investigated. It was found that incorporation of a low amount of silica (2 wt%) into the polymer matrix caused the increase of the Cu(II) ions adsorption capacity of PES. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Enhancing crystallization rate and melt strength of PLLA with four‐arm PLLA grafted silica: The effect of molecular weight of the grafting PLLA chains

To improve the crystallization rate and melt strength of polylactide (PLLA), nano‐size amino silica grafted by four‐arm PLLA (4A‐PLLA) with different molecular weight was synthesized. ¹H nuclear magnetic resonance proved that 4A‐PLLA had been grafted onto the surface of SiO₂ successfully, and the grafting ratios and the degradation behaviors of the grafted SiO₂ nanoparticles (g‐SiO₂) were studied. When the grafted silica was introduced into PLLA matrix, the crystallization rate and melt strength of composites were found to be improved and the length of grafted chain played an important role. The extension rheology indicated that long grafted 4A‐PLLA on the surface of SiO₂ was more efficient in enhancing the elongational viscosity of PLLA, owing to the stronger interactions between the grafted chains and the matrix. The crystallization behavior of ungrafted silica filled composite was similar to that of neat PLA, while g‐SiO₂ played a role of nucleating agent. The crystallinities and the crystallization rates of the composites depended on the content of g‐SiO₂ and the grafted chain length of 4A‐PLLA, especially the latter. Longer grafted chain acted as nucleation site in the matrix and significantly improved the crystallization behaviors of PLLA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45675.     

Homogeneous dispersion of SiO2 nanoparticles in an hydrosoluble polymeric network

The main difficulty still encountered in the elaboration of polymer/silica nanocomposites is the control of the nanoparticles dispersion homogeneity and the stability of the nanoparticle dispersion in the surrounding substance. The innovative point of this work is the elaboration of hybrid networks in aqueous solution performed with ASE (alkali swellable emulsion) thickeners grafted with silica nanoparticles. The thickening ability of the polymer should favour silica nanoparticles dispersion in fluid matrices. Two ASE copolymers were realised by copolymerisation in emulsion of MA (methacrylic acid) and EA (ethyl acrylate) and/or TFEM (trifluoroethyl methacrylate). The substitution of a part of EA by TFEM gave fluorinated ASE copolymers. Their free acid functions were then coupled with different ratio of amine functionalized silica nanoparticles to afford nanocomposites. The amounts of silica nanoparticles in the copolymers were determined by thermogravimetric experiments. Depending on the silica nanoparticles/copolymer ratio in basic aqueous solutions we achieved stable translucent gel like aqueous suspensions of silica nanoparticles containing 1 wt.% of the polymer/SiO₂ nanocomposite.     

Research of silica aerogels prepared by acidic silica sol under the condition of atmospheric pressure drying

Acidic silica sol was used as precursor to prepare SiO₂ aerogels using the atmospheric pressure drying technology. The influence of pH, water bath temperature and concentrations of silica sol on the structure parameters and morphology were systematically studied. SiO₂ aerogel prepared with the sol concentration of 20% possessed uniform structure and the best structure parameters. Water bath temperature exhibited an obvious effect on morphology, specific surface area and porosity. Moreover, the optimal SiO₂ aerogel showed a good heat resistance up to 700?°C. A lower thermal conductivity was 0.019 W/m · K at room temperature (25?°C) and 0.044 W/m · K at 600?°C.     

Thermal stability and abrasion resistance of polyacrylate/nano-silica hybrid coatings

Polyacrylate (PAE)/nano-silica (SiO₂) hybrids were prepared by an in situ sol–gel process of tetraethyl orthosilicate in the presence of PAE toluene solution. The hybrid coatings were fabricated using a PAE/SiO₂ suspension by the traditional casting. Their intermolecular interaction and morphology, as well as thermal, mechanical, and optical properties, were investigated using Fourier transform infrared spectroscopy, field-emission scanning electron microscope, differential scanning calorimetry and TG/DTA thermogravimetric analysis, coating impact testing, and UV–Vis spectroscopy, respectively. At the same time, their abrasive properties were carried out by abrasion resistance and nanoindentation tests. The results indicate that silica nanoparticles, with diameter about 30 nm, can disperse homogeneously in the PAE matrix, where hydrogen bonds between the PAE and nano-silica are formed. Therefore, homogeneous dispersion of nano-silica particles provides high transparency for the PAE/SiO₂ hybrid coating as the size of nano-silica phase is much smaller than the wavelength (390–770 nm) of visible light. PAE/nano-silica hybrid coatings have increased T _g and thermal stability including the onset decomposition temperature, 10 % weight loss temperature, and char at 700 °C. Additionally, the incorporation of nano-silica particles improves the glossiness of the PAE/nano-silica hybrid coatings and enhances their abrasion resistance and surface hardness. The nano-silica content has obvious effect on the thermal, mechanical, optical, and anti-abrasion properties of PAE/SiO₂ hybrid coatings. With the consideration of all the properties of hybrid coatings, the PAE/SiO₂ hybrid containing 10 phr of nano-silica has the optimal composition. These PAE/nano-silica hybrid coatings have potential applications in high-performance hologram image recording.     

Thermo-oxidative stability of poly(methyl methacrylate)/poly(methyl methacrylate)-grafted SiO2 nanocomposites

Thermo-oxidative stability of PMMA-grafted SiO₂ and PMMA/PMMA-grafted SiO₂ nanocomposites was investigated by conventional non-isothermal gravimetric technique. It was interesting to find that PMMA-grafted SiO₂ nanoparticles exhibited higher thermo-oxidative stability than that of PMMA. The apparent activation energy of PMMA-grafted SiO₂ nanoparticles increased with the grafting ratio of PMMA from SiO₂, which was estimated by Kissinger method. This indicates that the strong interactions existing between the grafted chains are responsible for the enhanced thermo-oxidative stability of PMMA-grafted SiO₂ nanoparticles. However, the grafting ratio of PMMA from SiO₂ in nanoparticles has only limited effect on the thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites due to a much lower content of grafted PMMA in the nanoparticles relative to PMMA. The increased thermo-oxidative stability of PMMA/PMMA-grafted SiO₂ nanocomposites is possibly resulted from the increased SiO₂ content in the nanocomposites, in which the grafting ratio of PMMA in PMMA-grafted SiO₂ nanoparticles is kept almost as a constant. The glass transition temperature (T _g) of PMMA/PMMA-grafted SiO₂ nanocomposites is about 25 °C and is higher than that of PMMA. The grafting ratio of PMMA from SiO₂ in the nanoparticles has no qualitative effects on the T _g of the nanocomposites.     

Silica coating of Fe3O4 magnetic nanoparticles with PMIDA assistance to increase the surface area and enhance peptide immobilization efficiency

The high efficiency of using N-(phosphonomethyl)iminodiacetic acid (PMIDA) as a surfactant for formation of a silica coating on Fe₃O₄ magnetic nanoparticles (MNPs) with a large surface area has been demonstrated. The coating of PMIDA-stabilized MNPs with silica and their further APS-functionalization significantly increased the specific area (up to 203 m² g^?1) and the number of amino groups (up to 1.12 mmol/g) grafted on their surface compared to nanomaterials synthesized without preliminary SiO₂-coating. The comparative study of the peptide modification efficiency, using as an example pH-low insertion peptide (pHLIP), of MNPs coated with 3-aminopropylsilane (APS) or SiO₂/APS was carried out. It has been shown that silica coating of PMIDA-stabilized MNPs leads to a significant increase in the degree of immobilization of the peptide (up to 22 μmol per g of MNPs). Comprehensive characterization of the obtained materials at each stage of the synthesis was carried out using scanning electron microscopy (SEM), energy dispersive X-ray fluorescence spectroscopy (EDX), BET analysis, ATR Fourier transformed infrared spectroscopy (FTIR), termogravimetric analysis (TGA), CHN-elemental analysis, dynamic light scattering (DLS), and vibrating sample magnetometry (VSM). The proposed approach to applying SiO₂-coating of MNPs can be useful for design of new materials for biomedical and chemical purposes.