In situ prepared PBSu/SiO2 nanocomposites. Study of thermal degradation mechanism

A series of nanocomposites consisted of poly(butylene succinate) (PBSu) and fumed silica nanoparticles (SiO₂) were prepared using the in situ polymerization technique. The amount of SiO₂ used directly affected the final molecular weight of the prepared polyesters. At a low SiO₂ content (0.5 wt.%) the molecular weight obtained was higher compared to neat PBSu, however at higher concentrations this was gradually reduced. The melting point of the matrix remained unaffected by the addition of the nanoparticles, in contrast to the crystallinity, which was dramatically reduced at higher SiO₂ contents. This was mainly due to the extended branching and cross-linking reactions that took place between the carboxylic end groups of PBSu and the surface silanols of the nanoparticles. Thermal degradation of the PBSu/SiO₂ nanocomposites was studied by determining theirs mass loss during heating. From the variations of the activation energies, calculated from the thermogravimetric curves, it was clear that nanocomposites containing 1 wt.% SiO₂ content had a higher activation energy compared to pure PBSu, indicating that the addition of the nanoparticles could slightly increase the thermal stability of the matrix. However, in PBSu/SiO₂ nanocomposite containing 5 wt.% SiO₂ the activation energy was smaller. This phenomenon should be attributed to the existence of extended branched and cross-linked macromolecules, which reduce the thermal stability of PBSu, rather than to the addition of fumed silica nanoparticles.     

In situ preparation of poly(ethylene terephthalate)-SiO2 nanocomposites

Poly(ethylene terephthalate) (PET)/silica nanocomposites were synthesized by using the in situ polymerization approach. Sol-gel transformation based on the hydrolysis and condensation of tetraethoxysilane (TEOS) is used to prepare the inorganic phase, concurrent with condensation polymerization of terephthalic acid and ethylene glycol to produce the PET matrix. Due to the simultaneous formation of the polymer matrix and the inorganic networks, a macrophase separation is avoided, and the resulting materials have a high degree of homogeneity. The morphology and the crystallization behavior of the composites were examined by scanning electron microcopy (SEM) and differential scanning calorimetry (DSC), respectively.     

Preparation of polypropylene/sepiolite nanocomposites using supercritical CO2 assisted mixing

Well dispersed polypropylene (PP)/sepiolite clay nanocomposites were prepared successfully using supercritical carbon dioxide (scCO₂) assisted mixing with and without the presence of maleic anhydride grafted polypropylene (PP-g-MA) as compatibilizer. The resulting morphology and polymorphism of nanocomposites were established using X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and scanning electron microscopy (SEM) observations. The mechanical properties of the nanocomposites were investigated and compared with those obtained by a traditional melt compounding method. Our results showed that by using scCO₂ in the process, we were able to obtain better sepiolite dispersions and reduce breakage of sepiolite fibres. Consequently, a significant improvement in the yield stress was observed for the nanocomposites processed in scCO₂ compared to those processed by the traditional melt compounding. XRD data also indicated that the resulting nanocomposites had only α-phase crystallites of PP while the presence of sepiolite could also induce preferred orientation of these α-phase crystallites.     

Preparation and properties of poly(vinyl alcohol)/silica nanocomposites derived from copolymerization of vinyl silica nanoparticles and vinyl acetate

Nanocomposites of poly(vinyl alcohol)/silica nanoparticles (PVA-SNs) were prepared by in-situ radical copolymerization of vinyl silica nanoparticles functionalized by vinyltriethoxysilane (VTEOS) and vinyl acetate with benzoyl peroxide (BPO, i.e., initiator), subsequently saponified via direct hydrolysis with NaOH solution. The resulting vinyl silica nanoparticles, PVA-SNs were characterized by means of fourier transformation spectroscopy (FTIR), transmission electron microscopy (TEM) and the elemental analysis method. Effects of silica nanoparticles on viscosity and alcoholysis of PVA-SNs were studied by a ubbelohode capillary viscometer and the back titration method. The morphological structure of PVA-SN films was investigated by scanning electron microscopy (SEM). Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and tensile test were used to determine the thermal and mechanical properties of PVA-SN films. The results indicated that the content of vinyl groups on the surface of the vinyl silica nanoparticles was up to 3.02 mmol/g and vinyl silica nanoparticles had been successfully copolymerized with vinyl acetate. Furthermore, compared to pure PVA, silica nanoparticles bonded with polymer matrix in a low concentration affected the viscosity and alcoholysis of the PVA-SNs materials. At the same time, it resulted in the improvement of the thermal and mechanical properties of the PVA-SN materials due to a strong interaction between silica nanoparticles and the polymer matrix via a covalent bond. It could be found that the optical clarity of the membrane was changed through UV-Vis absorption spectrum due to the introduction of silica nanoparticles.     

The amount of immobilized polymer in PMMA SiO2 nanocomposites determined from calorimetric data

For semicrystalline polymers there is an ongoing debate at what temperature the immobilized or rigid amorphous fraction (RAF) devitrifies (relaxes). The question if the polymer crystals are melting first and simultaneously the RAF devitrifies or the RAF devitrifies first and later on the crystals melt cannot be answered easily on the example of semicrystalline polymers. This is because the crystals, which are the reason for the immobilization of the polymer, often disappear (melt) in the same temperature range as the RAF. For polymer nanocomposites the situation is simpler. Silica nanoparticles do not melt or undergo other phase transitions altering the polymer-nanoparticle interaction in the temperature range where the polymer is thermally stable (does not degrade). The existence of an immobilized fraction in PMMA SiO₂ nanocomposites was shown on the basis of heat capacity measurements at the glass transition of the polymer. The results were verified by enthalpy relaxation experiments below the glass transition. The immobilized layer is about 2 nm thick at low filler content if agglomeration is not dominant. The thickness of the layer is similar to that found in semicrystalline polymers and independent from the shape of the nanoparticles. Nanocomposites therefore offer a unique opportunity to study the devitrification of the immobilized fraction (RAF) without interference of melting of crystals as in semicrystalline polymers. It was found that the interaction between the SiO₂ nanoparticles and the PMMA is so strong that no devitrification occurs before degradation of the polymer. No gradual increase of heat capacity or a broadening of the glass transition was found. The cooperatively rearranging regions (CRR) are either immobilized or mobile. No intermediate states are found. The results obtained for the polymer nanocomposites support the view that the reason for the restricted mobility must disappear before the RAF can devitrify. For semicrystalline polymers this means that rigid crystals must melt before the RAF can relax.     

溶胶-凝胶伴随相分离制备SiO2多孔块体

以正硅酸甲酯(TMOS)为前驱体, 0.01 mol·L^-1盐酸(HCl)为催化剂, 环氧丙烷(PO)为凝胶促进剂, 粘均分子量(M_v)为10000的聚氧化乙烯(PEO)为相分离诱导剂, 采用溶胶-凝胶伴随相分离制备SiO₂多孔块体材料,利用差热分析(DTA)、傅里叶变换红外(FT-IR)光谱、扫描电镜(SEM)、X射线衍射(XRD)、汞压、N₂吸附/脱附等测试技术对所制得的SiO₂多孔块体进行了表征, 探讨了环氧化物调控溶胶-凝胶以及PEO诱导相分离机理. 结果表明, 加入PEO能诱导SiO₂凝胶发生相分离, 当PEO/TMOS摩尔比为0.0018时, 可以获得共连续多孔结构的SiO₂块体材料, 其大孔孔径分布在1-3 μm之间, 比表面积达719 m²·g^-1, 孔体积为0.48 m³·g^-1. 环氧丙烷因其环氧原子的强亲核性和不可逆的开环反应, 促进溶胶-凝胶转换, 同时借助吸附在SiO₂低聚物上的PEO诱导SiO₂凝胶相分离, 从而制备共连续大孔及骨架结构的多孔块体.     

The release of TiO2 and SiO2 nanoparticles from nanocomposites

There is a growing interest in the development of nanocomposites consisting of organic polymers and TiO₂ or amorphous SiO₂ nanoparticles. These nanoparticles may be released from nanocomposites. There is evidence that amorphous SiO₂ and TiO₂ nanoparticles can be hazardous. Thus, in the design of nanocomposites with such nanoparticles, hazard reduction extending to the full nanocomposite life cycle would seem a matter to consider. Options for hazard reduction include: changes of nanoparticle surface, structure or composition, better fixation of nanoparticles in nanocomposites, including persistent suppression of oxidative damage to polymers by nanoparticles, and design changes leading to the release of relatively large particles.     

Anti-fungal activity of SiO2/Ag2S nanocomposites against Aspergillus niger

Submicron particles of amorphous SiO₂ have been used to grow Ag₂S nanophases at their surfaces. SEM and TEM analysis showed morphological well-defined nanocomposite particles consisting of Ag₂S nanocrystals dispersed over the silica surfaces. These SiO₂/Ag₂S nanocomposites were investigated as anti-fungal agents against Aspergillus niger in different experimental conditions, including as nanofillers in cellulosic fibres. The anti-fungal activity in these composite systems is suggested to result from a synergistic effect due to Ag₂S anti-fungal centres and the SiO₂ surfaces in promoting the adsorption of the fungus.     

Novel polyaniline-LiNi0.5La0.02Fe1.98O4 nanocomposites prepared via an in situ polymerization

Polyaniline (PANI)-LiNi_0.5La_0.02Fe_1.98O₄ nanocomposites were synthesized by an in situ polymerization of aniline in the presence of LiNi_0.5La_0.02Fe_1.98O₄ ferrite. The products were characterized by Fourier transform infrared (FTIR), atomic force microscopy (AFM), powder X-ray diffraction (XRD) and vibrating sample magnetometer (VSM). FTIR spectra and XRD indicated the formation of the PANI-LiNi_0.5La_0.02Fe_1.98O₄ composites. AFM study was shown that the average size of samples was less than 100 nm and the ferrite particles had an effect on the morphology of composites. The nanocomposites under applied magnetic field exhibited the hysteresis loops of the ferrimagnetic nature, the saturation magnetization and the coercivity varied with the ferrite content. The bonding model for the composites was also studied.     

A simple and green route to transparent boron nitride/PVA nanocomposites with significantly improved mechanical and thermal properties

A simple and green method is developed to prepare hexagonal boron nitride(h-BN)/poly(vinyl alcohol) (PVA) nanocomposites by using water as a common solvent of h-BN nanosheets and PVA.The obtained h-BN/PVA nanocomposites are highly transparent,and have significantly improved mechanical and thermal properties.They may outperform nano-clay and nano-alumina/PVA nanocomposites as flexible optoelectronic devices,optical windows and heat-releasing materials operated in oxidative or corrosive environment.     

Preparation of degradable polypropylene by an addition of poly(ethylene oxide) microcapsule containing TiO2 part II. Modification of calcium phosphate on the TiO2 surface and its effect

To prepare a novel photo-degradable polypropylene (PP) with a higher degradation rate, a PP composite containing a poly(ethylene oxide) (PEO)/modified TiO₂ microcapsule was prepared. The modification of the TiO₂ was performed by the synthesis of octacalcium phosphate intercalated with succinic acid ion (OCPC) under various Ca/P molar ratio conditions. It was found that the synthesis conditions of the Ca/P = 3.5 and 3.6 M ratios were suitable to prepare the OCPC. However, the microscopic composition on the TiO₂ surface was different between these Ca/P conditions and affected the PP photo-degradation rate in the PP/PEO/modified TiO₂ composite. It was found from the Fourier Transform Infrared (IR) and the tensile testing measurements that the existence of the OCPC covering material on the TiO₂ surface brought about the higher PP photo-degradation rate. The facilitation behavior of the degradation was due to the release of the acid species (succinic acid ion) from the OCPC in the degradation process. In addition, the higher coverage of the OCPC on the TiO₂ surface brought about an induction period for the degradation.     

Enhanced surface plasmon resonance by Au nanoparticles immobilized on a dielectric SiO2 layer on a gold surface

This paper introduces strategies for enhancement of a surface plasmon resonance (SPR) signal by adopting colloidal gold nanoparticles (AuNPs) and a SiO₂ layer on a gold surface. AuNPs on SiO₂ on a gold surface were compared with an unmodified gold surface and a SiO₂ layer on a gold surface with no AuNPs attached. The modified surfaces showed significant changes in SPR signal when biomolecules were attached to the surface as compared with an unmodified gold surface. The detection limit of AuNPs immobilized on a SPR chip was 0.1 ng mL⁻¹ for the prostate-specific antigen (PSA), a cancer marker, as measured with a spectrophotometer. Considering that the conventional ELISA method can detect ∼10 ng mL⁻¹ of PSA, the strategy described here is much more sensitive (∼100 fold). The enhanced shift of the absorption curve resulted from the coupling of the surface and particle plasmons by the SiO₂ layer and the AuNPs on the gold surface.     

Preparation and characterization of poly(imide siloxane) (PIS)/titania(TiO2) hybrid nanocomposites by sol-gel processes

Poly(imide siloxane)(PIS)/titania(TiO₂) hybrid nanocomposites with organic-inorganic covalent bonding have been successfully synthesized by sol-gel processes. The PIS copolymer synthesized in this study was characterized by the observed coexisting two segments: the polyimide (PI) segment and polydimethyldiphenylsiloxane segment, and the latter were specially featured with the introduction of a diphenyl group for improved homogeneity.The obtained TiO₂ networks in PIS matrix were well dispersed and their average diameter was less than 50 nm. Meanwhile, the PIS/TiO₂ hybrid nanocomposite films exhibited good optical transparency at 20 wt% of TiO₂ content. The thermal stability, tensile strength and elongation of the nanocomposites decreased with increasing TiO₂ content. The glass transition temperature (T_g) and Young’s modulus increased with increasing TiO₂ content. The chemical structure and morphologies of PIS/TiO₂ hybrid nanocomposites was characterized by Fourier transform infrared spectroscope (FT-IR), X-ray photoelectron spectroscopy (XPS), and transmission electron microscope (TEM). The T_g and thermal stability were measured by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA), respectively. The mechanical properties were examined by dynamic mechanical analysis (DMA) under controlled force mode.     

Preparation, thermal properties, morphology, and microstructure of phosphorus-containing epoxy/SiO2 and polyimide/SiO2 nanocomposites

A phosphorus-containing tri-ethoxysilane (dopo-icteos) reacting from the nucleophilic addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (dopo) and 3-(trieoxysilyl) isocyanate (icteos) was synthesized. The structure of dopo-icteos was confirmed by ¹H, ¹³C, ³¹P NMR and IR spectra. A triethylamine catalyzed mechanism for the dopo-icteos synthesis was proposed and verified by NMR spectra. The phosphorus-containing epoxy/SiO₂ and polyimide/SiO₂ nanocomposites were prepared from the in-situ curing of diglycidyl ether of bisphenol A (DGEBA)/4,4-diaminodiphenylmethane(DDM)/dopo-icteos, and imidization of poly(amic acid) of pyromellitic dianhydride (PMDA)/4,4′-oxydianiline (ODA)/dopo-icteos, respectively. The microstructure and morphology were investigated by ²⁹Si NMR, scanning electron microscope (SEM), EDS (Si and P mapping) analysis and atomic force microscope (AFM). The thermal properties, flame retardancy and dielectric properties of the organic-inorganic hybrids were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), limiting oxygen index (LOI), thermal gravimetric analysis (TGA) and dielectric analyzer (DEA).     

In-situ synthesis of magnetic (NiFe2O4/CuO/FeO) nanocomposites

In-situ synthesis of magnetic nanocomposites with (NiFe₂O₄/CuO/FeO) crystal phases has been done using a sol-gel method by taking a non-stoichiometric composition of the precursors. The average particle size of the nanocomposites was calculated using X-ray diffraction (XRD) and high resolution tunneling electron microscope (HR-TEM) and it turns out to be ∼20 nm. The vibrating sample magnetometer (VSM) measurements demonstrate the ferromagnetic nature of the nanocomposites. The synthesized nanocomposite was used to prepare magnetic fluid using tetramethylammonium hydroxide as a surfactant and its stability in the solution was also discussed.     

Effects of coating amount and particle concentration on the impact toughness of polypropylene/CaCO3 nanocomposites

The effects of the coating amount of surfactant and the particle concentration on the impact strength of polypropylene (PP)/CaCO₃ nanocomposites were investigated. Nanocomposites prepared with monolayer-coated CaCO₃ nanoparticles had the best mechanical properties, including Young’s modulus, tensile yield stress and impact strength because of the good dispersion of the nanoparticles in the polymer matrix. In addition, the good dispersibility of the monolayer-coated nanoparticles allowed us to study the effects of particle concentration on the impact strength of the nanocomposites. H-PP and E-PP, which were the low and high molecular weight PPs, respectively, were used as polymer matrices. Critical particle concentrations of 10 and 25 wt% corresponding to an abrupt increase in the impact toughness were determined for the E-PP and H-PP nanocomposites, respectively. Good particle dispersion in a polymer matrix is the prerequisite for the calculation of the critical ligament thickness using the critical particle concentration. We propose that the observed critical ligament thickness actually corresponds to the critical thickness at which the plane-strain to plane-stress transition occurs. In addition, the critical ligament thickness of a nanocomposite depends on the properties of the polymer matrix, such as molecular weight, even for a given type of polymer.     

Synthesis and characterization of PAni–SiO2 and PTh–SiO2 nanocomposites' thin films by plasma polymerization

In the present work, we explore the possibility to deposit polyaniline–silicon dioxide (PAni–SiO₂) and polythiophene–silicon dioxide (PTh–SiO₂) nanocomposites through a plasma polymerization route. The films were generated by spraying of mixtures of nano-sized silica particles dispersed in the liquid monomer into a plasma stream of the DC-plasma discharge reactor. The silica in the resulted polymer matrix changes the conduction mechanisms varying from ohmic to ballistic and traps inducing the space charged limited currents (SCLC). The silica modifies the morphology and composition of the deposited films.     

Fabrication and luminescent properties of Eu(BMPPA)3BPy complex and its functionalized silica nanocomposites

Luminescent silica nanocomposites functionalized with a Eu-complex have been prepared and characterized.The europium complex is composed of 2,2'-bipyridyl(BPy) and 2-(4-bromomethyI)-phenylpropionic acid(BMPPA),which contains highly active benzyl bromide substituents and can covalently bind with poly(4-vinylpyridine)(P4VP)-modified silica nanoparticles(nanoSiO_2P4VP) to form nanoSiO_2P4VPEuBPy composites.Microscopic images revealed that the nanoSiO_2P4VPEuBPy composites easily formed aggregates,due to an inter-particle binding caused by the benzyl bromide among the composites.The as-prepared nanocomposites showed the typical emissions of Eu(III) ions at the wavelengths from 580 nm to 750 nm designated to the ~5D_0→~7F_n transitions.Time-resolved fluorescence decay measurements revealed that the emission lifetime was approximately 0.204 ms and 0.576 ms for the nanoSiO_2EuBPy composites,a little shorter than that in the Eu(BMPPA)_3BPy complex.     

Synthesis and characterization of new semifluorinated linear and hyperbranched poly(arylene ether phosphine oxide)s through B2 + A2 and AB2 approaches

A new phosphorus containing trifluoromethyl-activated bisfluoro B₂ monomer has been synthesized successfully by coupling reaction of 4-methoxyphenylphosphonic dichloride and the Grignard salt of 5-bromo-2-fluorobenzotrifluoride. This monomer was converted to linear poly(arylene ether phosphine oxide)s by nucleophilic displacement of the fluorine atom on the benzene ring with several diphenols. The B₂ monomer was further demethylated to form an AB₂ monomer which on self condensation yielded hyperbranched poly(arylene ether phosphine oxide) with identical phosphorous containing moiety. The products obtained exhibit weight-average molecular weights as high as 600,000 g mol⁻¹ in SEC. These linear and hyperbranched poly(arylene ether phosphine oxide)s showed thermal stability as high as 516 °C for 10% weight loss in TGA in nitrogen and showed glass transition temperatures up to 253 °C in DSC. All the polymers were soluble in a wide range of organic solvents, e.g., CHCl₃, THF, NMP and DMF, however, the hb sample showed a significant lower solution viscosity compared to linear samples of similar molar mass. Transparent thin films of linear poly(arylene ether phosphine oxide)s casted from dichloromethane exhibited tensile strengths up to 50 MPa, a modulus of elasticity up to 0.95 GPa and elongation at break up to 36% depending on their exact repeating unit structures. No free standing films could be prepared from the hb analogue due to the missing entanglements, but stable thin polymer films on silicon wafers with high hydrophobicity were formed which showed water contact angles as high as 91°.     

New PVDF organic–inorganic membranes: The effect of SiO2 nanoparticles content on the transport performance of anion-exchange membranes

Organic–inorganic anion-exchange membranes based on poly(vinylidene fluoride)/SiO₂ were prepared and quaternary ammonium groups were introduced by the reaction of the epoxy groups of glycidyl methacrylate with trimethylamine. Various membranes were prepared with different weight fraction of nano-sized SiO₂ particles. The effect of silica content on the performance of these anion-exchange membranes was extensively characterized in terms of transport properties (TSP). The hydrophilic nature, swelling and TSP of these anion-exchange membranes were dependent on nanoparticles content in the membrane matrix. Higher TSP values of these membranes were obtained, which increased with increasing silica content. The hydrophilic property of the membranes was improved in presence of silica. Results of the effect of silica content on the membrane conductivity were confirmed by the analysis of phenomenological coefficients using non-equilibrium thermodynamic principles. It can be concluded that these anion-exchange membranes prepared with 2% loading with nanoparticles exhibited better transport properties, which may be used for their application in electro-driven separation or for other electrochemical processes.