Synthesis and characterization of PLA nanocomposites containing nanosilica modified with different organosilanes I. Effect of the organosilanes on the properties of nanocomposites: Macromolecular,morphological, and rheologic characterization

Polylactide nanocomposites containing different loadings of nanosilica were prepared by employing bulk ring opening polymerization from lactide. Nanosilica was used as such and after surface treatment with different amounts of two distinct silanes. The effects on the properties of the material were evaluated comparing the samples containing organosilane‐modified nanosilica with poly(lactic acid) (PLA) containing unmodified nanosilica. A standard linear PLA and an industrial “film grade” PLA (PLA Natureworks 4032D) were used as reference. Pure silica tends to decrease the molecular weight of the material, deactivating the catalytic system but when silanes are present on the surface, molecular weights are similar to the ones of standard and industrial PLA. Transmission electron microscopy analysis shows that silanes improve the dispersion of the mineral, while rheologic curves suggest that when silanes are present melt viscosity increases markedly at zero shear and decreases faster as the shear rate increases. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and physicochemical investigation of imide-functionalized silica nanocomposites

The incorporation of inorganic nanoparticles into polymers have gained significant attention to improving functional properties. The ultimate nanocomposite behaviors are influenced by many parameters, such as microstructural distribution that are produced during the treatment process. Herein, a hybrid material integrating a modified network into a polyimide PI matrix was produced via the sol–gel method by the reaction of pyromellitic dianhydride, 4, 4-oxydianaline, and 1, 5-diaminonaphthalene to synthesize copolyimides nanocomposite. The modified polyimide and unmodified polyimide silica (SiO₂) nanoparticles were incorporated in the polyimide matrix to have polyimide silica nanocomposite. In modified silica nanoparticles, 3-aminopropyltriethosilane was introduced to have better compatibility among inorganic–organic hybrid with similar chemical contact due to their flexible alkyl group. The surface morphology or structure of silica and polyimide was affirmed by scanning electron microscopy, Fourier transforms infrared spectroscopy confirmed the synthesis of pure polyimide, unmodified polyimide, and modified polyimide silica via presence and absence of certain peaks. Thermogravimetric analysis (TGA) results showed high thermal stability of nanocomposites as silica content increases. In contrast to unmodified silica, the modified silica provides more thermal stability to the nanocomposites. Dynamic mechanical analysis was used to investigate the tensile stress of pure polyimide, unmodified, and modified silica nanocomposites. Thermal stability, storage modulus, and moisture absorption of these hybrid materials were improved with silica nanoparticles. The TG mass spectrum confirms the successful synthesis of modified silica networks. The substituted silica nanoparticles show higher mechanical toughness and storage in modified compared to unmodified silica nanocomposite, which exhibits stronger binding attraction between silica nanoparticles and polyimide matrix.     

Synthesis and characterization of some polyacrylate/montmorillonite nanocomposites by in situ emulsion polymerization using redox initiation system

Intercalated modification of Montmorillonite clay (MMT) with three different amino acids—Alanine, Leucine, and Phenylalanine—in the presence of hydrochloric acid followed by surface modification by methyl triethoxy silane coupling agent to produce double modified Montmorillonite clay which is characterized by X‐ray diffraction (XRD) and Thermogravimetric analysis (TGA). The data shows an increase in d‐spacing of modified clay as a result of cationic exchange. Double modified MMT clay was used in the preparation of Polyacrylate/clay nanocomposites by using an in situ redox emulsion polymerization of polyglycidylmethacrylate (PGMA) and polymethylmethacrylate (PMMA). The structure and properties of the prepared nanocomposites were achieved by XRD, TGA, and SEM. The results show that all weight loses temperatures for the nanocomposite samples are higher than that of pure polymer in both PGMA and PMMA. It is also obvious that the increasing in the clay content plays an effective role in the increasing of thermal stability of these materials. SEM shows that the clay is more homogenously dispersed in PMMA than in PGMA matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nonisothermal crystallization kinetics of PLA/nanosized YVO4 composites as a novel nucleating agent

The influence of nanosized YVO₄ particles as a novel and efficient nucleating agent on the nonisothermal crystallization behaviors of poly(lactic acid) (PLA) was studied. A modified Avrami model was utilized to describe the nonisothermal crystallization kinetics of pure PLA and PLA nanocomposites. The differential isoconversional Friedmann formula was employed to calculate the effective activation energies (E_X(t) ) of nonisothermal crystallization from the glass state. The results showed that modified Avrami methods describe the nonisothermal crystallization kinetics of pure PLA and PLA nanocomposites well. The crystallization rate of PLA/1 mass% YVO₄ was faster than that of pure PLA sample by factor 5 × 10³ at a heating rate of 1 K min⁻¹. While the values of Lauritzen–Hoffman parameters (K_g and U*) of the PLA/YVO₄ nanocomposites were lower than those of pure PLA, indicating the nucleation efficiency of nanosized YVO₄ particles for PLA. Scanning electron microscopy images reflect the uniform dispersion of 1 mass% YVO₄ in PLA matrix. Thermogravimetric analysis results revealed that the thermal degradation parameters are slightly lowered by 7 °C on increasing the mass percentage of YVO₄ in the PLA nanocomposites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48340.     

Production and characterization of UHMWPE/fumed silica nanocomposites

Ultrahigh‐molecular‐weight polyethylene (UHMWPE)/fumed silica nanocomposites were prepared via in situ polymerization using a bi‐supported Ziegler‐Natta catalytic system. Nanocomposites with different nanoparticle weight fractions were produced in order to investigate the effect of fumed silica on thermal and mechanical properties of UHMWPE/fumed silica nanocomposites. The viscosity average molecular weight (M ) of all samples including pure UHMWPE as the reference sample and nanocomposites were measured. Scanning electron microscope (SEM) images showed the homogenous dispersion of nanoparticles throughout the UHMWPE matrix while no nanoparticle cluster has been formed. Crystallization behavior of nanocomposites was investigated by differential scanning calorimetry (DSC), which showed a slight increase in melting temperature by enhancing the nanoparticle concentration while no significant change was observed in the crystallization temperature as the fumed silica concentration enhanced. The improvement in all thermal stability parameters was recorded by thermogravimetric analysis (TGA). Besides, via tensile testing, it was confirmed that addition of nanoparticles caused considerable improvement in such mechanical properties as Young's modulus, yield stress, and tensile strength of samples while the elongation at break declined by addition of more nanoparticles. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Synthesis and characterization of linear low‐density polyethylene/sepiolite nanocomposites

Linear low‐density polyethylene (LLDPE)/sepiolite nanocomposites were prepared by melt blending using unmodified and silane‐modified sepiolite. Two methods were used to modify sepiolite: modification before heat mixing (ex situ) and modification during heat mixing (in situ). The X‐ray diffraction results showed that the position of the main peak of sepiolite remained unchanged during modification step. Infrared spectra showed new peaks confirming the development of new bonds in modified sepiolite and nanocomposites. SEM micrographs revealed the presence of sepiolite fibers embedded in polymer matrix. Thermogravimetric analysis showed that nanocomposites exhibited higher onset degradation temperature than LLDPE. In addition, in situ modified sepiolite nanocomposites exhibited higher thermal stability than ex situ modified sepiolite nanocomposites. The ultimate tensile strength and modulus of the nanocomposites were improved; whereas elongation at break was reduced. The higher crystallization temperature of some nanocomposite formulations revealed a heterogeneous nucleation effect of sepiolite. This can be exploited for the shortening of cycle time during processing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fumed silica/polyurethane nanocomposites: effect of silica concentration and its surface modification on rheology and mechanical properties

The effects of nanosilica type and its content on microstructure, mechanical properties, and rheology of thermoplastic polyurethane (TPU) nanocomposites were investigated. Three different types of silica which included: unmodified (Si-Un) and commercially modified with octylsilane (Si-OS) and polydimethylsiloxane (Si-PDMS) with 5, 10, and 15 wt% of all fillers, were prepared by solution casting method. Scanning electron microscopy (SEM) showed that surface treatment of nanosilica with OS and PDMS reduced the aggregation of particles and improved their dispersion at microlevel. The effect of adding nanoparticles on microdomain morphology of TPU was studied by transmission electron microscopy (TEM), infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). The results demonstrated a relatively good interaction between the hard and soft segments in the presence of treated nanosilica that hindered the crystallization of hard segments in TPU. Thermogravimetric analysis (TGA) and tensile test showed that nanocomposites with treated nanosilica have better thermal stability and mechanical properties. The dynamic rheological studies indicated that nanocomposites containing Si-OS and Si-PDMS (with better dispersion and higher interface between the soft and hard domains in TPU) have improved viscoelastic properties in comparison with nanocomposites with untreated silica. In this study, dynamic frequency sweep data were correlated by a generalized Maxwell model and found that elastic constants of TPU chains were improved in the presence of modified silica nanoparticles.     

Thermal properties of poly(lactic acid) fumed silica nanocomposites: Experiments and molecular dynamics simulations

Poly(lactic acid) (PLA) fumed silica nanocomposites were prepared by twin-screw extruder. Thermal properties were investigated by experiments and molecular dynamics simulations. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used and 1.34 °C increase of the glass transition temperature (T_g) and 12 °C improvement of thermal stability were observed for PLA–silica nanocomposites as compared to neat PLA. Molecular dynamics simulations (NPT ensemble) were carried out using modified OPLS-AA force field, and T_g and root-mean-square radii of gyration (R_g) were calculated. A good agreement between the simulation results and experiments was obtained.     

Synthesis and characterization of nanosilica/polyacrylate composite latex

The nanosilica/polyacrylate organic–inorganic composite latex was synthesized by in‐situ emulsion polymerization of methyl methacrylate (MMA) and butyl acrylate (BA) in the presence of silica nanoparticles, which were modified by silane coupling agent. The surface properties and dispersibility of silica nanoparticles modification, chemical structure, Zeta potential, diameter distribution of the composite latex prepared, surface roughness, and thermal stability of the hybrid film formed by the composite latex were investigated by fourier transform infrared spectrometer (FTIR), transmission electron microscopy (TEM), Zeta meter, ZetaPlus apparatus (dynamic light scattering method), atomic force microscopy (AFM), and thermogravimetric analysis (TGA), respectively. After modification with silane coupling agent, silane was grafted onto the surface of silica nanoparticles to form the organic layers, which was able to efficiently prevent the silica nanoparticles from aggregating to individually homogeneous disperse in the in‐situ emulsion polymerization system and improve the compatibility of silica nanoparticles with the acrylate monomers. The nanosilica/polyacrylate organic–inorganic composite latex prepared had the properties of silica nanoparticles and pure polyacrylate latex but was not simply a combination. Strong chemical bonding tethered the silica and acrylate chains to form the core/shell structural composite latex. Consequently, the hybrid film formed by nanosilica/polyacrylate composite latex exhibited a smooth surface and better thermal properties than the pure polyacrylate film. POLYM. COMPOS. 27:282–288, 2006. © 2006 Society of Plastics Engineers     

Preparation,characterization, and properties of TiO2/PLA nanocomposites by in situ polymerization

In situ polymerization method was used to prepare TiO₂/polylactide (PLA) nanocomposites with different contents of TiO₂ in this work. The size of the organically modified TiO₂ particles was investigated by X‐ray diffraction (XRD) analysis. Scanning electron microscope (SEM) shows that nano‐TiO₂ particles disperse in the PLA evenly when the content of TiO₂ is low (less than 3 wt%). The differential scanning calorimeter (DSC), thermogravimetry analysis (TGA), and tensile test were used to study the thermal and mechanical properties of the composites. Results show that both the thermal and mechanical properties are markedly improved when the content of TiO₂ is 3 wt%. UV light irradiation and solution degradation experiment show that degradation of the composites is higher when the content of TiO₂ increases and due to the introduction of TiO₂ particles in the nanocomposites, the TiO₂/PLA nanocomposites exhibit remarkable bacteriostasic activity. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Transparent PMMA/silica nanocomposites containing silica nanoparticles coating under supercritical conditions

This work reports the preparation of PMMA/silica nanocomposites with high optical transparency and enhanced mechanical properties using a melt compounding method. The surface of SiO₂ particles was modified with a γ-methacryloxypropyltrimethoxy silane coupling agent in a supercritical carbon dioxide-ethanol mixture and by conventional procedure. Dispersion of silica nanoparticles in ethanol at low temperatures plays an important role in deagglomeration and dispersion of nanosilica, which leads to the optimal particle-matrix bonding in composites. The optimal mechanical and optical properties were found for composites loaded with 5 wt% silica nanoparticles treated under supercritical coating method.     

Organic–inorganic hybrid boron‐containing phenol–formaldehyde resin/SiO2 nanocomposites

The organic–inorganic hybrid boron‐containing phenol–formaldehyde (BPFR) resin/SiO₂ nanocomposites was synthesized in‐situ from boric acid, phenol, and tetramethoxysilane. The structure of BPFR modified and the distributions of silicon element were studied by Fourier‐transform infrared spectroscopy, energy dispersive X‐ray spectrometry, and transmission electron microscope, respectively. The glass transition temperature (T_g) was determined by torsional braid analysis. The results show that silicon element distribution is homogeneous, and the size of nanosilica is about 40–60 nm. The thermal stability and kinetics parameters of thermal degradation were determined by thermogravimetry analysis (TGA). TGA results show that the resin modified has higher heat resistance property when the additive quantity of SiO₂ was 3 wt%. The temperature of 5% weight loss is 487.7°C, which is 12.4°C higher than that of common BPFR. The residual ratio of 3 wt% SiO₂/BPFR was 62.3% at the temperature of 900°C, which is 11.2% higher than that of common BPFR. The mechanics loss peak T_p of 3% SiO₂/BPFR is 33°C higher than common BPFR. Fiberglass‐reinforced BPFR modified by 3 wt% SiO₂ has better mechanical and dielectric properties than that of common BPFR. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Thermal degradation and flammability of nanocomposites composed of silica cross-linked to poly(methyl methacrylate)

The effect of polymer cross-linkages on thermal degradation of silica/poly (methyl methacrylate) (PMMA) nanocomposites is investigated using a single novel nanoparticle. Nanosilica surface treated with KH570, an organic surface treatment capable of free-radical polymerisation, was used to cross-link PMMA via an in situ method. Scanning electron microscopy was used to characterise nanosilica before use, while X-ray diffraction confirmed silica was well dispersed in PMMA. Thermogravimetric analysis (TGA) results showed that thermal degradation of silica cross-linked nanocomposites was significantly stabilised compared to PMMA, with a 30% reduction in the peak mass loss rate. Kinetic studies revealed the degradation of nanocomposites in this work abide by first-order kinetics, with an increase in the degradation activation energy of approximately 100?kJ?mol^?1. This is nearly double the improvement compared to conventional PMMA-silica nanocomposites in literature, showing dramatic enhancements to thermal stability. Analysis of high-temperature residuals from TGA tests suggest that cross-linked silica have increased char yields when compared with both PMMA and traditional silica nanocomposites. Cone Calorimetry results showed the materials in this work have reduced heat release rates compared to PMMA and traditional silica-PMMA nanocomposites.     

Synergistic effects of modified TiO2/multifunctionalized graphene oxide nanosheets as functional hybrid nanofiller in enhancing the interface compatibility of PLA/starch nanocomposites

The aim of this study is to investigate the synergistic effects of modified TiO₂/multifunctionalized graphene oxide nanosheets at different ratios on the interface compatibility between starch and poly(lactic acid) (PLA). To this end, silanylated nano-TiO₂ (MTiO₂, 1 and 2%) and alkylated maleic anhydride grafted graphene oxide (f-GO, 0.1, 0.2, and 0.4%) at different combinations are blended with the PLA-starch composites using solution blending technique. Then, the synergistic effects of MTiO₂ and f-GO on PLA/starch matrix are investigated in terms of the morphology, crystallinity, structural characterization, thermal stability, dynamic mechanical, and antiaging properties, and the related mechanisms. The Raman and Fourier transform infrared spectroscopy spectra verify the successful synthesis of the two modified nanofillers (f-GO and MTiO₂) and the formation of strong hydrogen bond within the PLA-starch nanocomposites. Due to the strong interfacial interaction and the synergistic effect from the combination of 1% MTiO₂ and 0.2% f-GO, obvious improvement was observed in PLA-starch versus other nanocomposites in terms of morphology, thermal stability, surface hydrophobicity, storage modulus, ultraviolet-shielding capacity, and aging-resistance. Furthermore, differential scanning calorimeter (DSC), isothermal crystallization kinetic, and X-ray diffraction analysis demonstrate that f-GO and the M-TiO₂ significantly synergize in enhancing the crystallization rate and crystallinity of PLA/starch matrix. These results provide novel insights for constructing high-performance nanocomposites and facilitate their applications in food packaging.     

Preparation of polymeric hybrid nanocomposites based on PE and nanosilica

In this study the realization of nanocomposites based on a melt dispersion of nanoscopic silica particles in a polyethylene matrix is described. Different silane coupling agents were used to improve the interaction between nanosilica and polyethylene and then to improve the dispersion of the filler. In one case vinyl groups-containing silane coupling agents containing were used. The nanocomposite obtained with this modifier was transformed in a crosslinked organic-inorganic hybrid after an electron beam radiation treatment. The nanocomposites and the hybrid were characterized with TEM and FTIR. The thermal decomposition was studied in TGA. Mechanical properties were also detected, in a small punch test and wear resistance in a rotative drum abrader.     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

In situ polymerized nanocomposites of poly(butylene succinate)/Tio2 nanofibers: molecular weight,morphology, and thermal properties

In this study, the nanocomposites of poly(butylene succinate) (PBS) and TiO₂ nanofibers were first synthesized via in situ polymerization. Molecular weight, morphology, and thermal properties of the nanocomposites were characterized. As the weight percentage of TiO₂ nanofibers increased from 0 to 2%, the molecular weight of PBS in the nanocomposites decreased gradually compared with that of pure PBS. In morphology, the nanocomposites were constituted by free PBS and PBS‐grafted TiO₂ nanofibers (PBS‐g‐TiO₂), which were proved by the Fourier transform infrared, scanning electron microscopy (SEM), and transmission electron microscopy. In addition, the SEM demonstrated the strong interfacial interaction and homogeneous distribution between TiO₂ nanofibers and PBS matrix. The thermal properties determined by differential scanning calorimetry and thermogravimetric analysis included the increasing of cold crystallization temperatures, the melting temperatures, and the thermal stability. Besides, the crystallinity and the rate of crystallization of the nanocomposites were enhanced, which were also observed by the X‐ray diffraction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of polypropylene/clay nanocomposites

Polypropylene/clay (PP/clay) nanocomposites were synthesized via intercalative polymerization. The nanostructure of the composites was investigated by wide‐angle X‐ray diffractometry (WAXD) and transmission electron microscopy (TEM). The WAXD patterns of the PP/clay nanocomposites indicated that the characteristic diffraction peak of the clay disappeared. The TEM image showed the clay was exfoliated into nanometer size and dispersed uniformly in the PP matrix. The composites exhibited much higher storage modulus compared to that of pure PP. At temperatures higher than T_g, the storage modulus of the PP/clay nanocomposites with 8.1 wt % clay content increased three times that of the pure PP. Additionally, the thermal stability of the nanocomposites significantly increased. The maximum decomposition temperature was increased by 44°C with the introduction of about 10 wt % clay. The heat‐distortion temperatures (HDTs) of the nanocomposites also increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3611–3617, 2001     

Influence of the processing parameters and composition on the thermal stability of PLA/nanoclay bio‐nanocomposites

Poly(lactic acid) (PLA) is one the most promising bio‐based and biodegradable polymer. However, its low thermal stability limits the range of applications and complicates its transformation via the most industrial common processes. The novelty of this work is studying the thermal stability of PLA and PLA/clay nanocomposites during use, as a function of the composition and using a wide range of extrusion and injection moulding processing parameters. To improve the thermal stability of the PLA, laminar silicates containing different organomodifications have been added (Cloisite 20A and Cloisite 30B). The results show that the processing conditions and composition define the morphology of the bio‐nanocomposites, which plays key role in defining final thermal properties of the material. In general, clays improve the thermal stability of the processed material, increasing the degradation temperature and decreasing the degradation rate under a wide range of processing conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40747.     

Preparation,Mechanical and Thermal Properties of Polyurethane/Nanosilica Composites via High Pressure Shearing Methods

Nanosilica particles were dispersed into polymer diols by high pressure shearing homogenizer (HPSH), then polyurethane nanocomposites were prepared via in-situ polymerization of diphenylmethane diisocyanate (MDI) and polymer diols. FTIR analysis indicated that the -NCO groups of MDI had reacted with the hydroxy on the surface of nanosilica during in-situ polymerization. TGA suggested that polyurethane/nanosilica composites obtained by in-situ polymerization had better thermal stability than pure polyurethane. Meanwhile, the tensile and dynamic mechanical properties of the samples prepared by HPSH were superior to those by directly ultrasonic dispersing nanosilica, accompanied by more homogeneous dispersion of nanosilica particles in the polymer matrix.