Analysis of the interfacial interactions in polypropylene/silica nanocomposites

Polypropylene‐based composites were prepared by melt blending with nano‐silica, which was pre‐treated by grafting polymerization onto the surface. Tensile moduli and strengths of the composites were determined as a function of the nano‐silica content and the amount of the grafting polymers chemically attached to the nanoparticles, ie percentage grafting. To analyse the relationships between the interfacial interactions in the composites and tensile performance, a number of models dealing with the static and dynamic mechanical behaviours of the particulate composites were applied. It was found that stronger interfacial interactions exist in the grafted nano‐silica‐filled polypropylene composites as compared to the composites with untreated nano‐silica. Since the interfacial interactions occur only within a very short range, the greatest interaction between the modified nanoparticles and the matrix is achieved in the case of low silica concentration and low percentage grafting. An increase in the percentage grafting for various grafted nanoparticles definitely results in an increase of interphase thickness, but the interfacial interactions and the tensile performance of the composites are not necessarily improved because the agglomeration structure of the nanoparticles and the miscibility between the components play the leading role. Copyright © 2004 Society of Chemical Industry     

Mechanical properties of low nano‐silica filled high density polyethylene composites

Modification of nanoparticles through graft polymerization is able to change the chemical nature of the particles' surfaces and provides an effective means for the preparation of nano‐fillers specified for composites manufacturing. The present work focuses on the mechanical role of grafted nano‐SiO₂ particles in high density polyethylene composites prepared by melt compounding. The experimental results show that at a content of 0.75 vol%, the modified nano‐silica results in a rise in tensile stiffness, tensile strength and impact strength of the composites. The grafted nanoparticles can improve the mechanical performance of the matrix polymer more effectively than the untreated version. In addition, a further enhancement of the composites stiffness and strength can be achieved by crosslinking the concentrated masterbatches, which has not yet been revealed in the authors' previous works on grafted nano‐SiO₂ particles/polypropylene composites. It is thus revealed that the introduction of the grafting polymers onto the nanoparticles increases the tailorability of the composites.     

Effect of interfacial interaction on the crystallization and mechanical properties of PP/nano‐CaCO3 composites modified by compatibilizers

To investigate the effect of interfacial interaction on the crystallization and mechanical properties of polypropylene (PP)/nano‐CaCO₃ composites, three kinds of compatibilizers [PP grafted with maleic anhydride (PP‐g‐MA), ethylene–octene copolymer grafted with MA (POE‐g‐MA), and ethylene–vinyl acetate copolymer grafted with MA (EVA‐g‐MA)] with the same polar groups (MA) but different backbones were used as compatibilizers to obtain various interfacial interactions among nano‐CaCO₃, compatibilizer, and PP. The results indicated that compatibilizers encapsulated nano‐CaCO₃ particles, forming a core–shell structure, and two interfaces were obtained in the compatibilized composites: interface between PP and compatibilizer and interface between compatibilizer and nano‐CaCO₃ particles. The crystallization and mechanical properties of PP/nano‐CaCO₃ composites were dependent on the interfacial interactions of these two interfaces, especially the interfacial interaction between PP and compatibilizer. The good compatibility between PP chain in PP‐g‐MA and PP matrix improved the dispersion of nano‐CaCO₃ particles, favored the nucleation effect of nano‐CaCO₃, increased the tensile strength and modulus, but reduced the ductility and impact strength of composites. The partial compatibility between POE in POE‐g‐MA and PP matrix had little effect on crystallization and mechanical properties of PP/nano‐CaCO₃ composites. The poor compatibility between EVA in EVA‐g‐MA and PP matrix retarded the nucleation effect of nano‐CaCO₃, and reduced the tensile strength, modulus, and impact strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Nonisothermal crystallization of PP/nano‐SiO2 composites

The kinetics of nonisothermal crystallization of polypropylene (PP) containing nanoparticles of silicon dioxide (SiO₂) were investigated by differential scanning calorimetry (DSC) at various cooling rates. Several different analysis methods were used to describe the process of nonisothermal crystallization. The results showed that the Ozawa equation and Mo's treatment could describe the nonisothermal crystallization of the composites very well. The nano‐SiO₂ particles have a remarkable heterogeneous nucleation effect in the PP matrix. The rate of crystallization of PP/nano‐SiO₂ is higher than that of pure PP. By using a method proposed by Kissinger, activation energies have been evaluated to be 262.1, 226.5, 249.5, and 250.1 kJ/mol for nonisothermal crystallization of pure PP and PP/nano‐SiO₂ composites with various SiO₂ loadings of 1, 3, and 5%, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1013–1019, 2004     

Effect of the mixing sequence on the morphology and properties of a polypropylene/polydimethylsiloxane/nano‐SiO2 ternary composite

Ternary composites of polypropylene (PP), polydimethylsiloxane (PDMS) elastomer, and nano‐SiO₂, prepared with three different mixing sequences, were studied for dispersion morphology and its effect on the crystallization of PP and the mechanical properties. The mixing sequence produced a significant effect on the dispersion morphology and, thereby, on the mechanical properties of the composites. A two‐step mixing sequence, in which nano‐SiO₂ was added in the second step to the PP/PDMS binary system, produced a significant encapsulation of nano‐SiO₂ by PDMS, and this, in turn, resulted in the poor modulus and impact strength of the composite. A one‐step mixing sequence of all three components produced a separated dispersion of PDMS and nano‐SiO₂ phases in the PP matrix with the occurrence of a fine band of nano‐SiO₂ particles at the boundaries of the PDMS domains and the presence of some nano‐SiO₂ filler particles inside the PDMS domains. This one‐step mixing sequence produced an improvement in the tensile modulus but a decrease in the impact strength with increasing nano‐SiO₂ content. In the third sequence of mixing, which involved a two‐step mixing sequence through the addition of PDMS in the second step to the previously prepared PP/nano‐SiO₂ binary system, the morphology of the dispersion showed separately dispersed PDMS and nano‐SiO₂ phases with a loose network of nano‐SiO₂ particles surrounding the PDMS domains. This latter series of ternary composites had the highest impact strength and exhibited high shear deformation under tensile and impact conditions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface functionalization of Si3N4 nanoparticles by graft polymerization of glycidyl methacrylate and styrene

To improve dispersibility and interfacial interaction of nano‐Si₃N₄ particles in epoxy‐based composites, graft of glycidyl methacrylate (GMA) and styrene (St)/GMA onto the nanoparticles' surface was carried out in terms of emulsion polymerization method. The grafting polymers proved to be chemically attached to the nanoparticles via the double bonds introduced during the coupling agent pretreatment. The factors affecting the graft parameters, such as monomer concentration, initiator consumption, reaction time, etc., were investigated. It was shown that higher concentrations of monomer and initiator are favorable for the graft polymerization. When St/GMA was employed as the grafting monomer, the nanoparticles were found to play the role of polymerization loci. The grafted nanoparticles exhibit greatly improved dispersibility in cured epoxy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 992–999, 2006     

Novel copolymer for SiO2 nanoparticles dispersion

High performance polymers exhibiting multifunctional characteristics can be achieved by the introduction of inorganic nanoparticles like SiO₂ into the functional polymers. In the present work a copolymer epoxy poly(dimethylacrylamide) was synthesized to disperse the SiO₂ nanoparticles. The aim of the work is to develop a new method/process/material for the dispersion of nanoparticles and evaluating the performance of these composites. FT‐IR studies of the polymer adsorbed SiO₂ nanoparticles confirmed that the polymer molecules chain was anchored on the surface of the SiO₂ nanoparticles. The improved interfacial interaction between the particles and polymer enhanced the thermal properties of the composites. The results also show the newly synthesized polymer disperse the nanoparticles well as evidenced by SEM analysis, the uniformly dispersed SiO₂ nanoparticles in the polymer matrix and the particles almost remained in their original shape and size even after incorporation in to the polymer matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Functionalisation of polypropylene by solid phase graft polymerisation and its effect on the mechanical properties of silica nanocomposites

Abstract

To prepare macromolecular compatibiliser for grafted nano-SiO₂/polypropylene (PP) composites, solid phase graft copolymers of PP with styrene and ethyl acrylate were synthesised, respectively. It was found that both percentage grafting and grafting efficiency can be adjusted by changing initiator concentration, reaction temperature and reaction time. Due to partial chain scission and deterioration of the ordered structure of PP during the graft polymerisation, the grafted PP exhibits worse thermal stability and crystallisability than the unmodified PP. Mechanical tests of grafted nano-SiO₂/PP composites indicated that the addition of PP copolymer with the same species of grafting polymer as that on the nanoparticles further improves the ductility of the composites. Molecular rigidity of the grafting polymers, presence of the homopolymer produced during the graft polymerisation, and strain rate of the load applied have important influences on the toughening effect of the functionalised PP.     

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.     

Role of reactive compatibilization in preparation of nanosilica/polypropylene composites

The effect of reactive compatibilization on the mechanical properties of nanosilica filled polypropylene (PP) composites was studied in this work. First, the nanoparticles were grafted with poly(glycidyl methacrylate) (PGMA) by solution free‐radical polymerization, and then melt blended together with PP matrix and aminated PP (PP‐g‐NH₂) that acts as reactive compatibilizer. The reaction between epoxide groups of the grafted PGMA on the nanoparticles and amine groups of PP‐g‐NH₂ during compounding greatly improved interfacial interaction in the composites. As a result, tensile strength, Young's modulus, and notch impact strength of PP composites were increased at rather low filler content. The experimental results indicated that the reinforcing and toughening effects were controlled by flexibility of the grafted polymer as well as processing methods. POLYM. ENG. SCI., 47:499–509, 2007. © 2007 Society of Plastics Engineers.     

Peroxide‐catalyzed swell grafting of maleic anhydride onto polypropylene

A new grafting method was developed to incorporate maleic anhydride directly onto solid‐state polypropylene powders. Maleic anhydride grafts altered the nonpolar characteristics of polypropylene so that much better mixing was achieved in blends and composites of polypropylene with many other polymers and fillers. Maleic anhydride was grafted onto polypropylene by the peroxide‐catalyzed swell grafting method, with a maximum extent of grafting of 4.60%. Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, tensile testing, and impact testing were used to characterize the isotactic polypropylene (iPP), maleic anhydride grafted polypropylene (MAH‐g‐iPP), and (isotactic polypropylene)/(calcium carbonate) composites (iPP/CaCO₃). The crystallinity and heat of fusion of the MAH‐g‐iPP decreased as the extent of grafting increased. The mechanical properties of the CaCO₃ filled polypropylene were improved by adding MAH‐g‐iPP as a compatibilizing agent. The dispersion of the fillers in the polymer matrix and the adhesion between the CaCO₃ particles and the polymer matrix were improved by adding the compatibilizer.     

Tribological behavior of epoxy composites containing reactive SiC nanoparticles

The present article evaluated the sliding wear behaviors of epoxy and its composites filled with SiC nanoparticles. Polyglycidyl methacrylate (PGMA) and a copolymer of glycidyl methacrylate and styrene were grafted onto the nanoparticles as a measure of surface pretreatment, respectively. The grafted polymers were selected because the epoxide groups on PGMA would take part in the curing reaction of epoxy resin and covalently connect the nanoparticles with the matrix, while styrene acted as a copolymerized monomer to adjust the amount of the reactive groups of the grafted macromolecular chains, and hence the compatibility between the grafted polymers and the matrix. In comparison to the composites filled with untreated nano‐SiC particles, the composites with the grafted nano‐SiC exhibit improved sliding wear resistance and reduced frictional coefficient owing to the chemical bonding at the filler/matrix interface. The results were analyzed in terms of structure‐properties relationship of the composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2608–2619, 2007     

Influences of polypropylene grafted to SiO<Subscript>2</Subscript> nanoparticles on the crystallization behavior and mechanical properties of polypropylene/SiO<Subscript>2</Subscript> nanocomposites

Influences of polypropylene (PP) grafted to SiO₂ nanoparticles (7 nm) were studied on the crystallization behavior and the mechanical properties of PP/SiO₂ nanocomposites. PP for the matrix and grafting was synthesized in order to have an identical primary structure, aiming at their co-crystallization and resulting reinforcement of filler-matrix interfaces. The grafted PP chains improved the dispersion of SiO₂, and notably accelerated nucleation in crystallization. It was plausible that the grafted chains whose one chain end was pinned to SiO₂ became nuclei of the crystallization (co-crystallization between the matrix and grafted chains), thus directly bridging between the matrix and SiO₂ nanoparticles. The Young’s modulus and tensile strength were most improved by the grafted PP chains at low filler contents such as 2.3 wt%, whose origin was attributed to effective load transfer to SiO₂ through the co-crystallization-mediated bridging.     

Study on depositing SiO2 nanoparticles on the surface of jute fiber via hydrothermal method and its reinforced polypropylene composites

To improve the interfacial compatibility of jute fiber reinforced polypropylene (PP) composites, hydrothermal method was used to deposit SiO₂ nanoparticles on the surface of pretreated jute fibers and the effect of reaction factors (tetraethoxysilane [TEOS] concentration, ammonia concentration, and reaction temperature) on the deposition of SiO₂ nanoparticles were evaluated. The results of FTIR, XRD, SEM, and TEM showed that the amorphous SiO₂ nanoparticles with an average particle size of 65.0 nm were successfully deposited on the surface of jute fibers at the TEOS/H₂O volume ratio of 1:2, ammonia of 0.55 M, reaction temperature of 100 °C (0.15 MPa) for 5 h. Compared with the sol–gel method, SiO₂ nanoparticles obtained by the hydrothermal method possessed smaller particle size and were less agglomerated, which can better fill in the surface defects of the jute fibers and result in a 12.9% increase in the tensile strength. The study on the mechanical properties and interface performance of the jute fiber reinforced PP composites indicated that the interfacial compatibility between jute fibers and PP was obviously improved. The tensile and impact strength of the composites reinforced with nano‐SiO₂ deposited jute fibers were increased by 26.87% and 25.65%, respectively, compared with the untreated jute fibers. J. VINYL ADDIT. TECHNOL., 26:43–54, 2020. © 2019 Society of Plastics Engineers     

Functionalisation of polypropylene by solid phase graft polymerisation and its effect on mechanical properties of silica nanocomposites

Abstract

To prepare macromolecular compatibiliser for grafted nano-SiO₂ /polypropylene (PP) composites, solid phase graft copolymers of PP with styrene and ethyl acrylate were synthesised, respectively. It was found that both per cent grafting and grafting efficiency can be adjusted by changing initiator concentration, reaction temperature and reaction time. As a result of partial chain scission and deterioration of ordered structure of PP during the graft polymerisation, the grafted PP exhibits poorer thermal stability and crystallisability than the unmodified PP. Mechanical tests of grafted nano-SiO₂ /PP composites indicated that the addition of PP copolymer with the same species of grafting polymer as that on the nanoparticles further improves the ductility of the composites. Molecular rigidity of the grafting polymers, presence of the homopolymer produced during the graft polymerisation, and strain rate of the load applied have an important influence on the toughening effect of the functionalised PP.     

Effects of interfacial adhesion on properties of polypropylene/Wollastonite composites

Wollastonite reinforced polypropylene (PP/CaSiO₃) composites were prepared by melt extrusion. A silane coupling agent and a maleic anhydride grafted PP (PP‐g‐MA) were used to increase the interfacial adhesion between the filler and the matrix. The increased adhesion observed by scanning electron microscopy (SEM) resulted in improved mechanical properties. A model was applied to describe the relationship between the interfacial adhesion and tensile properties of PP/CaSiO₃ composites. There is stronger interfacial adhesion between silane‐treated CaSiO₃ and polymer matrix containing PP‐g‐MA as a modifier. Results of dynamic mechanical thermal analysis (DMTA) showed that stronger interfacial adhesion led to higher storage modulus. The influence of CaSiO₃ particles on the crystallization of PP was studied by using differential scanning calorimetry (DSC). The introduction of CaSiO₃ particles does not affect the crystallization temperature and crystallinity of PP matrix significantly. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A novel method of hyperbranched poly(amide‐ester) modifying nano‐SiO2 and study of mechanical properties of PVC/nano‐SiO2 composites

A new method of surface chemical modification of nano‐SiO₂ was proposed in the paper. In the presence of catalyst, the active hydroxyl groups on the surface of nano‐SiO₂ reacted with AB₂‐type monomer (N,N‐dihydroxyethyl‐3‐amino methyl propionate) by one‐step polycondensation. And the product's Fourier transform infrared graphs and transmission electron microscopy (TEM) images proved that hyperbranched poly(amine‐ester) (HPAE) was grafted from nano‐SiO₂ surface successfully. Moreover, polyvinyl chloride (PVC)/modified nano‐SiO₂ composites were made by melt‐blending. The composites' structures and mechanical properties were characterized by TEM, scanning electron microscopy, and electronic universal testing machine. The results showed that nano‐SiO₂ grafted by HPAE increased obviously in dispersion in PVC matrix, and mechanical properties of PVC were effectively improved. Additionally, it was found that mechanical properties of PVC/nano‐SiO₂ composites reached the best when weight percent of nano‐SiO₂ in PVC matrix was 1%. Compared with crude PVC, the tensile strength of HPAE grafted nano‐SiO₂/PVC composite increased by 24.68% and its break elongation, flexural strength, and impact strength increased by 15.73, 4.07, and 184.84%, respectively. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Irradiation‐induced surface graft polymerization onto calcium carbonate nanoparticles and its toughening effects on polypropylene composites

Nano‐sized calcium carbonate was pretreated with silane coupling agent and then mixed with butyl acrylate that is of larger amount than the nanoparticles. Under γ‐irradiation, graft polymerization occurred on the nanoparticle surface, forming a nanocomposite structure consisting of grafted poly(butyl acrylate) (PBA), homopolymerized PBA, and the segregated nanoparticles. It was found that the silane pretreatment significantly promoted the graft reaction. When the grafted nano‐CaCO₃ particles were melt compounded with polypropylene (PP), an obvious synergistic effect, offered by (i) the chemical bonding between the elastomer type grafted PBA and nano‐CaCO₃ and (ii) the deliberately introduced thick interlayer mainly constructed by the homopolymerized PBA, led to a significant increase in notch impact strengths and elongation to break of PP at a rather low content of nano‐CaCO₃. Meanwhile, the tensile stiffness of the composites was also slightly increased and the yielding strength of the composites was almost unchanged. The results are different from those with conventional rubber‐toughened plastics, in which the improvement of ductility is acquired at high additive fraction and a great expense of strength performance. POLYM. ENG. SCI., 45:529–538, 2005. © 2005 Society of Plastics Engineers     

Coincorporation of nano‐silica and nano‐calcium carbonate in polypropylene

In this study, various polypropylene (PP) nanocomposites were prepared by melt blending method. The effects of different spherical nanofillers, such as 50 nm CaCO₃ and 20 nm SiO₂, on the linear viscoelastic property, crystallization behavior, morphology and mechanical property of the resulting PP nanocomposites were examined. Rheological study indicated that coincorporation of nano‐SiO₂ and nano‐CaCO₃ favored the uniform dispersion of nanoparticles in the PP matrix. Differential scanning calorimeter (DSC) and polarizing optical microscopy (POM) studies revealed that the coincorporation of SiO₂ and CaCO₃ nanoparticles could effectively improve PP crystallizability, which gave rise to a lower supercooling temperature (ΔT), a shorter crystallization half‐life (t_1/2) and a smaller spherulite size in comparison with those nanocomposites incorporating only one type of CaCO₃ or SiO₂ nanoparticles. The mechanical analysis results also showed that addition of two types of nanoparticles into PP matrix gave rise to enhanced performance than the nanocomposites containing CaCO₃ or SiO₂ individually. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of in situ surface‐modified nano‐SiO2 on the thermal and mechanical properties and crystallization behavior of nylon 1010

Nylon 1010 composites filled with two types of surface‐modified SiO₂ nanoparticles (RNS and DNS) were prepared by melt blending. The mechanical properties of the composites were evaluated. The influences of the surface‐modified nano‐SiO₂ on the thermal stability, crystallization behavior, and microstructure of nylon 1010 were investigated by thermogravimetric analysis, differential scanning calorimetry (DSC), X‐ray diffraction, and transmission electron microscopy. And the interfacial interactions between the fillers and polymer matrix were examined using a Fourier transformation infrared spectrometer. It was found that the addition of the surface‐modified nano‐SiO₂ had distinct influences on the thermal stability, mechanical properties, and crystallization behavior of nylon 1010. RNS and DNS as the fillers had different effects on the mechanical properties of nylon 1010. The composites filled with RNS at a mass fraction of 1–5% showed increased break elongation, Young's modulus, and impact strength but almost unchanged or even slightly lowered tensile strength than the unfilled matrix. The DNS‐filled nylon 1010 composites had obviously decreased tensile strength, whereas the incorporation of DNS also contributed to the increase in the Young's modulus of nylon 1010, but less effective than RNS. Moreover, the nylon 1010 composites had better thermal stability than the neat polymer matrix, and the composites filled with RNS were more thermally stable than those filled with DNS. The difference in the crystallinity of neat nylon 1010 and its composites filled with RNS and DNS was subtle, although the surface‐modified nano‐SiO₂ could induce or/and stabilize the γ‐crystalline formation of nylon 1010. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010