Preparation and performance of nano‐SiO2 stabilized Pickering emulsion type sizing agent for glass fiber

The nano‐SiO₂ particles modified by silane coupling agent A‐1100 were used for preparing the vinyl ester resin (VE) Pickering emulsion. The stable emulsion could be served as the film former of sizing agent for glass fiber (GF). The influence of the wettability and the addition amount of nano‐SiO₂ on the stability of film former emulsion was explored. The effect of nano‐SiO₂ Pickering emulsion type sizing agent on the properties of GF was investigated. SEM images show that there existed a layer of sizing agent film with nano‐SiO₂ particles evenly on the GF surface. The abrasion resistance of the sized GF reached 3,579 times and the stiffness was 69 mm. The strand integrity also performed well. The fracture strength of GF bundles treated by Pickering emulsion type sizing agent increased by 28.6% to 0.504 N/Tex compared with that of the unsized GF bundles. The interlaminar shear strength (ILSS) of GF/VE composites sized by self‐made sizing agent which contained nano‐SiO₂ has improved, compared to the unsized GF reinforced VE composite. POLYM. COMPOS., 37:334–341, 2016. © 2014 Society of Plastics Engineers     

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     

Effects of high nano‐SiO2 contents on properties of epoxy‐modified polybenzoxazine

High‐performance nanosilica composites based on epoxy‐modified polybenzoxazine matrices are developed. Chemorheological study of benzoxazine–epoxy resin mixtures reveals that processing window of the benzoxazine resin (BA‐a) is substantially broadened with an addition of the liquid epoxy. Glass transition temperature (T _g) of the BA‐a copolymerized with epoxy resin shows a synergistic behavior with a maximum T _g value (174°C) at the benzoxazine–epoxy mass ratio of 80:20. The copolymer at this composition is also used as a matrix for nano‐SiO₂ composites. A very low melt viscosity of the benzoxazine–epoxy mixtures promotes good processability with the maximum attainable nano‐SiO₂ loading up to 35 wt%. From scanning electron microscopy investigation, fracture surface of the 35 wt% nano‐SiO₂‐filled benzoxazine–epoxy composite reveals relatively homogeneous distribution of the nano‐SiO₂ in the copolymer with good particle wet‐out. In addition, very high reinforcing effect was also observed in such high content of the nano‐SiO₂, i.e., about 2.5 times in modulus improvement. This improvement is attributed to the strong bonding between the copolymer matrix and the nano‐SiO₂ through ether linkage as confirmed by Fourier‐transform infrared investigation. POLYM. COMPOS., 38:2261–2271, 2017. © 2015 Society of Plastics Engineers     

Effect of nano‐silica on the mechanical,thermal, and crystalline properties of poly(vinyl alcohol)/nano‐silica films

Poly(vinyl alcohol)/nano‐silica (PVA/nano‐SiO₂) films were prepared through extrusion blowing with the addition of water and glycerin as plasticizer. The characteristic properties of PVA/nano‐SiO₂ films were investigated by differential scanning calorimetry, dynamic mechanical analysis, Haake torque rheometry, and atomic force microscopy (AFM). The results showed that the mechanical properties of PVA/nano‐SiO₂ were improved dramatically. The tensile strength of the nanofilms increased from 62 MPa to 104 MPa with loading 0.3 wt % nano‐SiO₂ and the tear strength was improved from 222 KN/m to 580 KN/m. The crystallinity of the films loaded with 0.4 wt. % nano‐SiO₂ decreased from 32.2% to 21.0% and the AFM images indicated that the amorphous region of nanofilms increased with increasing nano‐SiO₂ content. The storage modulus and loss modulus increased to two and nearly three times with 0.3 wt % nano‐SiO₂ loading. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nano‐SiO2/PMMA‐PU composite particles with core‐shell structure via emulsion polymerization and their application in epoxy resin

A novel method of nano‐SiO₂/poly(methyl methacrylate)(PMMA)‐polyurethane(PU) composite particles modifying epoxy resin is reported. The composite particles with the obvious core‐shell structure were prepared by emulsion polymerization of PMMA and PU prepolymer on the surface of nano‐SiO₂. The diameter of the composite particles was 50–100 nm with dark core SiO₂ (30–60 nm) and light shell polymer of PMMA and PU (20–30 nm); moreover, PU was well distributed in PMMA with about 10 nm diameter. After nano‐SiO₂ was encapsulated by PMMA and PU, the Si content on the surface decreased rapidly to 2.08% and the N content introduced by PU was about 1.27%. The ratio of polymer to original nano‐SiO₂ (f_p), the grafting ratio of polymer to original nano‐SiO₂ (f_r) and the efficiency grafting ratio of polymer (f_e) were, respectively, about 116.7%, 104.4%, and 89.5%. The as‐prepared composite particles were an effective toughness agent to modify epoxy resin, and the impact strength of the modified epoxy resin increased to 46.64 kJ m^?2 from 19.12 kJ m^?2 of the neat epoxy resin. This research may enrich the field of inorganic nanoparticles with important advances toward the modification for polymer composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41919.     

Study of surface‐functionalized nano‐SiO2/polybenzoxazine composites

A series of the surface‐functionalized nano‐SiO₂/polybenzoxazine (PBOZ) composites was produced, and an attempt was made to improve the toughness of PBOZ material, without sacrificing other mechanical and thermal properties. A benzoxazine functional silane coupling agent was synthesized to modify the surface of nano‐SiO₂ particles, which were then mixed with benzoxazine monomers to produce the nano‐SiO₂‐PBOZ nanocomposites. The notched impact strength and the bending strength of the nano‐SiO₂‐PBOZ nanocomposites increase 40% and 50%, respectively, only with the addition of 3 wt % nano‐SiO₂. At the same load of nano‐SiO₂, the nano‐SiO₂‐PBOZ nanocomposites exhibit the highest storage modulus and glass‐transition temperature by dynamic viscoelastic analysis. Moreover, the thermal stability of the SiO₂/PBOZ nanocomposites was enhanced, as explored by the thermogravimetric analysis. The 5% weight loss temperatures increased with the nano‐SiO₂ content and were from 368°C (of the neat PBOZ) to 379°C or 405°C (of the neat PBOZ) to 426°C in air or nitrogen with additional 3 wt % nano‐SiO₂. The weight residue of the same nanocomposite was as high as 50% in nitrogen at 800°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of styrene‐acrylic emulsion by using nano‐SiO2 as seeds

A styrene‐acrylic/SiO₂ nanoparticle composite emulsion was prepared by using SiO₂ nanoparticles as seeds. The effect of factors such as the level of nano‐SiO₂, reaction temperature and ultrasound treatment of nano‐SiO₂ on the stability of the polymerization reaction was investigated. Water‐resistance of the emulsion was measured. The level of nano‐SiO₂ in the emulsion was determined by inductively coupled plasma (ICP) spectrometry. The particle morphology of the emulsion with nano‐SiO₂ was observed with transmission electron microscopy (TEM). The kinetics of the polymerization was also studied at various temperatures and various levels of nano‐SiO₂. They showed that the level of nano‐SiO₂ and reaction temperature had a great influence on the monomer conversion, particle size, coagulum content and viscosity of the emulsion. Nano‐SiO₂ treated by ultrasonics can increase the coagulum content greatly, but it does not improve the water resistance of the emulsion. The level of nano‐SiO₂ in the emulsion was lower than the theoretical value. The reaction kinetics indicated that the level of nano‐SiO₂ had less influence on the reaction rate than the reaction temperature. Even a small amount of nano‐SiO₂ can decrease the reaction rate. Copyright © 2004 Society of Chemical Industry     

Nanocomposites of a bismaleimide resin with octaphenylsilsesquioxane or nano‐SiO2

Nanocomposites were prepared from the resin of 4,4′‐bismaleimido‐diphenylmethane (BDM) with dipropargyl ethers of hexafluorobisphenol A (DPBPF) and octaphenylsilsesquioxane (OPS) or nano‐SiO₂. The nanocomposites were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, dynamic mechanical analysis and thermogravimetric analysis. The results exhibited that OPS or nano‐SiO₂ particles could be easily dispersed in the nanocomposites and the glass transition and decomposition temperatures of c‐BDM‐DPBPF‐OPS and c‐BDM‐DPBPF‐SiO₂ nanocomposites were higher than those of c‐BDM‐DPBPF resin. The reinforcement of OPS was more effective than that of nano‐SiO₂ in the nanocomposites. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Comprehensive high‐performance epoxy nanocomposites co‐reinforced by organo‐montmorillonite and nano‐SiO2

Comprehensive high‐performance epoxy nanocomposites were successfully prepared by co‐incorporating organo‐montmorillonite (o‐MMT) and nano‐SiO₂ into epoxy matrix. Because of the strong interaction between nanoscale particles, the MMT layers were highly exfoliated, and the exfoliated nanoscale MMT monoplatelets took an interlacing arrangement with the nano‐SiO₂ particles in the epoxy matrix, as evidenced by X‐ray diffraction measurement and transmission electron microscopy inspection. Mechanical tests and thermal analyses showed that the resulting epoxy/o‐MMT/nano‐SiO₂ nanocomposites improved substantially over pure epoxy and epoxy/o‐MMT nanocomposites in tensile modulus, tensile strength, flexural modulus, flexural strength, notch impact strength, glass transition temperature, and thermal decomposition temperature. This study suggests that co‐incorporating two properly selected nanoscale particles into polymer is one pathway to success in preparing comprehensive high‐performance polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on the preparation and thermal shrinkage properties of nano‐SiO2/UHMWPE/HDPE blend microporous membranes

Nano‐SiO₂/UHMWPE/HDPE blend microporous membranes (NBMs) with different content of nano‐SiO₂ particles were prepared via thermally induced phase separation process. Thermogravimetric analysis was used to investigation of the amount of nano‐SiO₂ particles reserved in NBMs. This approach showed that about 59% of total content of nano‐SiO₂ particles reserved in NBMs. The formation and development of the interface pores were studied by scanning electron microscopy. NBMs performance was characterized by a variety of metrics including thermal shrinkage, melting and crystallization behavior, porosity and pore diameter, and permeability. The results indicated that nano‐SiO₂ particles served as nucleating agent increasing the crystalline of NBMs. The comprehensive properties of NBMs were optimum when the content of nano‐SiO₂ particles was 1%. Compared with pure HDPE separators, NBMs exhibit higher porosity and lower thermal shrinkage due to its high crystalline and the enrichment of UHMWPE chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41321.     

Water‐dispersible conducting polyaniline/nano‐SiO2 composites without any stabilizer

A water‐dispersible conducting polyaniline/ nano‐SiO₂ composite, with a conductivity of 0.071 S cm^?1 at 25°C, was prepared by the oxidative polymerization of aniline in the presence of amorphous nano‐SiO₂ particles. And the structure, morphology, thermal stability, conductivity, and electroactivity of this composite were also investigated. This composite has been steadily dispersed in the aqueous solution for about 10–36 h without the need for any stabilizer. It would significantly impulse the commercial applications of conducting polyaniline/nano‐SiO₂ composite as fillers for antistatic and anticorrosion coatings. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

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     

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     

Fabrication of functionally graded nano‐TiO2‐reinforced epoxy matrix composites

Functionally graded nano‐TiO₂ epoxy matrix composites were successfully fabricated using a centrifugal method. In the preparation of the composite, the aggregation of nano‐TiO₂ occurred during curing, which had a negative effect on the composite performance. To solve this problem, we introduced a silane coupling agent to modify the surface of the nano‐TiO₂, thereby improving the performance and mechanical properties simultaneously. The modified nano‐TiO₂ (s‐TiO₂) had better dispersion in the epoxy resin, making it possible to produce depth gradients of the mechanical properties of functionally graded materials (FGMs). The s‐TiO₂ was characterized with respect to functional groups, morphology, and chemical elements using transmission electron microscopy, X‐ray photoelectron spectroscopy, and Fourier‐transform infrared spectroscopy. The results show that a silane layer was successfully coated on the surface. Also, the gradients of the mechanical and permittivity properties of the FGM indicated that by modifying the surface of the nano‐filler, it is possible to fabricate nano‐filler‐reinforced epoxy matrix FGMs using a centrifugal method. POLYM. COMPOS., 35:557–563, 2014. © 2013 Society of Plastics Engineers     

Nano‐sio2‐reinforced ultraviolet‐curing materials for three‐dimensional printing

As an additive manufacturing technology, ultraviolet (UV)‐curing three‐dimensional printing, which requires the use of a photocurable resin, is increasingly being used to produce customized end‐user parts of many complex shapes. In this study, to improve the strength and ductility of printing materials, nano‐SiO₂‐reinforced photocurable resins were prepared by a planetary ball mill; then, the morphology, photochemistry, thermal property, and mechanical properties of the nanocomposites were investigated and characterized. Transmission electron microscopy analysis indicated that the modified nano‐SiO₂ was well dispersed in the photocurable resin. The glass‐transition temperature increased from 67.2°C for the unfilled resin to 71.7 and 80.1°C for nanocomposites with nano‐SiO₂ contents of 0.3 and 0.7 wt %, respectively. The tensile strength and impact strength were increased by 46.7 and 165.3% for nanocomposites with 0.3 wt % nano‐SiO₂. The flexural modulus of the nanocomposites increased from 1.7 to 8.0 GPa when 0.7 wt % nano‐SiO₂ was added to the photocurable resin; this appeared to originate from the relatively high level of dispersion and the intimate combination of the nano‐SiO₂ with the matrix. The investigation of the physical and chemical properties of such UV‐curing materials showed that the low filler concentration (<1 wt %) of nano‐SiO₂ did not affect the processability of the nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42307.     

The tribological properties of benzoxazine‐bismaleimides composites with functionalized nano‐SiO2

To improve the tribological properties of benzoxazine (BOZ) resin, bismaleimides (BMI) resin is chosen as organic phase, hyperbranched polysilane functionalized SiO₂ nanoparticles (HBPSi‐SiO₂) are chosen as inorganic modifiers to prepare HBPSi‐SiO₂/BOZ‐BMI composites using high shear and ultrasonic processes. The effect of content of HBPSi‐SiO₂ on the mechanical properties and tribological properties of the composites are investigated. The results show that suitable addition of HBPSi‐SiO₂ can largely enhance the impact strength, reduce the friction coefficient, and wear rate of BOZ‐BMI resin. Scanning electron microscopy is employed to research the wearing mechanism of materials. The severe wear of the BOZ pure resin is owing to fatigue wear, and the moderate wear of BOZ‐BMI resin is attributed to adhesive wear. While, the mild wear of the composites with HBPSi‐SiO₂ is due to abrasive wear. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The influence of interphase on nylon‐6/nano‐SiO2 composite materials obtained from in situ polymerization

Three commercially available silane, titanate and aluminate based coupling agents were used to pretreat nano‐SiO₂ for the preparation of nylon‐6/nano–SiO₂ composites via in situ polymerization. The interphases formed in different composite systems and their influence on material properties were investigated. Results indicated that the interfacial interactions differed between composite systems, whereas rigidity and toughness of composites were all improved by addition of pretreated silicas at an optimal content of 4.3 wt%. The presence of pretreated silicas did not have a distinct influence in the non‐isothermal crystallization behaviour of the nylon matrix. The composites containing pretreated silicas had slightly higher dynamic viscosities and superior storage moduli at high frequency, compared with neat nylon‐6. Copyright © 2003 Society of Chemical Industry     

Structure and properties of nylon 1010/ethylene‐vinyl acetate rubber–based dynamically vulcanized thermoplastic elastomers filled with SiO2

Dynamically vulcanized Nylon 1010/ethylene‐vinyl acetate rubber (EVM)/SiO₂ nanocomposites were prepared. Maleic anhydride grafted ethylene‐vinyl acetate copolymer (EVA‐g‐MA) and nano‐silica (SiO₂) was used as a compatibilizer and a filler, and silane coupling agent (KH550, 3‐triethoxysilylpropylamine) was used to improve the dispersion of SiO₂ in the nanocomposites. The nanocomposites were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), dynamic mechanical analysis (DMA), differential scanning calorimeter (DSC), and rheology analysis and mechanical properties test. SEM and AFM images showed that the compatibility between Nylon 1010 and EVM was improved by adding the compatibilizer. An increase in SiO₂ content and the addition of the compatibilizer led to an increase in the tensile strength of the nanocomposite. A nanocomposite based on Nylon 1010/EVM/DCP (30/70/0.8) with tensile strength of 16.3 MPa and elongation at break of 180% was obtained by the addition of 15 phr EVA‐g‐MA and 40 phr SiO₂. The non‐isothermal crystallization processes of Nylon/EVM blend were investigated by DSC. It was observed that EVM rubber could act as heterogeneous nuclei for Nylon which was more effective in Nylon/EVM/DCP blend than in Nylon/EVM blend. POLYM. ENG. SCI., 55:581–588, 2015. © 2014 Society of Plastics Engineers     

Fabrication of a low‐cost nano‐SiO2/PVC composite ultrafiltration membrane and its antifouling performance

A novel low‐cost SiO₂/Polyvinylchloride (PVC) membrane with different nano‐SiO₂ particles loading (0–4 wt %) was prepared by the phase‐inversion process. The optimum nano‐SiO₂ dosage was determined as 1.5 wt % based on the casting solution compositions, the membranes' mechanical properties and hydrophilicities, the pure water fluxes, microstructures, and absorption of protein. Compared with the bare membrane, the membrane with 1.5 wt % nano‐SiO₂ addition presented better capabilities against the protein absorption and bacterial attachment, better antifouling performance, and higher flux recovery ratio in filtration of the supernatant liquor which collected from a secondary sedimentation tank in a municipal wastewater plant. The SiO₂/PVC membranes have applicable potential in the municipal wastewater treatment for their low price, good antifouling performance and high removal efficiencies of SS (over 97.2%), COD (up to 82.9%) and total bacteria (more than 93.6%). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41267.