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     

Effects of epoxy resin contents on the rheological properties of epoxy‐asphalt blends

Epoxy‐asphalt and its mixture have been proposed for the long span orthotropic steel deck bridges because it shows excellent heat resistance, free from bleeding, low temperature cracking resistance, and aggregate scattering resistance. In this study, the effects of epoxy resin contents on rheological properties of epoxy‐asphalt binders were studied using dynamic shear rheometer. Experimental results indicated that the improvement of the viscoelastic performance of asphalt binder is noticeable at high temperatures, at which the elasticity is increased (higher G* and lower δ) for epoxy‐asphalt with increase in epoxy resin contents. The viscous behavior of the asphalt also increased when epoxy resin is added. Creep test results indicated that epoxy‐asphalt binder can not only resist deformation at elevated temperatures but recover satisfactorily from strain. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Effect of amphoteric dispersant on the dispersion properties of nano‐SiO2 particles

An amphoteric polycarboxylate dispersant (APC) was synthesized by copolymerization of acrylic acid (AA), methacryloxyethyltrimethyl ammonium chloride (DMC), and isopentenol polyoxyethylene ether (IPEG). The molecular structure of APC was characterized by FT‐IR, ¹H‐NMR, and GPC. Effect of the dosage of APC on the rheological performance of nano‐SiO₂ suspension was investigated by measurements of the plastic viscosity. The results indicated that the best dispersion effect of APC was obtained when the dosage of APC was about 10 wt % (by the weight percent of nano‐SiO₂), which can maintain the dispersion of nano‐SiO₂ suspension uniformly for 4 h without settlement. Meanwhile, the zeta potential value on the surface of nano‐SiO₂ particles shows that the better dispersion performance of APC was attributed to the solvation water film formed by the polyoxyethylene side chains and the electrostatic repulsion formed by positively groups (C?N⁺) on the APC structure combined with ‐SiO^– groups on the surface of nano‐SiO₂ particles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45075.     

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     

The effect of the interface structure of different surface‐modified nano‐SiO2 on the mechanical properties of nylon 66 composites

The nylon 66‐based nanocomposites containing two different surface‐modified and unmodified SiO₂ nanoparticles were prepared by melt compounding. The interface structure formed in different composite system and their influences on material mechanical properties were investigated. The results indicated that the interfacial interactions differed between composite systems. The strong interfacial adhesion helped to increase tensile strength and elastic modulus of composites; whereas, the presence of modification layer in silica surface could enhance the toughness of composites, but the improvement of final material toughness was also correlated with the density of the adhered nylon 66 chains around silica nanoparticles. In addition, the results also indicated that the addition of surface‐modified silica nanoparticles has a distinct influence on the nonisothermal crystallization behavior of the nylon 66 matrix when compared with the unmodified silica nanoparticle. © 2007 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     

Preparation and properties of cardanol‐based polybenzoxazine/SiO2 hybrids by sol‐gel technique

A new cardanol‐based benzoxazine monomer containing a hydroxyl group (CBZ) was synthesized and characterized by FT‐IR and ¹H NMR spectroscopy. The formation mechanism of cardanol‐based polybenzoxazine/SiO₂ hybrids from CBZ and tetraethoxysilane (TEOS) by sol‐gel technique was invested by FT‐IR analysis. FT‐IR and SEM confirmed that there were many SiO₂ particles formed and embedded in the cardanol‐based polybenzoxazine. A phase separation occurred when the ratio (wt) of TEOS to CBZ was not less than 3 : 5. TGA results illuminated the thermal stability and char yield of cardanol‐based polybenzoxazine could be enhanced due to the formation of SiO₂ particles in the polybenzoxazine matrix. Incorporation of SiO₂ could improve the surface de‐wetting and anti‐ultraviolet properties of the films. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Rare‐earth‐doped SiO2‐CaF2 glass ceramic nano‐particle with upconversion properties

Rare‐earth‐doped upconversion nano‐phosphor shows new possibilities in the field of bioimaging because of its unique properties like higher penetration depth, low signal to noise ratio (SNR), good photo stability, and zero auto fluorescence. The oxyfluoride glass system is the combination of both fluoride and oxide where fluoride host offers high optical transparency due to low phonon energy and oxide network offers high physical stability. Thus, in the present work, an attempt has been made to synthesize 1 mol% Er³⁺ doped SiO₂‐CaF₂ glass ceramic nano‐particles through sol‐gel route. The synthesized glass ceramic particles were heat treated at 4 different temperatures starting from 600°C to 900°C.The X‐ray diffraction (XRD) analysis and Transmission electron microscopy (TEM) analysis confirmed the formation of CaF₂ nano‐crystals in the matrix which is 20‐30 nm in size. The vibrational spectroscopic analysis of the glass ceramics sample has been investigated by Fourier transform infrared (FTIR) spectroscopy. The UV‐Visible‐NIR spectroscopy analysis was carried out to analyze the absorption intensity in the near infrared region. Upon 980 nm excitation, the sample shows red emission corresponds to ⁴F_9/2→⁴I_15/2 energy level transition. The prepared nano‐particles showed excellent biocompatibility when tasted on MG‐63 osteoblast cells.     

Investigation of the thermal properties of novel adamantane‐modified polybenzoxazine

Two novel structures of adamantane‐modified benzoxazines were synthesized from 4‐(1‐adamantyl)‐phenol through the incorporation of adamantane as a pendant group into the polybenzoxazine backbone. Both ¹H‐NMR and Fourier transform infrared spectra were used to characterize these structures. The rigid structure of the adamantane tended to hinder the chain mobility (boat anchor effect) and substantially enhanced the thermal properties, including the glass‐transition temperature and decomposition temperature, especially for poly(6‐adamantyl‐3‐methyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine). In the poly(6‐adamantyl‐3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine) system, however, the opposite result for the glass‐transition temperature was observed and it was interpreted as lower crosslinking density. The phenyl group was bulkier than the methyl group, and the movement of the molecular chain was hindered between bridging points during the curing process; this resulted in a lower crosslinking density and a lower glass‐transition temperature than those of poly(6‐adamantyl‐3‐methyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 932–940, 2004     

Effect of nano‐SiO2 on granule characteristic and fusion process of Poly(vinyl chloride‐co‐vinyl acetate)/nano‐SiO2 composite resin

Poly(vinyl chloride‐co‐vinyl acetate) (PVVA)/nano‐SiO₂ composite resin was prepared by radical suspension polymerization of the monomers in the presence of fumed nano‐SiO₂ particles premodified with γ‐methylacryloxypropyl trimethoxysilane. The cool dioctyl phthalate absorption percentage, granule porosity, and specific surface area of the composite resin were enhanced through incorporation of nano‐SiO₂ into the PVVA. Scanning electron microscope pictures showed the resin had higher porosity. PVVA/nano‐SiO₂ composite resin was mixed with pure PVC resin to form a mixture sample (polymer‐composite blend [PCB]) and the mixture was fused in the torque rheometer. The rheological test results indicated that, at a certain nano‐SiO₂ content, the fusion speed of PCB was accelerated and the fusion temperature of PCB was decreased, owing to nano‐SiO₂ dispersed evenly in the polymer matrix. When excessive nano‐SiO₂ was loaded, the fusion torque, the fusion time, and the fusion temperature of PCB were all increased. These properties are correlative to the dispersive density of nano‐SiO₂ in the polymer matrix. This study also demonstrated that the introduction of small amounts of nano‐SiO₂ into the resin increased the impact strength and tensile strength of PCB simultaneously. J. VINYL ADDIT. TECHNOL., 20:230–236, 2014. © 2014 Society of Plastics Engineers     

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     

Study on the properties of nano‐TiO2 particles modified silk fibroin porous films

Using the freeze‐drying method, Nano‐TiO₂/silk fibroin porous films were synthesized with different ratios of TiO₂ to silk fibroin solution. Through scanning electron microscopy (SEM), X‐ray diffraction (XRD), thermogravimetric analysis (TGA), tensile strain, and water‐solubility tests, the structures and properties of these porous films were characterized. The SEM results indicated that the pores of the nano‐TiO₂/silk fibroin porous films were uniformly distributed by the freeze‐drying method. The XRD analysis indicated that the formation of nano‐TiO₂ particles might induce a conformational transition of silk fibroin from the typical Silk I to the typical Silk II structure partly with an increase in the crystallinity of the porous films. Compared with the pure silk fibroin porous films, the mechanical properties of nano‐TiO₂/silk fibroin porous films were improved, and its heat transition temperature was also enhanced; however, the water‐solubility of this material was diminished. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Free‐volume effects on the thermomechanical performance of epoxy–SiO2 nanocomposites

In this study, free‐volume effects on the thermal and mechanical properties of epoxy–SiO₂ nanocomposites were investigated. SiO₂ particles ranging from 15 nm to 2 µm were used, and the nature of the matrix–filler interphase was modified by surface grafting. Nanoparticles 15 nm in diameter yielded an increase in the glass‐transition temperature (T_g) of the composites up to 5 °C; at the same time, they increased the storage modulus (E′) from 2340 to 2725 MPa. Conversely, large particles markedly decreased both T_g and E′; this suggested the pivotal role of nanoparticle size on the final properties of the nanocomposite. The functionalization of SiO₂ nanoparticles markedly improved their dispersion within the epoxy matrix. The positron annihilation lifetime spectroscopy results indicate that the free volume strongly depended on the interphase. These experimental findings obtained here could be extrapolated to industrially relevant nanocomposites and could provide a rationale for the comprehension of free‐volume effects on the thermal and mechanical properties of nanocomposite materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45216.     

Flame retardancy behaviors and structural properties of polypropylene/nano‐SiO2 composite textile filaments

The number of efforts about modifying the properties of polymeric fibers by organic or inorganic particles has increased recently because of high‐tech applications of textiles. In addition to these attempts, the discovery of nanotechnology also leads to the development of nanoparticles for various end uses such as nanocomposite fibers. In this article, we aimed to produce slow burning or flame retardant polypropylene filaments for carpet pile yarns by incorporating SiO₂ nanoparticles into polymer. Therefore, we present the preparation of filaments incorporating 0.3, 1, and 3% SiO₂ nanoparticles and investigate the effects of nanoparticles on the flame retardancy and structural behavior of filaments. Polypropylene and nanoparticles were compounded by melt‐compounding using twin‐screw extruder before spinning. Filaments with trilobal cross sections were spun using pilot melt spinning equipment. The structural properties of nanocomposite fibers were analyzed using X‐ray difractometry, differential scanning calorymetry, scanning electron microscopy, and tensile tests. The flammability behaviors of filaments were evaluated using the oxygen index method. The effect of nanoparticles on structural properties and flame retardancy behaviors of filaments were summarized and discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of bipolar membranes modified using photocatalyst nano‐TiO2 and nano‐ZnO

The nano‐ZnO and nano‐TiO₂ were added into chitosan (CS) anion layer to prepare polyvinyl alcohol (PVA) ‐ sodium alginate (SA)/ TiO₂‐ZnO‐CS (here, PVA:polyvinyl alcohol; SA:sodium alginate) bipolar membrane (BPM), which was characterized using scanning electron microscopy, atomic force microscopy (AFM), thermogravimetric analysis (TG), electric universal testing machine, contact angle measurer, and so on. Experimental results showed that nano‐TiO₂‐ZnO exhibited better photocatalytic property for water splitting at the interlayer of BPM than nano‐TiO₂ or nano‐ZnO. The membrane impedance and voltage drop (IR drop) of the BPM were obviously decreased under the irradiation of high‐pressure mercury lamps. At a current density of 60 mA/cm², the cell voltage of PVA‐SA/TiO₂‐ZnO‐CS BPM‐equipped cell decreased by 1.0 V. And the cell voltages of PVA‐SA/TiO₂‐CS BPM‐equipped cell and PVA‐SA/ZnO‐CS BPM‐equipped cell were only reduced by 0.7 and 0.6 V, respectively. Furthermore, the hydrophilicity, thermal stability, and mechanical properties of the modified BPM were increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and properties of epoxy‐modified tung oil waterborne insulation varnish

This work aimed to develop a novel epoxy‐modified tung oil waterborne insulation varnish with blocked hexamethylene diisocyanate as a curing agent. The Diels–Alder reaction between tung oil and maleic anhydride, and the ring‐opening esterification reaction of epoxy resin were confirmed. The conversion rate of epoxy was explored as a function of reaction time and temperature. The effects of epoxy resin content on the thermal stability, water absorption and insulation properties (insulation strength, volume resistivity, and surface resistivity) of films were investigated, and the resistances of films to salted water were evaluated. The increase in epoxy resin contents could improve the thermal stability and insulation properties of films, and decreased the water adsorption of films, but when the epoxy resin content reached 30% and above, the water solubility of resin became poor. After being immersed in 3.5 wt % NaCl solution, the electrical insulation strength of films were lower than that in dry state, and decreased as the immersed time prolonged. In particular, the electrical insulation strength loss of films increased significantly for epoxy resin content at 15% and below. Furthermore, the increase of epoxy resin content could improve the hardness and adhesion of films, but the flexibility of films became worse. On the basis of experimental, the epoxy resin content at 25% was appropriate to prepare waterborne epoxy‐modified tung oil resin. The resulting varnish may have potential as an immersing insulation varnish for the spindle of electric motor. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42755.     

Investigation of epoxy‐resin‐modified asphalt binder

Epoxy asphalt (EA) binder has been used extensively for paving long‐span bridges in many countries because it shows excellent heat resistance, is free from bleeding, has a low‐temperature cracking resistance, and has aggregate scattering resistance. EA binders were prepared by the mixture of asphalt, epoxy resin, and a new curing agent (CR) with functional groups. The properties of the EA binder were characterized by their viscosity, tensile strength, elongation at break, compatibility, morphology, glass transition temperature (T_g), contact angle, and surface free energy. The curing process was analyzed. The results indicate that the curing temperature and asphalt content had significant effects on the properties of the EA binder. We observed that most of the strength was generated after the first 3 h at 165 °C; this provided good workability for EA pavement construction. The CR with various functional groups improved the compatibility and morphology of the EA binder. The test results show that T_g of the EA binder decreased and the contact angles increased with increasing asphalt content. It is worth noting the contact angles between water and the EA binder were always greater than 90°; this implied that the EA binder was hydrophobic and, hence, water repellent. The surface free energy and dispersion force increases with decreasing asphalt content. However, the polarity forces decreased with decreasing asphalt content. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43401.     

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     

Tribological properties of bismaleimide composites with surface‐modified SiO2 nanoparticles

In this article, the surface of SiO₂ nanoparticles was modified by silane coupling agent N‐(2‐aminoethyl)‐γ‐aminopropylmethyl dimethoxy silane. The bismaleimide nanocomposites with surface‐modified SiO₂ nanoparticles or unmodified SiO₂ nanoparticles were prepared by the same casting method. The tribological performance of the nanocomposites was studied on an M‐200 friction and wear tester. The results indicated that the addition of SiO₂ nanoparticles could decrease the frictional coefficient and the wear rate of the composites. The nanocomposites with surface‐modified SiO₂ nanoparticles showed better wear resistance and lower frictional coefficient than that with the unmodified nanoparticles SiO₂. The specific wear rate and the steady frictional coefficient of the composite with 1.0 wt % surface‐modified SiO₂ nanoparticles are only 1.8 × 10^?6 mm³/N m and 0.21, respectively. The dispersion of surface‐modified SiO₂ nanoparticles in resin matrix was observed with transmission electron microscope, and the worn surfaces of pure resin matrix and the nanocomposites were observed with scanning electron microscope. The different tribological behavior of the resin matrix and the filled composites should be dependent on their different mechanical properties and wear mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008