Influence of curing agent and compatibilizer on the physicomechanical properties of polypropylene/nitrile butadiene rubber blends investigated by positron annihilation lifetime technique

A series of thermoplastic vulcanizates of polypropylene (PP)/nitrile butadiene rubber (NBR) (50/50) have been prepared by melt‐mixing method, using phenolic resin/SnCl₂ as the curing system and maleic anhydride‐functionalized PP (PP‐g‐MA) and carboxylated NBR (NBRE‐RCOOH) as the compatibilizing system. Triethylenetetramine was also employed to promote the reaction between the functionalized polymers. The effects of curing agent and compatibilizer on the mechanical and morphological properties have been studied. A novel technique based on positron annihilation lifetime spectroscopy has been used to measure the free volume parameters of these systems. The positron results showed minimum free volume size and free volume fraction at 5.0% of the curing agent suggesting some crosslinking in the rubber phase. The reduction in free volume holes at 2.5% of the compatibilizer is interpreted as improvement in the interfacial adhesion between the components of the blend. The observed variation of free volume fraction is opposite to the tensile strength and exhibits the correlation that, lesser the free volume more is the tensile strength at 2.5% of the compatibilizer in the blend. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4672–4681, 2006     

Preparation and characterization of novel addition cured polydimethylsiloxane nanocomposites using nano‐silica sol as reinforcing filler

A series of novel addition cured polydimethylsiloxane (PDMS) nanocomposites with various amounts of nano‐silica sol were prepared via hydrosilylation for the first time. The influence of various amounts of nano‐silica sol on the morphology, thermal behavior, mechanical and optical properties of these PDMS nanocomposites was studied in detail. It was found that with an increment in the amount of nano‐silica sol the reinforcing effect of the nano‐silica sol on the thermal and mechanical properties of the PDMS nanocomposites was very noticeable compared with the reference material. The prominent improvements in resistance to thermal degradation and mechanical properties can probably be attributed to the strong interaction of PDMS chains and uniformly dispersed particles resulting from the nano‐silica sol. However, the transparency of the PDMS nanocomposites slightly decreased with an increment in weight fraction of nano‐silica, compared with that of PDMS composite without nano‐silica (Sol‐0), which can probably be ascribed to an increasing size of the aggregated particles in the PDMS nanocomposites. The optimum amount of nano‐silica sol for preparing novel addition curing PDMS nanocomposites was about 15 wt%. © 2015 Society of Chemical Industry     

Free‐volume hole properties of two kinds thermoplastic nanocomposites based on polymer blends probed by positron annihilation lifetime spectroscopy

Two type of nanocomposites—an immiscible blend, high density polyethylene/polyamide 6 (HDPE/PA‐6) with organomodified clay, and a compatibilized blend, high density polyethylene grafted with acrylic acid/PA‐6 (PEAA/PA‐6) with organomodified clay—were prepared via melt compounding. X‐ray diffraction and transmission electron microscopy results revealed that the clay was intercalated and partially exfoliated. Positron annihilation lifetime spectroscopy has been utilized to investigate the free‐volume hole properties of two type of nanocomposites. The results show a negative deviation of free‐volume size in PEAA/PA‐6 blend, and a positive deviation in HDPE/PA‐6 blend, and I₃ has a greater negative deviation in compatibilized blend than in immiscible blend due to interaction between dissimilar chains. For nanocomposites based on polymer blends, in immiscible HDPE/PA‐6/organomodified clay system, the variation of free‐volume size with clay content is not obvious and the free‐volume concentration and fraction decreased. While in the case of compatibilized PEAA/PA‐6/organomodified clay nanocomposites, complicated variation of free‐volume properties due to interactions between two phases and organomodified clay was observed. And the interaction parameter β shows the interactions between polymers and organomodified clay. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2463–2469, 2006     

Fullerene containing polyurethane nanocomposites for microwave applications

Novel flexible polyurethane (PU) composite films containing nano‐barium hexaferrite (BaF) and nano‐barium titanate (BT) have been synthesized and characterized. The PU nanocomposites were synthesized from fullerenol and prepolymer of hexamethylene diisocyante and polytetramethylene glycol by adding 1–3% each of BaF (high permeability) and BT (high permittivity). The incorporation of the nanopowders was confirmed by X‐ray diffraction (XRD), transmission electron microscopy, and energy dispersive X‐ray diffraction (EDX). Study of thermal properties by thermogravimetric analysis and dynamic mechanical analysis revealed enhanced thermal stability of the nanocomposites. Study of mechanical properties showed that the tensile strength had increased remarkably in the nanocomposites. The electromagnetic‐absorbing properties were studied by measuring the complex permeability and permittivity in the frequency range of 8.2 to 12.4 GHz. The good reflection loss of the nanocomposites at such low filler content suggests its potential applicability as a radar absorber. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nanocomposites of poly(vinyl chloride) and nanometric calcium carbonate particles: Effects of chlorinated polyethylene on mechanical properties,morphology, and rheology

Nanocomposites of poly(vinyl chloride) (PVC) and nano‐calcium carbonate (CaCO₃) particles were prepared via melt blending, and chlorinated polyethylene (CPE) as an interfacial modifier was also introduced into the nanocomposites through preparing CPE/nano‐CaCO₃ master batch. The mechanical properties, morphology, and rheology were studied. A moderate toughening effect was observed for PVC/nano‐CaCO₃ binary nanocomposites. The elongation at break and Young's modulus also increased with increasing the nano‐CaCO₃ concentration. Transmission electron microscopy (TEM) study demonstrated that the nano‐CaCO₃ particles were dispersed in a PVC matrix uniformly, and a few nanoparticles agglomeration was found. The toughening effect of the nano‐CaCO₃ particles on PVC could be attributed to the cavitation of the matrix, which consumed tremendous fracture energy. The notched Izod impact strength achieved a significant improvement by incorporating CPE into the nanocomposites, and obtained the high value of 745 J/m. Morphology investigation indicated that the nano‐CaCO₃ particles in the PVC matrix was encapsulated with a CPE layer through preparing the CPE/nano‐CaCO₃ master batch. The evaluation of rheological properties revealed that the introduction of nano‐CaCO₃ particles into PVC resulted in a remarkable increase in the melt viscosity. However, the viscosity decreased with addition of CPE, especially at high shear rates; thus, the processability of the ternary nanocomposites was improved. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2714–2723, 2004     

Toughening and reinforcement of rigid PVC with silicone rubber/nano‐CACO3 shell‐core structured fillers

To improve the mechanical properties and structure of poly(vinyl chloride) (PVC)/nano‐CaCO₃ nano composite, a core (nano‐CaCO₃)/shell (SR) structured filler (40–60 nm) was successfully prepared by refluxing methyl vinyl silicone rubber (SR) and nano‐CaCO₃ particles (coupling agent KH550, KH560, or NDZ‐101 as interfacial modifier) in toluene with vigorous stirring, according to an encapsulation model. It is effective in rigid PVC composite's toughness and reinforcement. The interfacial modifier's structure and interaction of nanocomposites of PVC/SR/nano‐CaCO₃ were studied. The results indicate that KH560 has the optimal interfacial modificatory effect. The environmental scanning electron microscope (ESEM) study testified that PVC/SR/nano‐CaCO₃ nanocomposites had a typical rubber–plastics‐toughening mechanism. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2560–2567, 2006     

Rubber toughening of polyamide 6/organoclay nanocomposites obtained by melt blending

Rubber toughening of polyamide 6 (PA6)/layered‐silicate nanocomposites was investigated. Different systems were prepared via melt blending according to different formulations. Wide‐angle X‐ray diffraction and transmission electron microscopy analyses showed that the nanocomposites had an appreciable degree of exfoliation. A linear elastic fracture mechanics approach was applied to characterize the material fracture behavior in dry conditions, whereas, because of the considerable ductility exhibited by the samples in the wet state, an elastic–plastic approach based on the essential work of fracture methodology was employed. In the absence of rubber, the presence of silicate layers makes the material fracture resistance decrease relative to neat polymer, depending on the degree of humidity. The results showed that the toughening action of rubber strongly depends on the degree of humidity of the material, at least for the rubber contents considered in this study (lower than 10 wt %). In particular, in slightly wet conditions, it was found that the addition of small amounts of rubber increased the fracture resistance of PA6/layered‐silicate nanocomposites without appreciably impairing the material stiffness. Thus, the results indicated that, for the given humidity conditions, a good balance between stiffness and toughness was obtainable by employing a suitable ratio of rubber to layered‐silicate content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3406–3416, 2006     

Fabrication of barium titanate nanoparticles‐epoxy resin composite films and their dielectric properties

A method for fabricating epoxy resin films dispersing the surface‐modified barium titanate (BT) particles (BT‐epoxy resin composite films) are proposed. BT particles with a size of 7.8 nm and a crystal size of 8.6 nm were synthesized with a complex alkoxide method. To introduce epoxy groups on the BT particle surface, the BT particles were surface‐modified with 2‐(3,4‐epoxycyclohexyl)‐ethyltrimethoxysilane. A precursor solution, which was prepared by prereacting 2,2‐bis(4‐glycidyloxyphenyl)propane (BGPP) and phthalic anhydride in 4‐butyrolactone and adding the surface‐modified BT particles to the prereacting solution, was spin‐coated on glass substrates to fabricate the composite films. An increase in BT volume fraction in film increased dielectric constant of the composite film while keeping dissipation factor below 0.03. The dielectric constant attained 10.8 at a BT volume fraction of 30% in film that was around twice higher than pure epoxy resin film. POLYM. COMPOS., 31:1179–1183, 2010. © 2009 Society of Plastics Engineers     

Interfacial effects on dielectric properties of polymethylmethacrylate‐titania microcomposites and nanocomposites

It is discussed that dielectric properties of polymethylmethacrylate (PMMA) composites are influenced by the particle size of titania as a result of changes in the structure and dynamics of polymer chains in the interphase regions around the particles. It is hypothesized that a loosely packed interphase layer, resulted from high stiffness and high cohesion energy of PMMA chains, provides enough free volume for segmental chain movements and dipole orientation along the applied electric field and causes an increase in dielectric properties of nanocomposites at low filler contents. It is shown that the attraction of PMMA toward micro‐titania and nano‐titania is similar by measuring the surface energy of fillers. Dynamics of polymer chains around fillers is investigated by dynamic‐mechanical‐thermal analysis and broadband‐dielectric spectroscopy, and presence of a loosely packed layer is confirmed by measuring thermal and mechanical glass transition temperature of composites. It is concluded that the anomalous enhancement in dielectric properties of 2 vol% nanocomposite, compared to the corresponding microcomposite, can be attributed to the higher volume fraction of loosely packed interphase layers in the nanocomposite. POLYM. COMPOS., 38:1158–1166, 2017. © 2015 Society of Plastics Engineers     

热固性树脂/纳米SiO2复合材料性能影响因素的分析

热固性树脂/纳米SiO2复合材料在添加纳米SiO2微粒后具有明显的成核效应。复合材料可显示低诱导期、高结晶速率和较小的半结晶时间等特点。同时纳米SiO2微粒的加入可提高储能模量(Es)、玻璃化转变温度(Tg),且二者的变化都与纳米SiO2微粒的质量分数成正比关系。这表明纳米SiO2微粒与热固性树脂之间存在较强的界面作用。对热固性树脂/纳米SiO2复合材料性能影响因素进行了分析。     

Preparation of nanocomposites of thermosetting resin from benzoxazine and bisoxazoline with montmorillonite

The thermosetting resin from 2,2′‐(1,3‐phenylene)‐bis(4,5‐dihydro‐oxazoles) (PBO) and bis(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine)isopropane (BZ) was prepared, and it was found that the thermal property of the final resin was affected greatly by the content of PBO. The nanocomposite from the thermosetting resin from BZ and PBO (molar ratio of PBO to BZ, 0.8 : 1) (PBZ–PBO) and organically modified montmorillonite (OMMT) was prepared by melt method. Differential scanning calorimetry showed that on the introduction of OMMT, the onset curing temperature of the copolymerization of BZ and PBO decreased. The X‐ray diffractometer and transmission electron micrograph characterization of the dispersion of OMMT in the PBZ–PBO matrix suggested that exfoliation structure of OMMT was achieved. Dynamic mechanical analyses indicated that the nanocomposites exhibited much higher T_g values than the PBZ–PBO resin and pristine polybenzoxazine, and storage modulus of the nanocomposites was maintained up to higher temperature with the increasing OMMT content. Dynamic thermogravimetric analysis showed that the dispersion of clay nanolayers in the PBZ–PBO copolymer gave better thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4741–4747, 2006     

Preparation and characterization of injection‐homo‐polypropylene filled with nano‐CaCO3

Nano‐CaCO₃/homo‐PP composites were prepared by melt‐blending using twin‐screw extruder. The results show that not only the impact property but also the bending modulus of the system have been evidently increased by adding nano‐CaCO₃. The nano‐CaCO₃ particles have been dispersed in the matrix in the nanometer scale which was investigated by means of transmission electron microscopy (TEM). The toughening mechanism of nano‐CaCO₃, investigated by means of dynamical mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM), lies on that the nano‐CaCO₃ particles take an action of initiating and terminating crazing (silver streak), which can absorb more impact energy than the neat PP. At the same time, the nano‐CaCO₃ particles, as the nuclear, decrease the crystal size of PP, the results of which were investigated by means of polarized optical microscope (POM). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and performance of high‐impact polystyrene (HIPS)/nano‐TiO2 nanocomposites

High‐impact polystyrene (HIPS)/nano‐TiO₂ nanocomposites were prepared by surface pretreatment of nano‐TiO₂ with special structure dispersing agent (TAS) and master batch manufacturing technology. The results show that when the nano‐TiO₂ content is 2%, the notched impact strength, tensile strength, and elastic modulus of HIPS/nano‐TiO₂ nanocomposites increased to a maximum. This result indicates that nano‐TiO₂ has both toughening and reinforcing effects on HIPS. The heat‐deflection temperature and flame‐retardance of HIPS/nano‐TiO₂ nanocomposites are also obviously improved as the nano‐TiO₂ content is increased. The nanocomposites manufactured by the two‐step method have better mechanical properties than that made by a one‐step method. HIPS/nano‐TiO₂ nanocomposites are also non‐Newtonian and pseudoplastic fluids. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 381–385, 2003     

High dielectric constant SU8 composite photoresist for embedded capacitors

A novel, photodefinable, high dielectric constant (high‐k) nanocomposite material was developed for embedded capacitor applications. It consists of SU8 as the polymer matrix and barium titanate (BT) nanoparticles as the filler. The UV absorption characteristics of BT nanoparticles were studied with a UV‐Vis spectrophotometer. The effects of BT nanoparticle size, filler loading, and UV irradiation dose on SU8 photopolymerization were systematically investigated. The dielectric properties of the photodefined SU8 nanocomposites were characterized. Embedded capacitors using the novel high dielectric constant SU8 composite photoresist were demonstrated on a flexible polyimide substrate by the UV lithography method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1523–1528, 2007     

Morphology,mechanical property,and modeling evaluation of P(3HB‐co‐4HB)/nano‐ZnO composites

Poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P(3HB‐co‐4HB)) and nanometer zinc oxide (nano‐ZnO) modified by solid titanate coupling agent (TMC980) were selected to prepare P(3HB‐co‐4HB)/nano‐ZnO composites via melt blending. Scanning electron microscope (SEM), capillary rheometer, polarized optical microscopy (POM), and universal testing machine were used to characterize the fracture morphology, rheological property, spherulitic morphology, and mechanical properties of P(3HB‐co‐4HB)/nano‐ZnO composites. Halpin‐Tsai equation was used to quantitatively evaluate the dispersion and enhancement effects of modified nano‐ZnO on P(3HB‐co‐4HB). The results demonstrated that modified nano‐ZnO at 0.2%∼0.3% of volume fraction could significantly improve the tensile strength, elastic modulus and toughness, increase the melt viscosity, refine the spherulitic size, and rough the fracture morphology of P(3HB‐co‐4HB)/nano‐ZnO composites. Based on the effective aspect ratio (ξ) from Halpin‐Tsai model evaluation, the optimal dosage of nano‐ZnO for P(3HB‐co‐4HB)/nano‐ZnO composites was also at 0.2%∼0.3% of volume fraction. The Halpin‐Tsai equation was found to predict the experimental data most accurately for the P(3HB‐co‐4HB)/nano‐ZnO composites. POLYM. COMPOS., 37:3113–3121, 2016. © 2015 Society of Plastics Engineers     

Effect of elastomer type and functionality on the behavior of toughened polyamide nanocomposites

The only shortcoming of PA6‐based nanocomposites is low toughness, which is the same as that of the matrix. This work is focused on optimization of toughening these nanocomposites by introduction of small amounts of finely dispersed elastomers. A comparison of reactively compatibilized and analogous nonreactive elastomer‐containing nanocomposites indicates the best‐balanced mechanical behavior for polar nonreactive elastomers such as NBR and E‐MA. This is explained by a significant compatibilizing effect of clay. Besides the elastomer particle size and its properties, the clay localization and its degree of ordering in the interfacial region also significantly influenced mechanical properties of the system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1571–1576, 2006     

Kinetics of thermal degradation of nanometer calcium carbonate/linear low‐density polyethylene nanocomposites

To improve the thermal properties of linear low‐density polyethylene (LLDPE), the CaCO₃/LLDPE nanocomposites were prepared from nanometer calcium carbonate (nano‐CaCO₃) and LLDPE by melt‐blending method. A series of testing methods such as thermogravimetry analysis (TGA), differential thermogravimetry analysis, Kim‐Park method, and Flynn‐Wall‐Ozawa method were used to characterize the thermal property of CaCO₃/LLDPE nanocomposites. The results showed that the CaCO₃/LLDPE nanocomposites have only one‐stage thermal degradation process. The initial thermal degradation temperature T₀ increasing with nano‐CaDO₃ content, and stability of LLDPE change better. The thermal degradation activation energy (E_a) is different for different nano‐CaCO₃ content. When the mass fraction of nano‐CaCO₃ in nanocomposites is up to 10 wt %, the nanocomposite has the highest thermal degradation E_a, which is higher (28 kJ/mol) than pure LLDPE. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of aluminum hydroxide on low‐molecular‐weight siloxane distribution and microstructure of high‐temperature vulcanized silicone rubber

This paper investigates the effect of aluminum hydroxide (ATH) content on the free volume and surface recovery property of polydimethylsiloxane (PDMS)–based silicone rubber containing low‐molecular‐weight siloxanes. With increasing ratio of ATH up to 43.1 wt %, the concentration of cyclic siloxanes (D_n = [(CH₃)₂SiO]_n, n = 4–12) in the PDMS matrix increases remarkably, indicative of a spacing effect of ATH particles on the crosslinking of PDMS chains. When more ATH is added, the concentration of D₄–D₁₂ began to decrease. PDMS network variation is verified by free volume size corresponding to τ₃ in positron annihilation lifetime spectroscopy. The o‐Ps intensity decreases linearly with ATH content. Data obtained from X‐ray photoelectron spectroscopy suggest the surface recovery property is weakened by ATH. This process is dominated by the amount of free volume holes in the sample. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45803.     

Rheological properties of PDMS filled with CaCo3: The effect of filler particle size and concentration

The effects of filler particle size and concentration on the rheological properties of hydroxyl terminated polydimethylsiloxane (HO‐PDMS) filled with calcium carbonate (CaCO₃) were investigated by an advanced rheometric expansion system (ARES). The Casson model was used to describe the relationship between shear stress and shear rate for steady‐state measurement. Micron‐CaCO₃ could not afford the CaCO₃/HO‐PDMS suspensions obvious shear thinning behavior and a yield stress high enough, whereas nano‐CaCO₃ could provide the suspensions with remarkable shear thinning behavior and high yield stress. Incorporation of nano‐CaCO₃ into HO‐PDMS resulted in the transformation of HO‐PDMS from a mainly viscous material to a mainly elastic material. With increasing nano‐CaCO₃ content, shear thinning behavior of nano‐CaCO₃/HO‐PDMS suspensions became more obvious. Remarkable yield stress was observed in nano‐CaCO₃/HO‐PDMS suspensions with high filler content, and increased with increasing nano‐CaCO₃ content. The degree of thixotropy was quantitatively determined using a thixotropic loop method. It was found that nano‐CaCO₃ favored more the buildup of filler network structure in the suspensions than micron‐CaCO₃ at the same weight fraction. Furthermore, increasing nano‐CaCO₃ content accelerated the establishment of filler network structure in the nano‐CaCO₃/HO‐PDMS suspensions. An overshoot phenomenon was observed in the nano‐CaCO₃/HO‐PDMS suspensions at high shear rates. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3395–3401, 2006     

Analysis of the structure and mass transport properties of nanocomposite polyurethane

In this work, nanocomposite adhesives obtained using an organically modified montmorillonite (OMM) in a polyurethane matrix were studied. The basal distance of OMM before and after mixing with the polyol and after curing was characterized by X‐Ray diffraction. The viscosity of polyols‐OMM systems was studied as function of shear rate in a cone‐plate rheometer in order to correlate the viscosity with the aggregation state of OMM. A simple model accounting for an apparent increase of rheological units size associated with the intercalation of macromolecules into OMM galleries is proposed. Curing was performed at room temperature for 1 week. The basal distances of crosslinked PU nanocomposites were obtained by X‐ray diffraction. The glass transition temperature, T_g, of PU nanocomposites, as measured using differential scanning calorimetry, increases with increasing volume fraction of OMM. Finally, the permeability to oxygen and water vapor of polyurethane clay‐nanocomposites was measured. The gas permeation through the composites was correlated to the volume fraction of the impermeable inorganic part of the OMM. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers