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1.
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 (Tg) 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 Tg 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.  相似文献   

2.
In composites of hydroxyapatite (HA) nanoparticles with a polymer matrix, the aggregation of nanoparticles would induce structural defects. In order to improve the dispersibility of HA nanoparticles in poly(ethylene glycol) dimethacrylate (PEGDMA) matrix and enhance mechanical properties of the HA/PEGDMA composite as potential bone substitute material, surface‐grafted HA nanoparticles with poly(ethylene glycol) monomethacrylate (PEGMA) were prepared, and crosslinked with PEGDMA under UV light to form a composite. The structure of HA‐g‐PEGMA was characterized by X‐ray diffraction (XRD) and thermal gravimetric analysis (TGA). The dispersibility of HA‐g‐PEGMA nanoparticles in poly(PEGDMA) was evaluated by SEM. The mechanical properties of the composites were investigated by compressive test. The dispersibility of HA‐g‐PEGMA nanoparticles in poly(PEGDMA) matrix was better than the bare HA. At a 1 wt % content of loading, the strength of composites increased by 14%, and the modulus increased by 9%. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

3.
Surfactant‐free nanoparticles of poly(DL ‐lactide‐co‐glycolide) (PLGA) nanoparticles were prepared with or without poly(L ‐lactide)‐poly(ethylene oxide) (LE) diblock copolymer (abbreviated as PLGA/LE and PLGA nanoparticles) by dialysis method. LE diblock copolymer was used to make PLGA nanoparticles to alternate conventional surfactant. The size of PLGA and PLGA/LE nanoparticles was 295.3 ± 171.3 and 307.6 ± 27.2 nm, respectively, suggesting LE diblock copolymer might be coated onto the surface of nanoparticles. Observation of scanning electron microscope (SEM) showed that PLGA/LE nanoparticles have spherical shapes ranging ~ 200–500 nm. In 1H‐NMR study, characteristic peaks of the methyl protons of PLGA disappeared in D2O, whereas characteristic peaks of the methyl proton of both PEG and PLGA were shown in both CDCl3 and D2O, indicating that LE diblock copolymer coated on the surface of the PLGA nanoparticles. The higher the initial content of drug, the higher the drug contents and the lower the loading efficiency. PLGA/LE nanoparticles at higher drug contents resulted in slower adriamycin·HCl (ADR) release rate than that of lower drug contents. Also, slower release rate of ADR was achieved by entrapped into the PLGA/LE nanoparticles, whereas LE polymeric micelles showed rapid ADR release. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1116–1123, 2003  相似文献   

4.
The purpose of this research was to study the thermal degradation kinetics of nanocomposites of poly(l ‐lactide) (PLLA) with carbon nanotubes (CNT) in order to provide further insight into their thermal stability. Nanocomposites were prepared by solvent casting with 1, 3, and 5% by weight of pristine CNT (P‐CNT) or functionalized CNT (F‐CNT), and were characterized using infrared spectroscopy, transmission electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and dynamic‐mechanical‐thermal analysis. The kinetic parameters of thermal decomposition were determined employing Coats‐Redfern method to calculate the reaction order and E2 function model to calculate the activation energy (Ea). We found no major changes in PLLA glass transition temperatures due to CNT presence, but melt‐crystallization temperature increased slightly in some composites. In general, composites consisting of 3% or 5% of F‐CNT had superior thermal stability than did pure polymer or P‐CNT composites. This improved thermal stability was revealed by slightly higher degradation and onset temperatures, and Ea obtained from kinetic analysis. In addition, 3% or 5% of F‐CNT in PLLA composites slightly enhanced the storage modulus above the glass transition. Therefore, functionalization promoted, in some extent, better morphology and dispersion of CNT into the matrix, which was responsible for improved thermal stability and thermomechanical performance of composites at higher temperatures relative to pure polymer. POLYM. ENG. SCI., 55:710–718, 2015. © 2014 Society of Plastics Engineers  相似文献   

5.
Positive temperature coefficient of resistivity (PTCR) characteristics of poly(styrene‐co‐acrylonitrile) copolymer (SAN)/stainless steel (SS) powder (80 wt %) composites prepared by melt‐mixing method has been investigated with reference to SAN/carbon black (CB) composites. The SAN/CB (10 wt %) composites showed a sudden rise in resistivity (PTC trip) at 125°C, above the glass transition temperature (Tg) of SAN (Tg ≈ 107°C). However, the PTC trip temperature of SAN/SS (80 wt %) composites appeared at 94°C, well below the Tg of SAN. Addition of 1 phr of nanoclay increased the PTC trip temperature of SAN/CB (10 wt %) composites to 130°C, while SAN/SS (80 wt %)/clay (1 phr) nanocomposites showed the PTC trip at 101°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between SAN and SS played a key role that led to a disruption in continuous network structure of SS even at a temperature below the Tg of SAN. The dielectric properties study of SAN/SS (80 wt %) composites indicated possible use of the PTC composites as dielectric material. DMA results showed higher storage modulus of SAN/SS composites than the SAN/CB composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

6.
Organ‐rectorite/thermoplastic polyurethane (OREC/TPUR) nanocomposites were synthesized via melt intercalation. The dynamic mechanical properties by dynamic mechanical analysis (DMA), thermal and oil‐resistant properties were investigated. The results show that the storage modulus (E′), loss modulus (E″), and glass‐transition temperature (Tg) of the nanocomposites have an increase to some extent than those of pure TPUR. The thermal stability of nanocomposites was also studied in detail by thermal gravity analysis (TGA), which was higher than that of pristine TPUR matrix when the content of organic REC is at 2 wt %, and the decomposition temperature at 10% weight loss of OREC/TPUR is greatly increased up to 330°C from 315°C. Oil uptake of the composites is also significantly reduced in comparison with TPUR matrix, which is ascribed to the good barrier effect of nanosheets of OREC. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1165–1169, 2005  相似文献   

7.
The important mechanical mechanism for the electrical conduction of anisotropic conductive films (ACFs) is the joint clamping force after the curing and cooling processes of ACFs. In this study, the mechanism of shrinkage and contraction stress and the relationship between these mechanisms and the thermomechanical properties of ACFs were investigated in detail. Both thickness shrinkages and modulus changes of four kinds of ACFs with different thermomechanical properties were experimentally investigated with thermomechanical and dynamic mechanical analysis. Based on the incremental approach to linear elasticity, contraction stresses of ACFs developed along the thickness direction were estimated. Contraction stresses in ACFs were found to be significantly developed by the cooling process from the glass‐transition temperature to room temperature. Moreover, electrical characteristics of ACF contact during the cooling process indicate that the electrical conduction of ACF joint is robustly maintained by substantial contraction stress below Tg. The increasing rate of contraction stresses below Tg was strongly dependent on both thermal expansion coefficient (CTE) and elastic modulus (E) of ACFs. A linear relationship between the experimental increasing rate and E × CTE reveals that the build‐up behavior of contraction stress is closely correlated with the ACF material properties: thermal expansion coefficient, glassy modulus, and Tg. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2634–2641, 2004  相似文献   

8.
The main focus of this study is to characterize the interfacial interactions between silica nanoparticles and polypropylene and to investigate how the surface properties and morphology of the silica nanoparticles affect the elastic response of the silica–polypropylene composites. The composites were prepared by melt compounding and injection molding. Both non‐functionalized and dimethyldichlorosilane‐functionalized silica nanoparticles were used. Three‐component composites were also prepared by including selected formulations of both poly(propylene‐g‐maleic anhydride) copolymer (PPgMA) and different types of silica. It was found that both silica types are nucleating agents for PP and significantly alter its crystallization behavior. A strong correlation between the glass transition temperature (Tg) and the tensile modulus in silica‐PP nanocomposites indicated the presence of a secondary reinforcing mechanism that is the pinning of the polymer chains on the silica surface. The presence of a complex constrained phase, represented by immobilized amorphous and transcrystalline phases, forming at the filler surface, was assessed by modulated differential scanning calorimetry and dynamic mechanical analysis. Finally, the interfacial interactions were correlated to the tensile and viscoelastic properties using the theoretical models proposed by Pukanszky and Sumita et al., respectively, and comparing the predictions of the models to experimental results. POLYM. COMPOS., 37:2018–2026, 2016. © 2015 Society of Plastics Engineers  相似文献   

9.
Composites of poly(D ,L ‐lactide) (PDLLA) with hydroxylapatite (HA) and PDLLA with tertiary calcium phosphate (TCP) were prepared by in situ modification with methylenediphenyl diisocyanate (MDI) and molded by piston extrusion at temperature between Tg and Tm of PDLLA. Mechanical properties of the composites increased obviously when compared with the unmodified bioactive ceramic particles/PDLLA composites. The effect of MDI contents on mechanical properties of the composites was studied. At the optimum conditions of 1.0/1.0molar ratios of ? NCO groups in MDI to ? OH groups in PDLLA, bending strength 68.4 MPa and bending modulus 2281.5 MPa, were achieved in composite HA/PDLLA/MDI with 15 wt % HA. Both increased by nearly 30% when compared with that of solution cast HA/PDLLA composites. Interfacial adhesion and compatibility between PDLLA and bioactive ceramic particles (HA and TCP) were investigated. Scanning electron microscopy (SEM) indicated that the interface between HA particles and PDLLA was blurred and HA particles were closely surrounded by PDLLA matrix in HA/PDLLA/MDI composites. Oriented fibrils along with longitudinal direction of extrusion die were also observed on the surfaces of HA/PDLLA/MDI composite. It is confirmed that MDI has improved interfacial adhesion and compatibility between HA particles and PDLLA phase. Fibril structures formed in the extrusion, and it contributed a great deal in enhancing the mechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4085–4091, 2006  相似文献   

10.
A new series of extended–conjugated and thermally stable thiophene‐containing imine‐linked polymers were synthesized via a Schiff‐base condensation reaction between aryl aldehydes and 2,6‐diaminopyridine building blocks. The backbones of the polymers were functionalized with phenyl, fluorosubstituted phenyl, thienyl, and pyridyl aromatic rings. The successful synthesis was confirmed with spectrochemical characterization techniques, including IR, 1H‐NMR, 13C‐NMR, and elemental analyses. The electronic properties of the polymers were investigated with ultraviolet–visible (UV–vis) absorption spectroscopy; the properties were collected experimentally and calculated with density functional theory (DFT) in the gas phase. The maximum absorption calculated from DFT was higher than the experimental values by about 60 nm; this was attributed to the absence of the solvent effect in the DFT case. The frontier molecular orbital ((HOMO) highest occupied molecular orbital and (LUMO) lowest unoccupied molecular orbital), optical band gap (Eg), and total energy (ET) values of the optimized structures were calculated. Apparently, there was a significant relation between the number of thiophene rings and the resulting Eg and ET values. As the number of thiophene rings in the polymer chain increased, Eg and ET decreased, and the thermal stability of the polymers increased. Eg and the absorption band edges were determined experimentally from the UV–vis and transmittance spectra, respectively. Poly(terthienyl–azomethine–pyridine–azomethine), with the highest thiophene content, had the lowest experimental and calculated Eg values (2.10 and 2.63 eV, respectively). In contrast, upon fluorination, poly[(2,5‐dithienyl–1,4‐difluorobenzene)–azomethine–pyridine–azomethine] exhibited the highest Eg (2.81 eV) and absorption band edges (2.94 eV), whereas the thermal stability decreased to 250 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44331.  相似文献   

11.
In previous studies, we reported the linear and nonlinear rheological properties of three‐component composites consisting of acrylic polymer (AP), epoxy resin (EP), and various SiO2 contents (AP/EP/SiO2) in the molten state. In this study, the dynamic mechanical properties of AP/EP/SiO2 composites with different particle sizes (0.5 and 8 μm) were investigated in the glass‐transition region. The EP consisted of three kinds of EP components. The α relaxation due to the glass transition shifted to a higher temperature with an increase in the volume fraction (?) for the AP/EP/SiO2 composites having a particle size of 0.5 μm, but the α relaxation scarcely shifted for the composite having a particle size of 8 μm as a general result. This result suggested that the SiO2 nanoparticles that were 0.5 μm in size adsorbed a lot of the low‐glass‐transition‐temperature (Tg) component because of their large surface area. The AP/SiO2 composites did not exhibit a shift in Tg; this indicated that the composite did not adsorb any component. The modulus in the glassy state (Eg) exhibited a very weak &phis; dependence for the AP/EP/SiO2 composites having particle sizes of 0.5 and 8 μm, although Eg of the AP/SiO2 composites increased with &phis;. The AP/EP/SiO2 composites exhibited a peculiar dynamic mechanical behavior, although the AP/SiO2 composites showed the behavior of general two‐component composites. Scanning electron microscopic observations indicated that some components in the EP were adsorbed on the surface of the SiO2 particles. We concluded that the peculiar behavior of the AP/EP/SiO2 composites was due to the selective adsorption of the EP component. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40409.  相似文献   

12.
An interesting correlation between initial loading and nature of wrapping of regioregular poly(3‐hexylthiophene) (rrP3HT) on multiwalled carbon nanotube and their combined effect on dynamic‐ and thermomechanical properties in ternary system (thermoplastic polyurethane as matrix) is highlighted. Wrapping of rrP3HT on carbon nanotube (CNT) makes the hexyl side chains thermally nonequivalent and composites more stable. Dynamic‐ and thermomechanical analysis ascertained the miscibility (single Tg = ?40°C), large mechanical reinforcement, and improved storage modulus of nanocomposites in the presence of CNT compared to its blends. Two breaks at ~ ?100 and ~ ?40°C for TPU‐P3HT composites (PHs) and TPU‐P3HT‐MWCNT composites (PHCs) in the loss modulus vs. temperature plot indicates two different types of transitions in P3HT chains. Dimensional stability by expansion probe technique measures low coefficient of thermal expansion of PHCs compared to its blends. Softening property by penetration probe technique suggests that 2.5 wt % loading of P3HT exhibits lowest degree of penetration compared to other nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

13.
A new high‐performance copolymer was successfully obtained via concerted catalysis polymerization of mono‐functional benzoxazine (P‐a) and self‐promoted 4‐aminophenoxy phthalonitrile (4‐APN) monomers. The FTIR and DSC curves of the P‐a/4‐APN in different blend ratios suggested that the monomer blends can be completely cured without the addition of curing additive. The P‐a/4‐APN copolymers were cured at relatively lower curing temperatures and time. The TGA curves revealed that the P‐a/4‐APN copolymers have good thermal stability in terms of T5, T10, and char yield. A gradual increase in the glass transition temperature (Tg) values and decline were seen in the storage modulus as the loading of 4‐APN was increased from 10 to 30 wt % in the copolymer. The SEM analyses showed that copolymer's fracture surface is dendritic, showing the stress has been dispersed to a certain extent. The study revealed that the poly(P‐a/4‐APN) copolymer have much better thermal stabilities than the poly(P‐a), and the prepared copolymer can be used as a high‐performance thermosetting resin. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46578.  相似文献   

14.
Polypropylene-based multifunctional nanocomposites were fabricated in melt by a one-step reactive extrusion using a twin-screw extruder. The in situ chemical and physical processes during the extrusion of polymer blend composites consisting (1) polypropylene as a matrix polymer, (2) polypropylene–g-maleic anhydride graft copolymer compatibilizer, (3) copolymer–g-SiO2 encapsulated nanoparticles, (4) biodegradable polyesters, and (5) reactive and nonreactive organoclay nanofillers were investigated. The crystallinity, thermal stability, rheological, mechanical parameters, and surface and internal morphologies of the nanocomposites have been improved compared to polypropylene and its composites. Moreover, the colloidal copolymer–silica nanoparticles play an important role in the formation of nanocomposites with well dispersion in morphology.  相似文献   

15.
Crystallization kinetics of the newly developed Al2O3‐Y3Al5O12 (YAG) amorphous ceramic coating fabricated by atmospheric plasma spraying (APS) were investigated via differential scanning calorimetry (DSC) under non‐isothermal conditions. The phase compositions and microstructure of the as‐sprayed coating were characterized by X‐ray diffraction (XRD) and Scanning electron microscopy (SEM). The glass transition temperature Tg, the onset temperature of crystallization Tc and the peak temperature of crystallization Tp presented heating rate dependence. The related kinetic parameters of activation energies (Eg, Ec, Ep) and Avrami exponents (n) were quantified using various methods including Kissinger, Augis–Bennett, Ozawa and Matusita–Sakka, etc., to understand the phase transition mechanism and crystallization process in depth. A series of parameters including devitrification interval ΔT, thermal stability (Tc, Ec), nucleation resistance Ec/RTg and fragility index F were quantified in order to evaluate the nucleation mechanism, crystallization behavior and thermal stability of Al2O3‐YAG amorphous ceramic coating. Excellent thermal stability was witnessed in the studied coating. Furthermore, the YAG crystalline phases can be reasonably controlled and independently precipitated from the amorphous matrix via proper annealing.  相似文献   

16.
Wheat gluten (10 g) was crosslinked (XL) using 10 units of transglutaminase. Different blends of XL gluten and poly(lactic acid) (PLA) were mixed in a Brabender mixer at 180°C for 10 min. Neat PLA and blends were analyzed using modulated DSC (MDSC). Neat PLA displayed a glass transition (Tg) and exothermic (Cry) followed by endothermic (Mel) transitions. The profile showed a Tg of 0.46 J/g/°C, Cry with 29.9 J/g, whereas Mel exhibited 28.7 J/g. XL wheat gluten displayed one Tg with 0.45 J/g/°C. Samples were subjected to repeated heating and cooling cycles to show the level of compatibility between the two polymers. The activation energy (Ea) and pre‐exponential factor (Z) were determined according to Borchardt and Daniels (B/D) kinetics approach. The blends showed increased Ea values with an increase in the amount of XL gluten. In the presence of 5 and 20% XL gluten, the Ea of PLA increased from 150 to 200 kJ/mol, respectively. A higher number of cycles caused an increase in Ea. The Tg temperature of different PLA/XL gluten blends can be predicted by Gordon–Taylor equation and its modified forms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007  相似文献   

17.
A study on effect of chemical treatment using maleic anhydride‐grafted polypropylene (MAPP) and 3‐aminopropyltiethoxysilane (3‐APE) was investigated. The performance of the MAPP and 3‐APE were investigated by means of torque development, mechanical properties, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy morphology, and water absorption. The results revealed that the use of MAPP or 3‐APE in the composites has increased the stabilization torque, tensile strength, Young's modulus, water absorption, and thermal stability of the PP/NR composites. The incorporation of MAPP in the composites shows higher stabilization torque, tensile strength, EB, Young's modulus, and lower water uptake when compared with the use of 3‐APE in the PP/NR composites. TGA and DSC results indicated that primary and secondary peak of DTG curve, initial degradation temperature (T0), degradation temperature (Tdeg), melting temperature (Tm), heat of fusion of composites (ΔHf(com)), crystallinity of composites (XPP), and PP (XPP) increased, while total weight loss and thermal degradation rate decreased for both treated composites. The MAPP‐treated RNP‐filled PP/NR composites were found to be more thermal resistance and more crystalline than 3‐APE‐treated filled PP/NR RNP composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers  相似文献   

18.
In this study, the effects of functionalization and weight fraction of mutliwalled carbon nanotubes (CNTs) were investigated on mechanical and thermomechanical properties of CNT/Epoxy composite. Epoxy resin was used as matrix material with pristine‐, COOH‐, and NH2‐functionalized CNTs as reinforcements in weight fractions of 0.1, 0.5, and 1.0%. Varying (increasing) the weight fraction and changing type (pristine or functionalized) of CNTs caused increment in Young's modulus and tensile strength as observed during mechanical tests. CNT reinforcement improved thermal stability of the nanocomposites as observed by thermogravimetric analysis. Thermomechanical analysis showed a slight reduction in free volume of the polymer, that is a drop in coefficient of thermal expansion, prior to glass transition temperature (Tg) beside a slight increase in Tg value. Dynamic mechanical analysis indicated an increase in storage modulus and Tg owing to the strength addition of CNT to the matrix alongside the hardener. Scanning electron microscopy analysis of the fractured surface(s) revealed that CNTs were well dispersed with no agglomeration and resulted in reinforcing the matrix. POLYM. COMPOS., 36:1891–1898, 2015. © 2014 Society of Plastics Engineers  相似文献   

19.
The imidization of poly(styrene‐co‐maleic anhydride) (SMA) was conducted, and the glass‐transition temperatures (Tg's) of the resulting products were measured with differential scanning calorimetry. The contributions from functional groups of maleic anhydride, N‐phenylmaleamic acid, and N‐phenylmaleimide to Tg were examined. Tg increased in the order of SMA < styrene–N‐phenyl maleimide copolymer < styrene–N‐phenyl maleamic acid copolymer and followed the Fox equation. Tg of the imidized products of SMA could be controlled by the conversions of both ring‐opening and ring‐closing reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2418–2422, 2007  相似文献   

20.
Poly(N‐isopropylacrylamide) (PNIPAAm)/poly(ethylene oxide) (PEO) semi‐interpenetrating polymer networks (semi‐IPNs) synthesized by radical polymerization of N‐isopropylacrylamide (NIPAAm) in the presence of PEO. The thermal characterizations of the semi‐IPNs were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and dielectric analysis (DEA). The melting temperature (Tm) of semi‐IPNs appeared at around 60°C using DSC. DEA was employed to ascertain the glass transition temperature (Tg) and determine the activation energy (Ea) of semi‐IPNs. From the results of DEA, semi‐IPNs exhibited one Tg indicating the presence of phase separation in the semi‐IPN, and Tgs of semi‐IPNs were observed with increasing PNIPAAm content. The thermal decomposition of semi‐IPNa was investigated using TGA and appeared at around 370°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3922–3927, 2003  相似文献   

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