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Considering the molar mass between entanglements to be an intrinsic property of ultra-high molecular weight polyethylene (UHMWPE), the number of entanglements per chain increases with increasing molar mass, correspondingly making the UHMWPE intractable. Herein, we dispersed TiO2 nanoparticles with different characteristics into UHMWPE solutions to disentangle the molecular chains. Compared with the UHMWPE pure solution, the viscosity of the mixture solution declines by 91.22%, and the critical overlap concentration increases from 1 wt% to 1.4 wt%. A rapid precipitation method was utilized to obtain UHMWPE and UHMWPE/TiO2 composites from the solutions. The melting index of UHMWPE/TiO2 is 68.85 mg, which is in sharp contrast to that of UHMWPE which is 0 mg. We characterized the microstructures of UHMWPE/TiO2 nanocomposites using TEM, SAXS, DMA, and DSC. Accordingly, this significant improvement in processability contributed to the reduction of entanglements and a schematic model was proposed to explain the mechanism by which nanoparticles disentangle molecular chains. Simultaneously, the composite demonstrated better mechanical properties than UHMWPE. In summary, we provide a strategy to promote the processability of UHMWPE without sacrificing its outstanding mechanical properties.
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This work aimed to investigate the CO2 gas barrier and mechanical properties of fluorine rubber nanocomposites filled with Ca/Al layered hydroxide (graphene oxide [GO]/LDH-Ca2Al) modified by GO. GO/LDH-Ca2Al nanocomposite fillers were prepared by depositing Ca/Al layered hydroxide (LDH-Ca2Al) into the surface of alkalized GO (Al-GO). The prepared GO/LDH-Ca2Al nanocomposite fillers and complexes were characterized by Fourier infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) for structural and micromorphological characterization. The results showed that GO/LDH-Ca2Al was successfully prepared with strong interactions between Al-GO and LDH, and the compatibility of GO/LDH-Ca2Al nanocomposite fillers with the polymer was significantly improved compared with that of LDH-Ca2Al. Consequently, both the fracture strength (σb) and strain (εb) of GO/LDH-Ca2Al nanocomplexes remarkably increased, and they exhibited excellent mechanical properties. Differential scanning calorimetry and thermogravimetric analysis were used to characterize the thermal stability of GO/LDH-Ca2Al nanocomposite fillers, and GO/LDH-Ca2Al nanocomposite fillers have better thermal stability than LDH-Ca2Al. The reaction products (S-LDH-Ca2Al and S-GO-Ca2Al) of LDH-Ca2Al and GO/LDH-Ca2Al with CO2 were characterized using XRD and TGA, respectively, and the results show that LDH-Ca2Al reacts readily and chemically with CO2, resulting in a lower diffusion coefficient of CO2 in the LDH-Ca2Al nanocomplexes than that of the GO/LDH-Ca2Al nanocomplexes and leading to the destruction of the laminar structure of LDH-Ca2Al, while GO/LDH-Ca2Al has better CO2 resistance stability. GO/LDH-Ca2Al nanocomplexes exhibited a reduced content of hydroxyl groups with pro-CO2 nature exposed on the surface of LDH-Ca2Al, improving the interfacial interaction between the nanofillers and the rubber matrix and enhancing the dispersion of GO/LDH-Ca2Al in the polymers. Moreover, CO2 in the soluble GO/LDH-Ca2Al nanocomposites was significantly reduced, while the diffusion properties demonstrated weak temperature dependence on solubility. The mechanism of the CO2 gas barrier of polymers filled with GO/LDH-Ca2Al was proposed on the basis of the Arrhenius equation.
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Research on the rheological performance and mechanism of polymer nanocomposites (PNCs), mainly focuses on non-polar polymer matrices, but rarely on strongly polar ones. To fill this gap, this paper explores the influence of nanofillers on the rheological properties of poly (vinylidene difluoride) (PVDF). The effects of particle diameter and content on the microstructure, rheology, crystallization, and mechanical properties of PVDF/SiO2 were analyzed, by TEM, DLS, DMA, and DSC. The results show that nanoparticles can greatly reduce the entanglement degree and viscosity of PVDF (up to 76%), without affecting the hydrogen bonds of the matrix, which can be explained by selective adsorption theory. Moreover, uniformly dispersed nanoparticles can promote the crystallization and mechanical properties of PVDF. In summary, the viscosity regulation mechanism of nanoparticles for non-polar polymers, is also applicable to PVDF, with strong polarity, which is of great value for exploring the rheological behavior of PNCs and guiding the process of polymers.
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Bio-inspired superhydrophobic Polyphenylene sulfide/Polytetrafluoroethylene (PPS/PTFE) coatings were prepared by a simple curing process. The surface morphology characterization by SEM shows that these superhydrophobic coatings have the similar macro-nano-structures to that of lotus leaf. Effect of the content of PTFE as well as the curing condition on the water contact angle of the superhydrophobic coating surface was then systematically studied. A series of tests show that the superhydrophobic coatings exhibit high cohesional strength, excellent impact resistance and high thermal stability. Moreover, we studied the stability of chemical resistance of the as-prepared superhydrophobic PPS/PTFE coatings, and the electrochemical impedance values kept on a high level even after 8 days. The superhydrophobic PPS/PTFE coatings with high performance have potential applications in some specific fields.
Assuntos
Polímeros/química , Politetrafluoretileno/química , Microscopia Eletrônica de VarreduraRESUMO
The rich -SO3H groups enable sulfonated poly (ether ether ketone) (SPEEK) to possess excellent proton conductivities in proton exchange membrane (PEM), but cause excessive water absorption, resulting in the decline of dimensional stability. It is a challenge to resolve the conflict between conductivity and stability. Owing to its unique structural designability, covalent organic frameworks (COFs) have been used to regulate the performances of PEMs. The authors propose the use of COFs with acidic and basic groups for meeting the requirements of proton conductivity and dimensional stability. Herein, COFs containing different groups (sulfoacid, pyridine, and both) were uniformly dispersed into the SPEEK matrix by in situ synthesis, and the effects on the properties of SPEEK matrix PEMs were revealed. The sulfoacid group significantly improves proton conductivities. At 60 °C, under 95% RH, the conductivity of the SPEEK/TpPa-SO3H-20 composite membrane was 443.6 mS·cm-1, which was 3.3 times that of the pristine SPEEK membrane. The pyridine group reduced the swelling ratio at 50 °C from 220.7% to 2.4%, indicating an enhancement in dimensional stability. Combining the benefits of sulfoacid and pyridine groups, SPEEK/TpPa-(SO3H-Py) composite membrane has a conductivity of 360.3 mS·cm-1 at 60 °C and 95% RH, which is 1.86 times that of SPEEK, and its swelling ratio is 11.8%, about 1/20 of that of SPEEK membrane. The method of in situ combination and regulation of groups open up a way for the development of SPEEK/COFs composite PEMs.
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Acidic gas penetration through the internal pressure sheath of a flexible riser tends to cause a corrosive environment in the annulus, reducing the service life of the flexible riser. Nanoparticles can act as gas barriers in the polymer matrix to slow down the gas permeation. Herein, we prepared PA11/SiO2 composites by the melt blending method. The effect of adding different amounts of SiO2 to PA11 on its gas barrier properties was investigated by conducting CO2 permeation tests between 20 °C and 90 °C. As the temperature increased, the lowest value of the permeability coefficient that could be achieved for the PA11 with different contents of SiO2 increased. The composites PA/0.5% SiO2 and PA/1.5% SiO2 had the lowest permeation coefficients in the glassy state (20 °C) and rubbery state (≥50 °C). We believe that this easy-to-produce industrial PA/SiO2 composite can be used to develop high-performance flexible riser barrier layers. It is crucial for understanding riser permeation behavior and enhancing barrier qualities.