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1.
Polyesters based on polyols and sebacic acid, known as poly(polyol sebacate)s (PPS), are attracting considerable attention, as their properties are potentially useful in the context of soft‐tissue engineering applications. To overcome the drawback that PPSs generally display rather low strength and stiffness, we have pursued the preparation of nanocomposites based poly(mannitol sebacate) (PMS), a prominent example of this materials family, with cellulose nanocrystals (CNCs). Nanocomposites were achieved in a two‐step process. A soluble, low‐molecular‐weight PMS pre‐polymer was formed via the polycondensation reaction between sebacic acid and D‐mannitol. Nanocomposites with different CNC content were prepared by solution‐casting and curing under vacuum using two different profiles designed to prepare materials with low and high degree of crosslinking. The as‐prepared nanocomposites have higher stiffness and toughness than the neat PMS matrix while maintaining a high elongation at break. A highly crosslinked nanocomposite with a CNC content of 5 wt % displays a sixfold increase in Young's modulus and a fivefold improvement in toughness. Nanocomposites also exhibit a shape memory effect with a switch temperature in the range of 15 to 45 °C; in particular the materials with a thermal transition in the upper part of this range are potentially useful for biomedical applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3123–3133  相似文献   

2.
Nanocomposite films were successfully prepared from cellulose and tourmaline nanocrystals with mean diameters of 70 nm in a 1.5 M NaOH/0.65 M thiourea aqueous solution by coagulation with 5 wt % CaCl2 and then a 3 wt % HCl aqueous solution for 2 min. The structure and properties of the composite films were characterized by X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and tensile testing. The results indicated that the tourmaline nanocrystals were dispersed in a cellulose matrix, maintaining the original structure of the nanocrystals in the composite films. The loss peaks (tan δ) in the DMA spectra and the decomposition temperatures in the DSC curves of the composite films were significantly shifted toward low temperatures, suggesting that the nanocrystals broke the partial intermolecular hydrogen bonds of cellulose, and this led to a reduction in the thermal stability. However, the nanocomposite films exhibited a homogeneous structure and dispersion of the nanocrystals. When the tourmaline content was in the range of 4–8 wt %, the composite films possessed good tensile strength (92–107 MPa) and exhibited obvious antibacterial action against Staphylococcus aureus. This work provides a potential way of preparing functional composite films or fibers from cellulose and nanoinorganic particles with NaOH/thiourea aqueous solutions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 367–373, 2004  相似文献   

3.
A new method of synthesis of TiO2 nanoparticles as well as preparation of the organic–inorganic hybrid nanocomposite films of (hydroxypropyl)cellulose (HPC)/TiO2 is presented. At the first stage, the oxotitanium hydrogel phase was obtained by the mineralization of (tetra‐isopropyl)orthotitanate (TIPT) modified by the methacrylic acid (MAA) in 15 wt% solution of H2O2 at room temperature and subsequent annealing at the temperature of 85°C. The crystallization of the nanoparticles of TiO2 was conducted at the oxotitanium hydrogel phase at temperatures around 120°C in the closed vessel. Nanocomposite hybrid films were prepared by the casting method from a solution of HPC and TiO2 nanoparticles in the water. The films of nanocomposite with 10 µm thickness are transparent to visible light and have a lower glass transition temperature compared with HPC in the bulk. This shift of the glass transition is interpreted in terms of packing density of HPC in the interface of HPC nanocomposite with TiO2. The X‐ray diffraction pattern of the nanocomposite film suggests a lower amount of mesomorphic phase of HPC in the composite compared with HPC in the bulk. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

4.
Ternary polycarbonate (PC)/amorphous polyamide–nanoclay (naPA) nanocomposite (PC/naPA) films were obtained by melt mixing and drawing, and the effects of the naPA content and the draw ratio (DR) on the structure, morphology and mechanical and barrier properties were studied. Despite the presence of nanoclay, the films exhibited a negligible roughness and the excellent optical properties of PC and amorphous polyamide (aPA). The dispersed naPA phase was pure and small, indicating compatibility. The naPA did not hinder the drawing ability of PC. At low DRs the dispersed phase was elongated and oriented along the machine direction (extrusion flow direction), but at high DRs, it fibrillated due to the higher non‐isothermal elongational flow induced by drawing. The laminar structure of the nanoclay allowed the films to be reinforced both in the machine and the transverse directions. The oxygen permeability of PC was reduced by 42% in the nanocomposite with 25% of naPA, and dropped further with the DR, which is attributed to the increased tortuosity of the oxygen path induced by fibrillation. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

5.
Bio‐based nanocomposite films were successfully developed using cellulose whiskers as the reinforcing phase and chitosan as the matrix. Cellulose whiskers, with the lengths of 400 ± 92 nm and diameters of 24 ± 7.5 nm on average, were prepared by hydrolyzing cotton linter with sulfuric acid solution. The effects of whisker content on the structure, morphology and properties of the nanocomposite films were characterized by SEM, XRD, FTIR, UV‐vis spectroscopy, DMA, TG, tensile testing, and swelling experiment. The results indicated that the nanocomposites exhibited good miscibility, and strong interactions occurred between the whiskers and the matrix. With increasing whisker content from 0 to 15–20 wt %, the tensile strength of the composite films in dry and wet states increased from 85 to 120 MPa and 9.9 to 17.3 MPa, respectively. Furthermore, the nanocomposite films displayed excellent thermal stability and water resistance with the incorporation of cellulose whiskers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1069–1077, 2009  相似文献   

6.
In recent years, because of the limited availability of oil resources and the increasing concerns regarding environment protection, much attention has been drawn to produce packaging films based on degradable biopolymers instead of synthetic polymers. On the other hand, because of the high costs of oil extraction, raw materials and film production, and disposing of the waste products of synthetic films, the need to replace these films with less pollutant and more cost‐effective films is growing globally. In this study, to answer the need for replacing synthetic polymer films, nanocomposite films based on thermoplastic starch reinforced with cellulose nanofibers and graphene oxide nanoplatelets were produced and characterized. The results implied that the synergistic effect of cellulose nanofibers and graphene oxide nanoplatelets has played an important role in improving the mechanical properties of the films. The results showed that with the addition of cellulose nanofibers and graphene oxide nanoplatelets, the tensile strength and elastic modulus of starch film were increased from 3 and 32 MPa to 13 and 436 MPa, which corresponds to 438% and 1435% improvement, respectively. In addition, the oxygen permeability resistance and the water vapor transmission for samples containing 3 wt% of graphene oxide nanoplatelets was decreased by 78% and 30% compared with the thermoplastic starch film, respectively. The permeability coefficient of the samples containing 3 wt% graphene oxide nanoplatelets for oxygen, nitrogen, and carbon dioxide have proved to be 0.051, 0.054, and 0.047 barrer, which shows that these films can perform well as packaging films.  相似文献   

7.
Vulcanization is a vital process in rubber processing, it endows rubber with valuable physical and mechanical properties, making rubber a widely used engineering material. In addition to vulcanization agent, reinforcing fillers play a non-ignorable influence on the vulcanization of rubber nanocomposites. Herein, the effects of cellulose nanocrystals (CNCs) on the vulcanization of natural rubber (NR)/CNCs nanocomposite was studied. It was found that even though the addition of CNCs can effectively improve the dispersion of ZnO in NR matrix, the vulcanization of NR was inhibited. This may be attributed to the CNCs' adsorption of vulcanizing agents (DM, ZnO) and the acidic chemical environment on the surface of CNCs. In order to improve the vulcanization properties of NR/CNCs nanocomposite, tetramethyldithiochloram (TMTD) and triethanolamine (TEOA) were used as a combination accelerator and curing activator, respectively, and polyethylene glycol (PEG) was introduced to screen hydroxyl groups on the surface of CNCs to prohibit the CNCs' adsorption of vulcanizing agents. The results indicate that TMTD and TEOA effectively improved the vulcanization rate of NR/CNCs nanocomposite and increased the crosslink density by an order of magnitude. Subsequently, the tensile strength, tear strength, and so forth. of NR/CNCs nanocomposite were significantly improved. However, PEG hardly help to improve the vulcanization properties of NR/CNCs nanocomposite. In addition, the control samples without CNCs were prepared and characterized, the comparation between NR and NR/CNCs nanocomposite shows that the synergistic effect of crosslink density and CNCs' reinforcement more effectively improve mechanical properties of NR. This work not only elucidates the inhibiting mechanisms of CNCs on the vulcanization of NR, but also provides practical strategies for improving the vulcanization and properties of NR/CNCs nanocomposite. It may accelerate the application of CNCs as rubber reinforcing filler.  相似文献   

8.
This work presents the effect of driven nickel nanoparticles (NiNPs) towards the surface of (PS-PANI)/NiNPs nanocomposite upon the application of a uniform magnetic field. The purpose is to obtain distinguishable optoelectronic and electrical properties. This process increases the surface roughness and its reactivity, and enables the tuning of the optical and electrical properties. Based on the results from X-ray photoelectron and Fourier-transform infrared spectroscopies, the magnetically-driven NiNPs to the surface are oxidized, forming NiONPs and NiOHNPs. This oxidation effect transforms the surface from a hydrophilic to a hydrophobic state. In addition, the optical bandgap energy decreases from 4.04 to 3.77 eV, and the electrical conductivity increases from 12.77 μS/cm to 57.80 μS/cm and 77.52 μS/cm, for 50 and 100 mT magnetic fields, respectively, which is attributed to the well-dispersed magnetic nanoparticles in the PS-PANI polymer matrix, resulting in a high homogeneous nanocomposite film.  相似文献   

9.
10.
In the aim of producing fully organic bionanocomposite based on poly(lactide) (PLA), cellulose nanowhiskers (CNW) were grafted by n-octadecyl-isocyanate (CNW-ICN) applying an in situ surface grafting method. The compatibilizing effect of the long aliphatic grafted chain was investigated by thermal, mechanical and permeability analysis of solvent cast nanocomposite films. The grafted CNW-ICN could be successfully dispersed in the polymer matrix. The gained compatibility brought about a nucleating effect, decreasing the half time of isothermal crystallization from 25 min for the neat PLA to 8.4 min for the nanocomposite including 2.5 wt% CNW-ICN, e.g., tensile strength was improved by 10 MPa for the same 2.5 wt% CNW-ICN/PLA composite. Mechanical reinforcement was also effective in the rubbery state of PLA and increased the tensile modulus of the rubbery plateau providing thereby thermal resistance to the polymer. Oxygen barrier properties did not change significantly upon the inclusion of CNW-ICN, even when the quantity of CNW-ICN was increased to 15 wt%. More interestingly, the water vapour permeability of the CNW-ICN nanocomposite was always lower than the one of ungrafted CNW composites, which led to the conclusion that the hydrophobic surface graft and improved compatibility could counteract the effect of inclusion of hydrophilic structures in the matrix on water vapour transport. In conclusion, the surface grafting of CNW with isocyanates might be an easy and versatile tool for designing fully organic bionanocomposites with tailored properties.  相似文献   

11.
Using poly(amic acid) (PAA) as a precursor followed by thermal imidization, the polyimide/silica nanocomposite films were prepared via an improved sol–gel process and a blending process, respectively. FT‐IR, TEM and TGA measurements were used to characterize the structure and properties of the obtained films. The results confirmed that the introduction of silica did not yield negative effects on the conversion of the PAA precursor to the polyimide. With the increase of silica content, the aggregation of silica appeared in the polyimide matrix, and the thermal stability decreased slightly for both kinds of films. The dielectric constant (ε) of both films increased slowly with the increase of the silica concentration. The dielectric constant of the obtained polyimide/silica nanocomposite films displayed good stability within a wide range of temperatures or frequency. Based on modeling relation between ε and silica content, the difference in dielectric properties for two kinds of nanocomposites are discussed. Copyright © 2007 John Wiley & Sons, Ltd.  相似文献   

12.
New crosslinked cellulose‐based plastic films were synthesized with olefin metathesis as a crosslinking reaction. Microcrystalline cellulose was first dissolved in a lithium chloride/N,N‐dimethylacetamide solvent system and acylated by ω‐undecenoyl chloride under microwave irradiation with N,N‐dimethyl‐4‐aminopyridine as the catalyst. Cellulose unsaturated fatty acyl esters with a degree of substitution (DS) ranging from 1.4 to 2.0 were then crosslinked by olefin metathesis with a first generation Grubbs catalyst. Crosslinking ratios (T) ranging from 20 to 90% were obtained for low catalyst amounts (<1.2%), but gels appeared when T was too high. To avoid this gel formation, cellulose was acylated with a mixture of lauroyl and ω‐undecenoyl chlorides. This internal dilution allowed us to obtain films of every case and various T (varying from 10 to 80% for a catalyst amount below 3.5%). Plastics were characterized by Fourier transform infrared (FTIR) spectroscopy, and the fatty acid mixture resulting from the hydrolysis of cellulose esters were analyzed by gas chromatography (GC) and NMR spectroscopy. Mechanical properties showed that the elastic modulus and tensile failure stress was higher when the plastic films were crosslinked. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 407–418, 2005  相似文献   

13.
Amorphous poly(lactide) (PLA) and nanocomposite films were prepared from melt‐blending with precipitated calcium carbonate nanofillers (PCC). Nanocomposites based on uncoated PCC (PCC‐UT), stearic acid coated PCC (PCC‐S), and poly(ε‐caprolactone) coated PCC (PCC‐P) were investigated for an inorganic content fixed to 8 wt %. Using coated nanofillers allowed preserving both PLA average molar mass and thermal stability while enhancing the nanofiller dispersion state. Poly(ε‐caprolactone) was identified as the best coating for optimized morphology and thermal properties. Maxwell law accurately described the increase in oxygen barrier properties observed for the nanocomposites based on PCC‐S. A modified Maxwell law was proposed to take account of the additional increase in barrier properties evidenced for the PLA/PCC‐P nanocomposites and assigned to the particularly strong compatibility between PCL and PLA. Different annealing conditions were investigated to respectively study the impact of physical ageing and PLA crystallization on gas permeability. Different extents of physical ageing did not significantly modify the oxygen transport properties. However, a high permeability decrease was observed for the semicrystalline nanocomposites with respect to the amorphous reference PLA film. Finally, the gain in barrier properties was shown to result from both contribution of the nanofillers and the crystalline phase. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 649–658  相似文献   

14.
《先进技术聚合物》2018,29(1):61-68
Bio‐based nanocomposites of poly (butylene adipate‐co‐terephthalate) (PBAT)/silver oxide (Ag2O) were prepared by the composite film casting method using chloroform as the solvent. The prepared Ag2O at different ratios (1, 3, 5, 7, and 10 wt%) is incorporated in the PBAT. The PBAT nanocomposite films were subjected to structural, thermal, mechanical, barrier, and antimicrobial properties. The electron micrographs indicated uniform distribution of Ag2O in the PBAT matrix. However, the images indicated agglomeration of Ag2O particles at 10 wt% loading. The thermal stability of the nanocomposite films increased with Ag2O content. The tensile strength and elongation of the composite films were found to be higher than those of PBAT and increased with Ag2O content up to 7 wt%. The PBAT‐based nanocomposite films showed the lower oxygen and water vapor permeability when compared to the PBAT film. Antimicrobial studies were performed against two food pathogenic bacteria, namely, Klebsiella pneumonia and Staphylococcus aureus.  相似文献   

15.
These days, Ophthalmic wound treatment is a major problem; due to its nature, bio/materials are the best choices as wound dressing materials. The main objective of the current survey is to develop and investigate effective wound dressing materials for skin care applications. In these ways, we combined the good biological properties of Cobalt-doped hydroxyapatite particles (CoHAp) with the structural properties of Polycaprolactone (PCL)/ carboxymethyl cellulose (CMC) nanofibers. Electrospinning and co-precipitation methods were used to synthesize nanofibers and CoHAp particles, respectively. Nanocomposites were synthesized in the absence and different percentages of CoHAp. The PCL/CMC, PCL/CMC/CoHA 5 %, PCL/CMC/CoHA 10 %, and PCL/CMC/CoHA 15 % formulated nanocomposites have the diameter of 383 ± 50, 391 ± 84, 441 ± 65, and 495 ± 99 nm, respectively. The synthesized nanofibrous wound dressing porosity and water absorption capacity were in the range of 40 to 60 % and 32 to 63 %, respectively. Hemo and cytocompatibility of the nanofibrous wound dressing were analyzed by in vitro evaluation, and the results were satisfactory and the structures were fully biocompatible. The PCL/CMC/CoHA 10 % wound dressing, were selected as the best nanocomposites for wound healing based on our animal studies on the healing outcomes. The results showed that the PCL/CMC nanofibers-Cobalt-doped HAp wound dressing is an effective bioactive nano-biomaterials for the wound healing process.  相似文献   

16.
Currently, long-chain cellulose esters are not produced commercially because of high price, and since their preparation typically requires a large quantity of chemicals. To reduce the chemical consumption, cellulose reactivity needs to be increased without losing its quality. One way to increase the reactivity of cellulose is to decrease its molar mass in a controlled manner. In this study, we have synthesized cellulose esters with different side-chain length (C6–C18) in a homogeneous system using ozone molar mass-controlled cellulose. The target was to keep the degree of substitution as low as possible while still ensuring the suitability of cellulose esters for solvent casting. Thermal, barrier and mechanical properties were studied depending on cellulose fatty acid ester side-chain length. All our molar mass-controlled cellulose esters form optically transparent, flexible and heat-sealable films with good water barrier properties and are processable without the addition of an external plasticizer. Furthermore, the films have mechanical properties comparable to some generally used plastics. These good properties suggest that our molar mass-controlled cellulose esters could be potential candidates for various applications such as films and composites.  相似文献   

17.
Novel ultrahigh molecular weight polyethylene (UHMWPE)/cellulose nanofiber (CNF) (F100CNFy) and UHMWPE/modified cellulose nanofiber (MCNFx) (F100MCNFxy) as‐prepared nanocomposite fibers were successfully prepared by gel‐spinning F100CNFy and F100MCNFxy gel solutions, respectively. CNF nanofillers with a specific surface area at 120 m2/g and a nanofiber diameter of 20 nm were successfully prepared by proper acid hydrolysis of cotton fibers using sulfuric acid solution. MCNFx nanofillers were prepared by grafting various contents of maleic anhydride grafted polyethylene (PEg‐MAH) onto CNF nanofillers. The ultimate σf value of the best‐prepared F100MCNFxy drawn fiber reached 4.5 GPa, which is about 67% higher than that of the UHMWPE drawn fiber prepared without the addition of any nanofiller. To understand the interesting ultradrawing, orientation, and tensile properties of F100CNFy and F100MCNFxy fibers, Fourier transform infrared, transmission electron microscopic analyses of the CNF and MCNFx nanofillers, and scanning electron microscopic analyses of profile surfaces of the etched drawn fibers were performed. This is the first work in this area of research wherein very small amounts of MCNFx nanofillers prepared from cotton fibers were efficiently used as nucleating agents to enhance the ultradrawing and ultimate tensile properties of F100MCNFxy fibers. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

18.
Gelatin was extracted from Alaska pollock (Theragra chalcogramma) and Alaska pink salmon (Oncorhynchus gorbuscha) skins and cast into films. The fish gelatin films’ tensile, thermal, water vapor permeability, oxygen permeability, and biodegradation properties were compared to those of bovine and porcine gelatin films. In addition, fish gelatin films were cross-linked with glutaraldehyde. Pollock and salmon gelatin films had comparable tensile properties, but had lower tensile strength and percent elongation than mammalian gelatin films. The lower strength and elongation might have been due to lower structural gelatin levels present in fish gelatin films. The addition of cross-linkers had little effect on tensile properties and melting temperatures of fish gelatin films. Pollock gelatin films had the lowest water vapor and oxygen permeability values, whereas mammalian gelatin films had the highest permeability values. Cross-linking resulted in lower water vapor permeability for salmon gelatin films and higher oxygen permeability for pollock gelatin films. However, all fish gelatin films had better water vapor and oxygen barrier properties than mammalian gelatin films. Also, fish gelatin films degraded faster than mammalian gelatin films.  相似文献   

19.
The influence of the plasticizer content and film preparation procedure on the morphology, density, thermal and mechanical properties of cellulose acetate (CA) films plasticized with poly‐(caprolactone triol) (PCL‐T), were studied. Differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), scanning electron microscopy (SEM), wide‐angle X‐ray diffraction (WAXD) and infrared spectroscopy (FT‐IR) techniques were used. The films were prepared by dry‐casting CA and CA/PCL‐T in acetone or acetone/water solutions, which produced transparent and opaque films, respectively. In contrast to the transparent films, which were dense, the opaque films presented a porous morphology. However, the presence of PCL‐T reduced the opaque film porosity, increasing, in consequence, its bulk density. The TMA results revealed that PCL‐T reduced the glass transition temperature more significantly in the transparent than in opaque films. Only the transparent CA/PCL‐T films presented a melting temperature, that reduced with higher concentrations of PCL‐T, suggesting a higher ordering (crystallinity) when the films were prepared in the absence of water, as observed from WAXD curves. The mechanical properties also showed that the transparent films were more soft and tough than the opaque films. In summary, PCL‐T was a good plasticizer agent for CA films due to the presence of hydrogen bonds between the components (FT‐IR spectra). The presence of water in the dry casting process has a significant effect mainly on film morphology and mechanical properties. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

20.
Polyhedral oligomeric silsequioxane (POSS), having eight hydroxyl groups for the preparation of nanocomposites with polyimide (PI) was synthesized by the direct hydrosilylation of allyl alcohol with octasilsesquioxane (Q8M8H) with platinum divinyltetramethyl disiloxane Pt(dvs) as a catalyst. The structure of allyl alcohol terminated‐POSS (POSS‐OH) was confirmed by FTIR, NMR, and XRD. A high performance, low‐k PI nanocomposite from pyromellitic dianhydride (PMDA)‐4,4'‐oxydianiline (ODA) polyamic acid cured with POSS‐OH was also successfully synthesized. The incorporation of POSS‐OH into PI matrix reduced dielectric constant of PI without loosing mechanical properties. Furthermore, the effects of POSS‐OH on the morphology and properties of the PI/POSS‐OH nanocomposites were investigated using UV–vis, FTIR, XRD, SEM, AFM, transmission electron microscope (TEM), TGA, and contact angle. The homogeneous dispersion of POSS particles was confirmed by SEM, AFM, and TEM. The nanoindentation showed that the modulus increased upon increasing the concentration of POSS‐OH in PI, whereas the hardness did not increase very much with respect to loading of POSS, due to soft‐interphase around POSS molecules in the resulting nanocomposites. Overall results demonstrated the nanometer‐level integration of the polymer and POSS‐OH. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5887–5896, 2008  相似文献   

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