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1.
The investigation of aerogels made from cellulose nanofibers and poly(vinyl alcohol) (PVOH) as a polymeric binder is reported. Aerogels based on different nanocellulose types were studied to investigate the influence of the nanocellulose dimensions and their rigidity on the morphology and mechanical properties of the resulting aerogels. Thus, cellulose nanocrystals (CNCs) with low (10), medium (25), and high (80) aspect ratios, isolated from cotton, banana plants, and tunicates, respectively, microfibrillated cellulose (MFC) and microcrystalline cellulose (MCC) were dispersed in aqueous PVOH solutions and aerogels were prepared by freeze‐drying. In addition to the cellulose type, the PVOH‐ and the CNC‐concentration as well as the freeze‐drying conditions were varied, and the materials were optionally cross‐linked by an annealing step or the use of a chemical cross‐linker. The data reveal that at low PVOH content, rigid, high‐aspect ratio CNCs isolated from tunicates afford aerogels that show the least amount of shrinking upon freeze‐drying and display the best mechanical properties. However, with increasing concentration of PVOH or upon introduction of a chemical cross‐linker the differences between materials made from different nanocellulose types decrease. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41740.  相似文献   

2.
The creep behavior and solid and melt linear viscoelasticity of novel polyamide 6 (PA6) nanocomposites reinforced with cellulose nanocrystals (CNCs) prepared via in situ anionic ring‐opening polymerization (ROP) were investigated to accelerate research efforts to develop new polymeric materials with improved properties for lightweight, load‐bearing applications. The obtained results showed that incorporation of relatively small amounts of ≤ 2wt% CNCs into the PA6 thermoplastic matrix gave nanocomposite samples with significantly enhanced creep and viscoelastic materials functions of the PA6 as indicated by lower creep strain, lower creep compliance, improved elastic recovery after removal of load, and reduced Arrhenius activation energies for time‐dependent viscoplastic flow. The obtained results were analyzed and interpreted by theoretical equations for predicting the viscoelasticity and creep behavior of polymeric systems. The melt rheological properties showed enhanced melt strength and elasticity. The formation of a percolated network structure of CNC was revealed by morphological observations that were consistent with the dynamic structure break‐up and reformation rheological experiments. The stiffness, rigidity of the CNCs along with their special ROP‐facilitated intrinsic strong chemical interactions with the PA6 matrix is believed to be responsible for the observed superior creep and viscoelastic materials functions even with very little CNC concentration. POLYM. ENG. SCI. 56:1045–1060, 2016. © 2016 Society of Plastics Engineers  相似文献   

3.
Cellulose nanocrystals (CNCs) are ideal reinforcing agents for polymer nanocomposites because they are lightweight and nano‐sized with a large aspect ratio and high elastic modulus. To overcome the poor compatibility of hydrophilic CNCs in non‐polar composite matrices, we grafted poly(methyl methacrylate) (PMMA) from the surface of CNCs using an aqueous, one‐pot, free radical polymerization method with ceric ammonium nitrate as the initiator. The hybrid nanoparticles were characterized by CP/MAS NMR, X‐ray photoelectron spectroscopy, infrared spectroscopy, contact angle, thermogravimetric analysis, X‐ray diffraction, and atomic force microscopy. Spectroscopy demonstrates that 0.11 g/g (11 wt %) PMMA is grafted from the CNC surface, giving PMMA‐g‐CNCs, which are similar in size and crystallinity to unmodified CNCs but have an onset of thermal degradation 45 °C lower. Nanocomposites were prepared by compounding unmodified CNCs and PMMA‐g‐CNCs (0.0025–0.02 g/g (0.25–2 wt %) loading) with PMMA using melt mixing and wet ball milling. CNCs improved the performance of melt‐mixed nanocomposites at 0.02 g/g (2 wt %) loading compared to the PMMA control, while lower loadings of CNCs and all loadings of PMMA‐g‐CNCs did not. The difference in Young's modulus between unmodified CNC and polymer‐grafted CNC composites was generally insignificant. Overall, ball‐milled composites had inferior mechanical and rheological properties compared to melt‐mixed composites. Scanning electron microscopy showed aggregation in the samples with CNCs, but more pronounced aggregation with PMMA‐g‐CNCs. Despite improving interfacial compatibility between the nanoparticles and the matrix, the effect of PMMA‐g‐CNC aggregation and decreased thermal stability dominated the composite performance.  相似文献   

4.
Building blocks made from renewable sources attract increasing attention for the design of new polymer systems. Recently, in this particular context, cellulose nanocrystals (CNCs) have gained great interest in both academic research and industry, mainly on account of their ability to reinforce range of polymer matrices and afford nanocomposites with attractive mechanical properties. The limited thermal stability of conventionally produced cellulose nanocrystals (CNCs) has, however, so far limited the range of polymers that could be used as basis for melt‐processed CNC nanocomposites. We herein show that a commercially accessible nanocrystal source, a particular grade of microcrystalline cellulose (MCC), can easily be converted into thermally stable CNCs by ultrasonication in phosphoric acid. A scalable melt‐mixing process was used to produce nanocomposites of these CNCs with a thermoplastic polyurethane (TPU) elastomer. A significant improvement of the room temperature storage modulus from 40 MPa (neat polymer) to 120 MPa (10% w/w CNC) was observed. The introduction of CNCs not only increased the stiffness of the polymer matrix, but also improved the shape memory properties of the nanocomposite. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45033.  相似文献   

5.
The preparation and investigation of functionally graded polymer nanocomposites, which have a concentration gradient of cellulose nanocrystals (CNCs) along one direction, is reported here. As a test bed, a series of nanocomposites consisting of a thermoplastic polyurethane (PU) and 0–15% w/w CNCs is prepared via solvent casting and the mechanical properties of films of these materials are characterized by dynamic mechanical analyses and tensile tests. The formation of graded materials is accomplished by lamination of films with varying CNC content. The processing conditions are optimized to achieve intimate fusion of the individual layers. The elimination of internal interfaces is evidenced by an elongation at break of up to 500%. In order to explore potential applications of graded PU/CNC nanocomposites, structure‐dependent actuation in response to water is demonstrated in a bioinspired architecture. In addition, the damping behavior of cylindrical shaped composites is investigated by way of compression tests. The results show that functionally graded PU/CNC composites show good damping behavior over a much larger range of forces than the neat PU or the homogeneous nanocomposites.  相似文献   

6.
Poly(3‐hydroxybutyrate) (PHB)‐based bionanocomposites were prepared using various percentages of cellulose nanocrystals (CNCs) by a solution casting method. CNCs were prepared from microcrystalline cellulose using sulfuric acid hydrolysis. The influence of CNCs on PHB properties was evaluated using differential scanning calorimetry, Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetry and tensile testing. Vapor permeation and light transmission of the materials were also measured. Differential scanning calorimetric tests demonstrated that CNCs were effective PHB nucleation agents. Tensile strength and Young's modulus of PHB increased with increasing CNC concentration. Moreover, the PHB/CNC bionanocomposites exhibited reduced water vapor permeation compared to neat PHB and had better UV barrier properties than commodity polymers such as polypropylene. It was found that nanocomposites with 6 wt% of CNCs had the optimum balance among thermal, mechanical and barrier properties. © 2016 Society of Chemical Industry  相似文献   

7.
Cellulose nanocrystals (CNCs) have received considerable attention recently because CNCs can be produced from renewable materials such as straw, wood, cotton, and sea animals (tunicates). CNCs are one of the stiffest organic materials, with an estimated tensile modulus (E) of 80–160 GPa depending on the starting material. In addition, composites incorporating CNCs have been fabricated from a variety of polymer matrices and CNCs have been shown to increase the E significantly and to a lesser extent the tensile strength (TS). A copolymer of poly(vinylidene fluoride) (PVDF), PVDF‐co‐hexafluoropropylene) (PVDFHFP), has received interest over the years in the area of lithium ion battery separator technology. However, the mechanical properties of neat PVDFHFP do not meet the necessary requirements for commercial separators, especially the low E. In this work, novel PVDHFHFP/CNC nanocomposite films were fabricated and characterized. It was found that incorporation of CNCs improves the E and TS. The improvement in mechanical properties of PVDFHFP upon addition of CNCs makes PVDFHFP a more suitable candidate for polymer separators in lithium ion batteries. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

8.
Freeze‐dried cellulose nanocrystals (CNCs) were dispersed in the thermoplastic polyurethane [Pellethane 2363‐55D (P55D)] by a solvent casting method to fabricate CNC‐reinforced nanocomposites. This study demonstrated that the addition of small amounts (1–5 wt %) of CNCs to P55D increased the thermal degradation temperature while maintaining a similar stiffness, strength, and elongation of the neat P55D. CNC additions to P55D did not alter the glass‐transition temperature, but the onset decomposition temperature was shifted from 286 to 327°C when 1 wt % CNCs was dispersed in the matrix. The higher onset decomposition temperature was attributed to the formation of hydrogen bonds between the hydroxyl groups on the CNC surface and urethane groups in the hard block of P55D. The ultimate tensile strength and strain to failure (εf) of the nanocomposites were minimally affected by additions up to 5 wt % CNCs, whereas the elastic modulus was increased by about 70%. The observation that εf was unchanged with the addition of up to 5 wt % CNCs suggested that the flow/sliding of the hard blocks and chains were not hindered by the presence of the CNCs during plastic deformation. The ramifications of this study was that CNC additions resulted in wider processing temperatures of P55D for various biomedical devices while maintaining a similar stiffness, strength, and elongation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41970.  相似文献   

9.
In this study, we reported the preparation and prospective application of the nanocomposites of poly(butylene adipate‐co‐terephthalate) (PBAT) reinforced with cellulose nanocrystals (CNCs). CNCs were isolated from bleached sugarcane bagasse by acid hydrolysis and functionalized with adipic acid. Nanocomposites were prepared with different concentration of CNCs (0.8, 1.5, and 2.3 wt% CNC) by solution‐casting method and then were covered with silver thin film by magnetron sputtering. The results showed that the surface modification increased the degree of crystallinity of nanocrystals from 51% to 56%, decreasing their length and diameter. Moreover, AFM‐IR spectroscopy revealed that the modified CNCs were covered by adipic acid molecules, improving the dispersion of nanocrystals in PBAT. Well‐dispersed modified CNCs acted as heterogeneous nuclei for crystallization of PBAT, and increased the storage modulus of the polymer by more than 200%. These improvements in thermal and mechanical properties of CNC‐based PBAT associated with the decrease of 56% in the Escherichia coli biofilm formation on nanocomposites (antibacterial properties) qualify the CNC/PBAT nanocomposites covered with silver thin films to be used as food packaging. POLYM. ENG. SCI., 59:E356–E365, 2019. © 2019 Society of Plastics Engineers  相似文献   

10.
Cellulose nanocrystals (CNCs) have emerged as fillers of interest to the polymer nanocomposite community due to their inherent properties and renewable precursors. However, challenges persist to incorporate CNCs into polymer matrices due to component incompatibility and/or thermal stability limitations of the nanoparticles. Therefore, the objective of this research is to examine the efficacy of different processing methods in producing CNC/polymer composites. In this work, CNCs were incorporated into polyethylene-co-vinyl alcohol (EVOH) using either a solution casting method or a multi-step method involving the same solution casting method followed by a melt mixing step. The resulting neat EVOH and composite materials were characterized to understand how the viscoelastic character and mechanical properties were influenced by CNC loading and processing method. The results of characterization experiments and micromechanical modeling suggested that the nanoparticle networks produced by each method were different and that a combined solution-melt processing method is beneficial in producing composites with improved properties, particularly at higher CNC loadings. This processing strategy may be more broadly applied to other nanocomposites.  相似文献   

11.
Cellulose nanocrystals (CNCs) prepared via sulfuric acid hydrolysis are decorated with sulfate groups that yield a stable water suspension. To make the CNCs adaptable for use in composites, the hydroxyl groups on the surface are usually hydrophobized. In this article, an alternative hydrophobization method is described in which the sulfate groups are conjugated with azetidinium salts. The results of this study show that the sulfate groups can be functionalized with azetidinium salts and from thermal studies, it was discovered that the functionalization led to a 100 °C increase in thermal stability, compared with unmodified CNCs. The nanocomposites prepared by extrusion of CNC‐coated low‐density polyethylene powder displayed similar mechanical properties as the CNC‐reference sample, but without the discoloration, due to the increased thermal stability. In conclusion, the azetidinium reagent reacts preferentially with sulfate groups, and this new type of chemical conversion of sulfate groups on polysaccharides will be beneficial in nanocomposite manufacturing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45963.  相似文献   

12.
The present study focuses on the isolation and characterization of the cellulose nanocrystals (CNCs) from the pineapple peel waste (PPW) (agro-waste) and sisal fiber (SiF) (natural fiber) employing the acid hydrolysis method, and its comparison with the commercially available CNCs (CNC-C). Furthermore, the CNCs from PPW, SiF, and CNC-C were subjected to transmission electron microscopy (TEM), Fourier transform electron microscopy, X-ray diffraction, particle size distribution, and zeta potential analysis. The studied properties of the isolated CNCs are considerably different from the PPW and SiF. The CNCs so formed have been estimated by TEM to be around 10–40 nm wide and length of several micrometers. Fourier transform electron microscopy studies described the removal of the noncellulosic components like lignin, hemicellulose, and pectin substances from the base materials in both the cases by employing acid hydrolysis method. Additionally, nanocomposites of CNC isolated from PPW along with polypropylene (PP) matrix were fabricated using melt blending method followed by injection molding. Maleic anhydride grafted PP (MAPP) acts as a compatibilizer for improving the dispersibility of hydrophilic CNC within the nonpolar PP matrix. The addition of CNC (3 wt%) along with MAPP at 5 wt% showed optimum tensile strength and modulus to the tune of 10.39 and 25.53%, respectively, when compared to their counterparts without MAPP. Dynamic mechanical analysis revealed an increased stiffness of PP in its nanocomposite system due to the addition of CNC. Scanning electron microscopy studies revealed uniform distribution of CNC within the nonpolar PP matrix in the presence of MAPP.  相似文献   

13.
Cellulose nanocrystal (CNCs)‐reinforced poly(lactic acid) (PLA) nanocomposites were prepared using twin screw extrusion followed by injection molding. Masterbatch approach was used to achieve more efficient dispersion of CNCs in PLA matrix. Modified CNCs (b‐CNCs) were prepared using benzoic acid as a nontoxic material through a green esterification method in a solvent‐free technique. Transmission electron microscopy images did not exhibit significant differences in the structure of b‐CNCs as compared with unmodified CNCs. However, a reduction of 6.6–15.5% in the aspect ratio of b‐CNCs was observed. The fracture surface of PLA‐b‐CNCs nanocomposites exhibited rough and irregular pattern which confirmed the need of more energy for fracture. Pristine CNCs showed a decrease in the thermal stability of nanocomposites, however, b‐CNCs nanocomposites exhibited higher thermal stability than pure PLA. The average storage modulus was improved by 38 and 48% by addition of CNCs and b‐CNCs in PLA, respectively. The incorporation of b‐CNCs increased Young's modulus, ultimate tensile stress, elongation at break, and impact strength by 27.02, 10.90, 4.20, and 32.77%, respectively, however, CNCs nanocomposites exhibited a slight decrease in ultimate strength and elongation at break. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46468.  相似文献   

14.
Conductive polyphenylene sulfide (PPS)/polyamide 6 (PA6)/multiwalled carbon nanotube (MWCNT) composites having 10–30 wt % PA6 and 1 wt % MWCNTs are prepared by melt mixing at 300°C for 8 min using a high concentration PPS/MWCNT masterbatch approach, and the migration kinetics of MWCNTs from thermodynamically unfavored PPS to favored PA6 was investigated. The morphology of the composites was investigated by field emission scanning electron microscopy and transmission electron microscopy, showing the localization of most MWCNTs in the PPS phase and at the interface, being different from the case of direct melt mixing where non‐conductive materials were obtained with most MWCNTs found in the PA6 phase and at the interface. The electrical resistivity and morphology of the materials as a function of time were investigated, showing that the conductive materials can be prepared within a mixing time of 4–16 min because of the slow migration rate of MWCNTs from PPS toward PA6, and MWCNTs can eventually migrate into the PA6 phase after a long mixing time of 30 min. The slow migration rate of MWCNTs was attributed to the high viscosity ratio of the two phases. This article shows a good example where the migration of MWCNTs was slow enough to control and can be used to prepare conductive polymer blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42353.  相似文献   

15.
Ternary composites were prepared by twin screw extrusion from polybutylene‐succinate (PBS), poly(ethylene‐glycol) (PEG), and cellulose nanocrystals (CNC). The aim of the work is to improve the physical–mechanical properties of PBS by the addition of CNC. A PEG/CNC masterbatch was prepared in order to achieve a good dispersion of hydrophilic CNC in the hydrophobic PBS. The influence of the nanoparticle content on the polymer properties was studied. Regarding the thermal properties fractioned crystallization phenomena of PEG was observed during cooling from the melt. No significant nucleating effect of the nanocellulose was observed. The material containing 4 wt % of CNC showed the best mechanical performance among the nanocomposites studied due to the combination of high modulus and elongation at break with a low detrimental in strength compared with the PBS/PEG blend. Moreover, no nanocellulose agglomerations were observed in its FESEM micrograph. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43302.  相似文献   

16.
The objective of the study is to investigate the effect of inclusion of nanotalc on the strength properties of polyamide 6 (PA6)‐based binary and ternary nanocomposites. Binary nanocomposites were prepared by melt compounding of PA6 with varying content of nanotalc (1, 2, and 4 wt%). Ternary nanocomposites were prepared by melt compounding of compatibilized blend of PA 6 and ethylene‐co‐butyl acrylate (EBA elastomer) with varying content of nanotalc (1, 2, and 4 wt%). Both the binary and ternary nanocomposites registered a very high improvement in the strength/stiffness‐related properties at lower filler loading of 1 wt%. Phase morphology of the composites studied by SEM, TEM, and XRD revealed the formation of extended brane‐like structures and delaminated talc layers in the binary nanocomposites. The modulus predicted by Halpin‐Tsai and Mooney equation suggests that the composites retained a very good aspect ratio after melt mixing. Orientation effects of nanotalc enhanced the melt flow behavior in the composites. POLYM. ENG. SCI., 50:1978–1993, 2010. © 2010 Society of Plastics Engineers  相似文献   

17.
The influence of processing methods on the thermo‐mechanical properties of poly (lactic acid) (PLA) nanocomposites were investigated by preparing nanocomposites reinforced by halloysite nanotubes (HNTs) (from 0 to 10 [w/w%]) using solution casting (SC) and melt compounding (MC) methods. Statistical analysis revealed that the processing methods have a significant influence on the tensile properties, where nanocomposites prepared by MC have higher tensile properties compared to those by SC. Experimental results illustrated higher tensile strength and a drop in ductility under the higher strain rate as compared to the low strain rate for PLA/HNTs nanocomposites. At lower concentrations micrographs revealed that, HNTs dispersion was better for SC films as compared to MC, but more prominent HNTs aggregation at higher loadings. MC nanocomposites exhibited a high crystallinity as compared to SC, due to the recrystallization and nucleation effects. The thermal stability and activation energy increased with addition of HNTs, regardless of the processing methods. POLYM. COMPOS., 37:861–869, 2016. © 2014 Society of Plastics Engineers  相似文献   

18.
Both polyamide 12 (PA 12)/clay and polyamide 6–polyamide 66 copolymer (PA 6/6,6)/clay nanocomposites were prepared by melt intercalation. The incorporation of 4–5 wt % modified clay largely increased the strength, modulus, heat distortion temperature (HDT), and permeation resistance to methanol of the polyamides but decreased the notched impact strength. Incorporation of the clay decreased the melt viscosities of both the PA 12 and PA 6/6,6 nanocomposites. Incorporation of the clay increased the crystallinity of PA 6/6,6 but had little effect on that of PA 12, which explained why the clay obviously increased the glass‐transition temperature of PA 6/6,6 but hardly had any effect on that of PA 12. The dispersion and orientation of both the clay and the polyamide crystals were studied with transmission electron microscopy, scanning electronic microscopy, and X‐ray diffraction. The clay was exfoliated into single layers in the nanocomposites, and the exfoliated clay layers had a preferred orientation parallel to the melt flow direction. Lamellar crystals but not spherulites were initiated on the exfoliated clay surfaces, which were much more compact and orderly than spherulites, and had the same orientation with that of the clay layers. The increase in the mechanical properties, HDT, and permeation resistance was attributed to the orientated exfoliated clay layers and the lamellar crystals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4782–4794, 2006  相似文献   

19.
The poor mechanical properties of alginate when exposed to aqueous solution have been a problem plaguing researchers within the biomedical field. In order to be able to improve the mechanical properties in a systematic manner functionalized cellulose nanocrystals (CNCs) were added to alginate and UV‐induced crosslinked following an azo‐initiated free radical polymerization. CNCs were functionalized with 4‐pentenoic acid (PA‐g‐CNCs) using a simple, environmentally friendly solvent‐free esterification. The dimensional and crystallinity properties of PA‐g‐CNCs remained unchanged following esterification. Thermogravimetric analysis, Fourier transform infrared spectroscopy, and 13C nuclear magnetic resonance indicated that 4‐pentenoic acid was present on the surface of CNCs through bulk analysis. These PA‐g‐CNCs were then used in the creation of composites with an azo‐initiator to induce UV‐dependent crosslinking for the improvement of the mechanical properties of alginate. It was shown that the properties of alginate can be enhanced with the addition of functionalized CNCs to nanocomposites in mechanical testing in wet and dry conditions. These results suggest that the addition of PA‐g‐CNCs and crosslinking by UV‐dependent free radical polymerization improves the performance of alginate when tested in dry conditions, but without any apparent dependence to azo‐initiated crosslinking when exposed to water in regards to mechanical properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45857.  相似文献   

20.
Cellulose nanocrystals (CNCs) are an environmentally friendly natural material, consisting of rod‐like crystalline nanoparticles, called whiskers, or nanocrystalline cellulose. The derivation of different natural sources, aligned to their biocompatibility, biodegradability, and versatility, make them a class of fascinating materials with widespread industrial use. In addition, the cellulose species possess intriguing physicochemical and mechanical properties. This paper provides an overview of recent progress in the area of cellulosic nanocomposites, along with details of their structure and liquid crystalline behavior as nematic and cholesteric lyotropic materials. Guidance is subsequently provided for the physicochemical analysis of these materials, including X‐ray diffraction, transmission electron microscopy, optical evaluation, thermogravimetric analysis, and differential scanning calorimetry. Additionally, the functional chemical and physical properties of CNCs are correlated to the resulting nanotoxicity in in vitro and in vivo assays. This review points to relevant concerns, such as sources for the synthesis of CNCs, the nanomaterial size, and the surface chemistry, that must be overcome in order to attain safe use of CNC‐based nanomaterials. The challenging perspectives on the ongoing research are presented in order to explore the technological and industrial perspectives on the use of CNC for the generation of cost‐effective advanced nanomaterials based on cellulosic fibers.  相似文献   

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