Pullulan–nanofibrillated cellulose composite films with improved thermal and mechanical properties

Novel bionanocomposite films with improved thermal and mechanical properties, were prepared by casting water-based suspensions of pullulan and nanofibrillated cellulose. The effect of the addition of glycerol, as a plasticizer, on the properties of the materials was also evaluated. The ensuing materials were characterized in terms of morphology, thermal stability, crystalline structure and mechanical properties. All bionanocomposites were very homogeneous, translucent and showed considerable improvements in thermal stability (increments of up to 20 °C in the degradation temperature) and mechanical properties (increments of up to 5500% and 8000% in the Young’s modulus and tensile strength, respectively, for films plasticized with glycerol) when compared to the unfilled pullulan films. Additionally, these novel bionanocomposite could be labeled as sustainable materials since they were prepared entirely from renewable resources and through a green approach.     

聚乳酸/酯化纤维素纳米晶体共混膜性能研究

以聚乳酸(PLA)为基体,酯化纤维素纳米晶体(ECNC)为添加剂,制备了PLA/ ECNC共混膜。探讨了原始纤维素纳米晶体(CNC)与ECNC对PLA膜的透光率、表面形貌、热稳定性、亲疏水性及力学性能的影响。结果表明,与CNC相比,ECNC与PLA的相容性提高,透光率、热稳定性及力学性能也显著增强;经酯化的纤维素纳米晶体能降低CNC的亲水性,从而增强与PLA的界面黏合力,使CNC在PLA共混膜中的质量分数由小于1%提高到5%。该PLA/ECNC共混膜在包装塑料领域具有潜力,为制备出性能更加优良的可降解包装用塑料提供了一种简单可行的方法。     

聚乳酸/乙基纤维素复合膜的制备及其性能

以烯基琥珀酸酐( ASA) 作为新型增塑剂, 使用三氯甲烷作为聚乳酸( PLA) 和乙基纤维素( EC) 的共溶剂, 采用溶液浇铸法成功制备了聚乳酸/ 乙基纤维素复合膜。用红外光谱( FT IR) 、X 射线衍射(XRD) 表征了复合膜结构, 并测试了其吸水性和力学性能。FTIR 测试结果显示, 复合膜中存在强烈的氢键相互作用。XRD 表明,ASA 显著提高了PLA 和EC 2 种高聚物的界面黏合性。力学测试结果表明, ASA 对该复合膜具有良好的增塑效果。当膜中PLA 质量分数[ 37%时, PLA 对复合膜起增强作用。复合膜的吸水性随ASA 含量的增大而降低, 随PLA 含量的增大而提高。该复合膜作为一种潜在的药物缓释材料, 将具有广阔应用前景。      

Mechanical properties of cellulose nanofiber (CNF) reinforced polylactic acid (PLA) prepared by twin screw extrusion

The aim of this study was to develop cellulose nanofiber (CNF) reinforced polylactic acid (PLA) by twin screw extrusion. Nanocomposites were prepared by premixing a master batch with high concentration of CNFs in PLA and diluting to final concentrations (1, 3, 5 wt.%) during the extrusion. Morphology, mechanical and dynamic mechanical properties (DMA) were studied theoretically and experimentally to see how different CNF concentrations affected the composites’ properties. The tensile modulus and strength increased from 2.9 GPa to 3.6 GPa and from 58 MPa to 71 MPa, respectively, for nanocomposites with 5 wt.% CNF. The DMA results were also positive; the storage modulus increased for all nanocomposites compared to PLA; being more significant in the high temperature region (70 °C). The addition of nanofibers shifted the tan delta peak towards higher temperatures. The tan delta peak of the PLA shifted from 70 °C to 76 °C for composites with 5 wt.% CNF.     

Semi-rigid biopolyurethane foams based on palm-oil polyol and reinforced with cellulose nanocrystals

In this study, water-blown biopolyurethane (BPU) foams based on palm oil were developed and cellulose nanocrystals (CNC) were incorporated to improve the mechanical properties of the foams. In addition, the foams were compared with petroleum polyurethane (PPU) foam. The foam properties and cellular morphology were characterized. The obtained results revealed that a low-density, semi-rigid BPU foam was prepared using a new formulation. CNC as an additive significantly improved the compressive strength from 54 to 117 kPa. Additionally, cyclic compression tests indicated that the addition of CNC increased the rigidity, leading to decreased deformation resilience. The dimensional stability of BPU foams was increased with increasing CNC concentration for both heating and freezing conditions.Therefore, the developed BPU nanocomposite foams are expected to have great potential as core material in composite sandwich panels as well as in other construction materials.     

Isocyanate-rich cellulose nanocrystals and their selective insertion in elastomeric polyurethane

Cellulose nanocrystals (CNC) were successfully obtained and modified with 1,6-hexamethylene diisocyanate (HDI) by means of in situ polymerization varying the CNC/HDI molar ratio to evaluate the number of anchored chains to the CNC. The modification was examined by elemental analysis, nuclear magnetic resonance (¹³C NMR) and attenuated total reflection Fourier transform infrared spectroscopy (IR-ATR). Nanocomposites containing 1.5 wt% CNC, modified and unmodified, were prepared by solvent casting. Thermal and mechanical properties of the resulting films were evaluated from the viewpoint of polyurethane microphase separated structure, soft and hard domains. CNC were effectively dispersed in the polyurethane matrix and depending on surface chemistry, the nanoreinforcement interacts selectively with matrix nanodomains. This interpretation is supported by differences in thermal and mechanical properties of the nanocomposites and also confirmed by AFM images. Isocyanate rich cellulose nanocrystals interacted with matrix hard phase, promoting physical association with hard segments, enhancing stiffness and dimensional stability versus temperature of the nanocomposite.     

Functionalized cellulose nanocrystals as biobased nucleation agents in poly(l-lactide) (PLLA) – Crystallization and mechanical property effects

The important industrial problem of slow crystallization of poly(l-lactide) (PLLA) is addressed by the use of cellulose nanocrystals as biobased nucleation reagents. Cellulose nanocrystals (CNC) were prepared by acid hydrolysis of cotton and additionally functionalized by partial silylation through reactions with n-dodecyldimethylchlorosilane in toluene. Such silylated cellulose nanocrystals (SCNC) were dispersible in tetrahydrofuran and chloroform, and formed stable suspensions. Nanocomposite films of PLLA and CNC or SCNC were prepared by solution casting. The effects of surface silylation of cellulose nanocrystals on morphology, non-isothermal and isothermal crystallization behavior, and mechanical properties of these truly nanostructured composites were investigated. The unmodified CNC formed aggregates in the composites, whereas the SCNC were well-dispersed and individualized in PLLA. As a result, the tensile modulus and tensile strength of the PLLA/SCNC nanocomposite films were more than 20% higher than for pure PLLA with only 1 wt.% SCNC, due to crystallinity effects and fine dispersion.     

Preparation,optical and thermal properties of CdSe–ZnS/poly(lactic acid) (PLA) nanocomposites

In this study, CdSe–ZnS/poly(lactic acid) (PLA) nanocomposite films, containing different concentrations of surface-modified CdSe–ZnS quantum dots (QDs), were prepared via a solution casting method. The optical microstructural and thermal properties of the as-prepared QDs/PLA films were investigated. The QDs/PLA films exhibited strong and stable photoluminescence (PL) intensity with concentration dependent amplitudes. The transmission electron microscopy (TEM) pictures revealed that QDs of ∼5 nm diameter were uniformly dispersed in the PLA matrix. According to the results of thermogravimetric analysis, the weight-loss onset temperature of PLA clearly decreased with the QD content. A combination of Fourier transform infrared (FT-IR) spectroscopy, X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) results suggested that the QDs exhibit obvious nucleation activity on the crystallization behavior of the PLA matrix. This research provides useful information to the foundations of practical applications of QDs/PLA nanocomposites as fluorescent and biodegradable functionalized materials.     

Processing of cellulose nanowhiskers/cellulose acetate butyrate nanocomposites using sol-gel process to facilitate dispersion

Biobased nanocomposites based on cellulose nanowhiskers (CNWs) and cellulose acetate butyrate (CAB) were prepared using solvent exchange of CNWs to ethanol by sol-gel method followed by casting. The strong flow birefringence of the solutions indicated evenly dispersed cellulose nanowhiskers in the dissolved polymer CAB. Scanning electron microscopy of the nanocomposites confirmed well dispersed CNWs in the CAB matrix, which was further supported by the high transparency exhibited by the nanocomposites. The results of tensile tests indicated significant improvements in the mechanical properties of nanocomposites by increasing the CNWs contents. The Young’s modulus and strength increased 83% and 70%, respectively, for nanocomposites with 12 wt% of CNW, and the strain was not suppressed compared to the neat CAB. The dynamic mechanical thermal analysis demonstrated significant improvement in storage modulus with increasing CNW contents, and the tan δ peak position was moved towards higher temperature when CNW was added. It is expected that solvent exchange by the sol-gel route followed by casting of nanocomposites from the same solvent will provide a promising route for obtaining cellulose nanocomposites with well dispersed CNW, leading to improved mechanical properties, even with low nanowhisker contents.     

Effects of grafted chain length on mechanical and electrical properties of nanocomposites containing polylactide-grafted carbon nanotubes

We herein report the effects of interfacial reinforcement on mechanical and electrical properties of nanocomposites based on polylactide (PLA) and multi-walled carbon nanotube (MWCNT). For this purpose, a series of MWCNTs grafted with PLA chains of various lengths (MWCNT-g-PLAs) were prepared by ring-opening polymerization of l-lactide with carboxylic acid-functionalized MWCNT (MWCNT-COOH). MWCNT-g-PLAs were then mixed with commercial PLA to obtain PLA/MWCNT-g-PLA nanocomposites with 1.0 wt.% MWCNT content. It was revealed that morphological, mechanical, and electrical properties of PLA/MWCNT-g-PLA nanocomposites were strongly dependent on the PLA chain length of MWCNT-g-PLAs. FE-SEM images exhibited that the nanocomposites containing MWCNT-g-PLA with longer PLA chain length exhibited better dispersion of MWCNTs in the PLA matrix. Initial moduli and tensile strengths of PLA/MWCNT-g-PLA composites increased with the increment of chain length of PLA grafted on MWCNTs, which attributes to the improved interfacial adhesion between the grafted PLA chains of MWCNT-g-PLA and the PLA matrix. As a result, the experimental initial modulus (2775 ± 193 MPa) of the nanocomposite including MWCNT-g-PLA with PLA chains of average molecular weight of 530 g/mol was quite close to the theoretical value (2911 MPa) predicted for the nanocomposite with perfect interfacial adhesion. Unexpectedly, electrical resistivities of PLA/MWCNT-g-PLA nanocomposites were found to increase from ∼10⁴ to ∼10¹² Ω/sq with increasing the PLA chain length of MWCNT-g-PLA, which is due to the fact that the PLA chains grafted on MWCNTs prevent the formation of the electrical conduction path of MWCNTs in the PLA matrix.     

Effect of crystallite size of zinc oxide on the mechanical,thermal and flow properties of polypropylene/zinc oxide nanocomposites

ZnO nanoparticles were prepared using zinc chloride and sodium hydroxide in chitosan medium. Prepared ZnO (NZO) and commercial ZnO (CZO) was characterized by scanning electron microscopic and X-ray diffraction studies. PP/ZnO nanocomposites were prepared using 0–5 wt% of zinc oxide by melt mixing. It was then compression moulded into films. Transparency of the composite films were improved by reducing the crystallite size of ZnO. Melt flow index studies revealed that NZO increased the flow characteristics of PP while CZO decreased. X-ray diffraction studies indicated α-form of isotactic polypropylene. An increase in mechanical properties, dynamic mechanical properties and thermal stability of the composites were observed by the addition of ZnO. Uniform dispersion of the ZnO was observed in the scanning electron micrographs of the tensile fractured surface of composites.     

The relationship between microstructure and mechanical properties of carbon nanotubes/polylactic acid nanocomposites prepared by twin-screw extrusion

Twin-screw extrusion was applied to prepare the carbon nanotubes/polylactic acid (CNT/PLA) nanocomposites. Five different extruded plates were produced under variation of CNT concentrations. The internal microstructures were also observed by optical microscope to examine the distribution and dispersion of CNT in the PLA. Besides, the crystallinity of the CNT/PLA nanocomposites was investigated by differential scanning calorimetry (DSC) and density method. The effects of the CNT concentrations on the mechanical and electrical properties of the nanocomposites were investigated. Scanning electron microscope (SEM) was performed to observe the CNT dispersion in the nano-scale. These results suggested that the crystallinity was increased with the increase of CNT concentrations, demonstrating that CNT played a role as a nucleating agent in PLA. Moreover, the mechanical and electrical properties of PLA have been improved by a proper incorporation of CNTs due to a good distribution and dispersion of the CNTs.     

Crosslinked natural rubber nanocomposites reinforced with cellulose whiskers isolated from bamboo waste: Processing and mechanical/thermal properties

Crosslinked natural rubber (NR) nanocomposites were prepared using cellulose nanowhiskers (CNWs) that were extracted from bamboo pulp residue of newspaper production, as the reinforcing phase. The coagulated NR latex containing bamboo nanowhiskers (master batch) was compounded with solid NR and vulcanizing agents using a two-roll mill and subsequently cured to introduce crosslinks in the NR phase. No evidence of micro-scaled aggregates of cellulose nanowhiskers in NR matrix was observed in Scanning Electron Microscopy (SEM) images. The addition of CNWs had a positive impact on the tensile strength, E-modulus, storage modulus, tan delta peak position and thermal stability of the crosslinked NR. Theoretical modeling of the mechanical properties showed a lower performance than predicated and therefore further process optimization and/or compatibilization are required to reach the maximum potential of these nanocomposites.     

Processing and characterization of solid and microcellular poly(lactic acid)/polyhydroxybutyrate-valerate (PLA/PHBV) blends and PLA/PHBV/Clay nanocomposites

The morphology, microstructure, tensile properties, and dynamic mechanical properties of solid and microcellular poly(lactic acid) (PLA)/polyhydroxybutyrate-valerate (PHBV) blends, as well as PLA/PHBV/clay nanocomposites, together with the thermal and rheological properties of solid PLA/PHBV blends and PLA/PHBV/clay nanocomposites, were investigated. Conventional and microcellular injection-molding processes were used to produce solid and microcellular specimens in the form of ASTM tensile test bars. Nitrogen in the supercritical state was used as the physical blowing agent in the microcellular injection molding experiments. In terms of rheology, the PLA/PHBV blends exhibited a Newtonian fluid behavior, and their nanocomposite counterparts showed a strong shear-thinning behavior, over the full frequency range. An obvious pseudo-solid-like behavior over a wide range of frequencies in the PLA/PHBV/clay nanocomposites suggested a strong interaction between the PLA/PHBV blend and the nanoclay that restricted the relaxation of the polymer chains. PLA/PHBV/clay nanocomposites possess a higher modulus and greater melt strength than PLA/PHBV blends. The addition of nanoclay also decreased the average cell size and increased the cell density of microcellular PLA/PHBV specimens. As a crystalline nucleating agent, nanoclay significantly improved the crystallinity of PHBV in the blend, thus leading to a relatively high modulus for both solid and microcellular specimens. However, the addition of nanoclay had less of an effect on the tensile strength and strain-at-break.     

Experimental and theoretical analyses of mechanical properties of PP/PLA/clay nanocomposites

Compatibilized and non-compatibilized blends of polypropylene (PP) and poly(lactic acid) (PLA) with various compositions containing nanoclay particles were prepared by one step melt compounding in a twin screw extruder. Two nanocomposite systems with different matrices i.e. PP-rich (75/25 composition) containing Cloisite 15A and PLA-rich (25/75 composition) containing Cloisite 30B were selected for investigation of effect of nanoclays and n-butyl acrylate glycidyl methacrylate ethylene terpolymers (PTW) as compatibilizer on mechanical properties of PP/PLA/clay nanocomposites. Tensile and impact properties of the nanocomposite systems were investigated and correlated with their microstructures. Tensile modulus and strength of the blends were increased while elongation at break decreased by increasing PLA content. There was an irregular relationship between impact strength of the blends and PLA content. Several proposed models for blends and nanocomposites were used for prediction of tensile modulus of the samples. Most of the proposed models for blends could predict the tensile modulus of the blends successfully at low content of PLA. Another notable point was that most of the micromechanical models for nanocomposites fitted well to experimental values at low content of the clays and showed deviations at high clay loadings.     

Barium titanate as a filler for improving the dielectric property of cyanoethyl cellulose/antimony tin oxide nanocomposite films

CEC/ATO and CEC/BTO/ATO nanocomposite films were fabricated by introducing barium titanate (BTO) and antimony tin oxide (ATO) in cyanoethyl cellulose (CEC) via simple solution blending technique. The morphology, microstructure, thermal stability, mechanical, optical and dielectric properties of the nanocomposite films were investigated. The results indicated that CEC/BTO/ATO nanocomposite films possessed better dielectric property and mechanical property compared with CEC/ATO nanocomposite films. This could be ascribed to the homogeneous dispersion of ATO in CEC matrix due to the introduction of BTO. The nanocomposite films with only ATO nanoparticles had a certain optical transmissibility. In addition, all the nanocomposite films possessed better thermal stability than CEC polymer.     

Preparation and properties of microfibrillated cellulose polyvinyl alcohol composite materials

This work reports the preparation of MFC–PVA composite films, and the thermal and mechanical properties of these films. Microfibrillated cellulose (MFC), which was separated from kraft pulp by a mechanical process, was used as the reinforcement in polyvinyl alcohol (PVA) matrix. This MFC reinforcement has an interconnected web-like structure with fibrils having a diameter in the range of 10–100 nm, as observed by TEM. MFC–PVA composite films were created by casting from a water suspension to produce a homogeneous dispersion of MFC in the polymer matrix. DMA shows an increase of the storage modulus in the glassy state with increasing MFC content, but a more significant increase in modulus is detectable above the glass transition temperature. There is a steady increase in both the modulus and strength of the composite films until a plateau is reached at 10 wt% MFC. The thermal stability of the PVA composite films is slightly increased with the addition of MFC.

As a result of this research, it has been shown that MFC is an excellent reinforcement comparable to cellulose nanowhiskers. Furthermore, by combining MFC with PVA in addition to good mechanical properties, this composite has good chemical resistance and biodegradability. The water soluble characteristics of PVA combined with a water dispersion of MFC are also easily processable.     

Enhanced ductility and tensile properties of hybrid montmorillonite/cellulose nanowhiskers reinforced polylactic acid nanocomposites

Montmorillonite (MMT)/cellulose nanowhiskers (CNW) reinforced polylactic acid (PLA) hybrid nanocomposites were prepared by solution casting. CNW were isolated from microcrystalline cellulose using a chemical swelling method. An initial study showed that the optimum MMT content, for mechanical properties, in a PLA/MMT nanocomposite is five parts per hundred parts of polymer (phr). Various amounts of CNW were added to the optimum formulation of PLA/MMT to produce PLA/MMT/CNW hybrid nanocomposites. FT-IR analysis indicated the formation of some polar interactions, resulting in enhanced tensile properties of the hybrid nanocomposites. The highest tensile strength for the hybrid nanocomposites was obtained for a 1 phr CNW content. Young’s modulus was also found to increase with an increasing CNW content. Interestingly, the strain to failure (or ductility) of the hybrid nanocomposites increased significantly from ~10 to ~90 % with the addition of 1 phr CNW. This increase in ductility was proposed to be due to the nucleation of crazes and the formation of shear bands in the PLA.     

Low density polyethylene – Chitosan composites

With the aim of develop new materials for active food packaging, composites of low-density polyethylene (LDPE) with chitosan (CS) or chitosan sodium montmorillonite clay nanocomposites (CSnano), with or without Irganox 1076 commercial synthetic antioxidant or vitamin E (VE) as natural antioxidant were prepared by melt processing. The obtained materials have been characterized by processing behavior, mechanical and thermal properties, positive groups determination, atomic force microscopy and standard tests to assess antimicrobial and antioxidant activities. The compositions assuring insignificant decrease in mechanical and thermal properties were selected as LDPE/3CSnano/VE and LDPE/6CSnano/VE. It has been shown the chitosan imparts antimicrobial properties to LDPE films while the vitamin E increased the oxidation induction period, especially for materials containing chitosan nanocomposites. The incorporation of both chitosan nanocomposites and vitamin E in polyethylene gave films with good antimicrobial and thermal properties because of significant increase of charge surface and important changes in surface topology and antimicrobial activity because of a synergistic effect. The nanocomposites cannot only passively protect the food against environmental factors, but they may enhance shelf life of food products.     

Multifunctional graphene nanoplatelets/cellulose nanocrystals composite paper

We demonstrate a water-based method to fabricate strong, electrically and thermally conductive hybrid thin films (papers) made from the combination of graphene nanoplatelets (GnP) and cellulose nanocrystals (CNC). Unpressed and hot-pressed GnP papers containing CNC ranging from 0 wt% to 25 wt% were prepared. It is found that the GnP is well aligned within the hybrid paper, and a higher degree of alignment is induced by the hot-pressing process. The mechanical properties of the resulting papers increased with increasing content of CNC. The hot-pressed 25 wt% CNC hybrid paper showed the best mechanical properties among all the papers studied and improved the tensile strength by 33% and the modulus by 57% compared to neat GnP paper. Both the highest in-plane and though-plane thermal conductivity of 41 W/m K and 1.2 W/m K were measured respectively for the hot-pressed 15 wt% CNC hybrid paper. The electrical conductivity decreased continuously with increasing content of CNC but the thin film was still conductive at the highest CNC content in this study. The low-cost, environmental-friendly, thermally and electrically conductive flexible GnP/CNC hybrid papers have a set of properties making them suitable for many potential applications.