Development of Nanocomposites from Bacterial Cellulose and Poly(vinyl Alcohol) using Casting-drying Method

Nanocomposites of bacterial cellulose (BC) and poly(vinyl alcohol) (PVA) were prepared by cast-drying method as an easy way in producing nanocomposite films and to expand the use of BC. The contribution of PVA in nanocomposites was evaluated by measurement of cross-sectional surface, moisture uptake and mechanical properties. Morphological analysis shows that PVA covered a number of cellulosic fibres and formed denser material as a function of PVA addition. Based on the tensile test, the addition of PVA causes a very slight reduction compared with bacterial cellulose itself. The BC/PVA nanocomposites still have similar stiffness to BC with elongation at break less than 5%, while PVA film shows ductile properties with elongation at break more than 80%. On the other hand, the presence of BC fibres in the PVA matrix enhanced the tensile strength and the elastic modulus of pure PVA about two to three times, but it decreased the toughness of pure PVA. The highest tensile strength and elastic modulus of the nanocomposites are 164 MPa and 7.4 GPa, respectively at BC concentration of 64%. Increasing BC concentration is proportional to reducing moisture uptake of BC/PVA nanocomposites indicating that the existence of BC fibres inhibits moisture absorption.     

Synthesis of regenerated bacterial cellulose-zinc oxide nanocomposite films for biomedical applications

Regenerated bacterial cellulose (RBC) composites with zinc-oxide nanoparticles (ZnO) were prepared using a new strategy for enhanced biomedical applications of BC. Powdered BC was dissolved in N-methylmorpholine-N-oxide, and different concentrations of ZnO nanoparticles were mixed into the BC solution. RBC, RBC-ZnO1 (1 % ZnO) and ZnO-RBC2 (2 % ZnO) nanocomposite films were prepared by casting the solutions through an applicator. FE-SEM images confirmed the structural features and impregnation of the RBC films by nanoparticles. XRD analysis indicated the presence of specific peaks for RBC and ZnO in the composites. The RBC nanocomposites were found to have greatly enhanced thermal, mechanical and biological properties. Specifically, the degradation temperatures were improved from 334 °C for RBC to 339 and 344 °C for RBC-ZnO1 and RBC-ZnO2, respectively. The mechanical strength and Young’s modulus of the composites were also higher than those of pure RBC. The greatly improved antibacterial properties of the RBC-ZnO nanocomposites are the most striking feature of the present study. The bacterial growth inhibition measured for the RBC was zero, but reached up to 34 and 41 mm for RBC-ZnO1 and RBC-ZnO2, respectively. In addition to their antibacterial properties, the RBC-ZnO nanocomposites were found to be nontoxic and biocompatible with impressive cell adhesion capabilities. These RBC-ZnO nanocomposites can be used for different biomedical applications and have the potential for use in bioelectroanalysis.     

Compatibilized polyethylene—thermally reduced graphene nanocomposites: Interfacial interactions and hyperspectral mapping for component distribution

Ethylene-co-acrylic acid (EAA) and ethylene-co-methacrylic acid ionomer (EMAZ) copolymers were used as compatibilizers for polyethylene-graphene nanocomposites generated by melt mixing. At 5 wt% content, the EAA compatibilizer enhanced the tensile modulus of PE by 40 % and shear modulus by >300 % (1 rad/s) due to efficient dispersion of graphene platelets which helped in effective stress transfer. These also resulted in enhanced thermal stability for PE-EAA-G nanocomposite as compared to nanocomposite with EMAZ. The properties of the nanocomposites were significantly better than the conventional nanocomposites based on layered silicate materials. Mapping of the component distribution in the nanocomposites was demonstrated by using hyperspectral imaging. The nanocomposite with EAA exhibited higher extent of spectral signal mixing due to better mixing of filler and compatibilizer in PE matrix. On the other hand, nanocomposite with EMAZ had no spectral mixing as the components did not mix optimally with each other. The DSC thermogram for this nanocomposite also exhibited a small shoulder at low temperature probably due to immiscibility of the compatibilizer with the matrix polymer. The hyperspectral imaging and mapping was thus demonstrated to be a useful method for determination of component distribution in complex nanocomposite systems.     

Recyclable and transparent bacterial cellulose/hemiaminal dynamic covalent network polymer nanocomposite films

Recyclable and transparent nanocomposite films based on bacterial cellulose (BC) and hemiaminal dynamic covalent network polymer (HDCN) have been synthesized by in situ polymerization of 4,4′-diaminodiphenyl ether (ODA) with paraformaldehyde. Transparency and structural and mechanical properties of such nanocomposite films are investigated. It was found that BC/HDCN nanocomposite films exhibits a high optical transparency (86 % at 550 nm). Scanning electron microscopy reveals excellent compatibility of the reinforcement of BC nanofibers and HDCN matrix, which leads to the improvement of 20 and 200 % in tensile strength and storage modulus, respectively, as compared to neat HDCN films. BC hydrogels are readily recoverable from nanocomposite films by the sulphuric acid treatment and ODA monomer is deposited and also recycled.     

Characterization of kaolinite/emulsion-polymerization styrene butadiene rubber (ESBR) nanocomposite prepared by latex blending method: Dynamic mechanic properties and mechanism

The latex blending method was chosen to prepare Kaolinite/emulsion-polymerization styrene butadiene rubber (ESBR) nanocomposite to improve the interaction between filler particles and rubber matrix chains. The influences of kaolinite particles size, filler contents, and flocculants types on dynamic mechanical properties and the relative reinforcement mechanism of the prepared composite were systematic investigated and proposed. The transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the kaolinite particles were finely dispersed into the rubber matrix and arranged in parallel orientation. The prepared nanocomposites by latex blending exhibited improved crosslinking characteristic and dynamic mechanical parameters. The KAl (SO₄)₂ flocculant presented obvious modification in dynamic properties and crosslinking characteristic. Both the decrease in kaolinite particle size and the increase in kaolinite content can greatly improve the storage modulus and reinforcing effect of kaolinite/ESBR nanocomposites. The dynamic reinforcement mechanism of kaolinite can be explained by filler network including a certain thickness of rubber shell on the surface of kaolinite lamellar structure and the aggregations network between kaolinite particles The optimum way to balance the dynamic properties of rubber nanocomposites at different temperatures is to reduce the surface difference between kaolinite and rubber matrix and the degree of filler-filler networking on the basis of kaolinite with nanoscale (nanometer effect).     

Effect of poly(amid–imide)/Al2O3 hybrid with various ratios on the physicochemical properties of poly(vinyl alcohol) nanocomposites films

To study the effect of the various ratios of poly(amide–imide)/Al₂O₃ nanocomposites (PANC)s on the mechanical and thermal properties of nanocomposites films, poly(vinyl alcohol) (PVA)/PANCs based on various ratios of 2, 4, and 6 wt% were prepared and characterized. In the first step, the surface of alumina nanoparticles was treated with 15 wt% of biosafe diacid and consequently, about 10 wt% of these modified nanoparticles were loaded into the poly(amide–imide) matrix. Then, various contents of the obtained PANCs were incorporated into a PVA solution using a sonochemical treatment. The effects of PANC on the structure and morphology of PVA matrix were studied using powder X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, atomic force microscopy (AFM), and thermal gravimetric analysis (TGA). The results show that the tensile strength and decomposition temperature were improved as the portion of PANC into PVA matrix are increased from 2 to 6 wt%. Also, AFM pictures of the fracture surfaces of PVA/PANCs showed a significantly rougher surface than the neat PVA.     

Dynamic electrical thermal analysis on zinc oxide/epoxy resin nanodielectrics

The dielectric response of ZnO/epoxy resin nanocomposites was studied by means of dynamic electrical thermal analysis in the frequency range of 10^?1 to 10⁷ Hz, and over the temperature range of 30–160 °C, varying the content of the reinforcing phase. Scanning electron microscopy pictures were used for assessing the composites morphology and for examining the particles’ dispersion. The thermal properties of nanocomposites were examined by differential scanning calorimetry in the temperature range of 0–170 °C. Dielectric data were analyzed via dielectric permittivity and electric modulus formalisms. Recorded relaxation phenomena include contributions from both the polymeric matrix and the presence of the reinforcing phase. Processes related to the polymer matrix are attributed to the glass to rubber transition (α-relaxation) of the epoxy resin and local motions of polar side groups of the main polymer chain (β-relaxation). Finally, the slower process appearing at low frequencies and high temperatures, originates from interfacial phenomena due to the accumulation of unbounded charges at the system’s interface.     

Surface modified graphene oxide/poly(vinyl alcohol) composite for enhanced hydrogen gas barrier film

A series of novel polyethyleneimine (PEI) modified graphene oxide (PEI-mGO) filled poly(vinyl alcohol) (PVA) nanocomposite (PEI-mGO/PVA) films were prepared by solution-casing for hydrogen gas barrier applications. Hydrophilic PEI was used to simultaneously reduce and modify graphene oxide sheets, thereby facilitating a homogeneous dispersion of PEI-mGO in the PVA matrix. The effects of PEI-mGO on the morphology and properties of the nanocomposite films were examined by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and field emission scanning electron microscopy. Analogous GO/PVA composites were also prepared and characterized for comparative purposes. The PEI-mGO/PVA nanocomposites showed higher thermal and mechanical stability as well as remarkable improvement in hydrogen gas barrier properties compared to the PVA film; specifically, the PEI-mGO/PVA film having 3.0 wt% of PEI-mGO content exhibited almost 95% decrease in GTR and permeability values compared to PVA film.     

Click coupled graphene for fabrication of high‐performance polymer nanocomposites

An effective technique of using click coupled graphene to obtain high‐performance polymer nanocomposites is presented. Poly(ε‐caprolactone) (PCL)‐click coupled graphene sheet (GS) reinforcing fillers are synthesized by the covalent functionalization of graphene oxide with PCL, and subsequently the PCL‐GS as a reinforcing filler was incorporated into a shape memory polyurethane matrix by solution casting. The PCL‐click coupled GS has shown excellent interaction with the polyurethane matrix, and as a consequence, the mechanical properties, thermal stability, thermal conductivity, and thermo‐responsive shape memory properties of the resulting nanocomposite films could be enhanced remarkably. In particular, for polyurethane nanocomposites incorporated with 2% PCL‐GS, the breaking stress, Young's modulus, elongation‐at‐break, and thermal stability have been improved by 109%, 158%, 28%, and 71 °C, respectively. This click coupling protocol offers the possibility to fully combine the extraordinary performance of GSs with the properties of polyurethane. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Cellulose Nanocrystals (CNCs) Induced Crystallization of Polyvinyl Alcohol (PVA) Super Performing Nanocomposite Films

This study is aimed to explore the properties of cellulose nanocrystals (CNC)/polyvinyl alcohol (PVA) composite films with and without 1,2,3,4‐butane tetracarboxylic acid (BTCA), a nontoxic crosslinker. CNC and CNC‐PVA nanocomposite films are prepared using solution‐casting technique. Differential scanning calorimetry (DSC) analyses show that crosslinking increased the glass transition temperature but reduced the melting temperature and crystallinity. Furthermore, high CNC concentrations in the PVA matrix interfere with PVA crystallinity, whereas in specific ratio between CNC and PVA, two different crystalline structures are observed within the PVA matrix. Film surfaces and fracture topographies characterized using scanning electron microscope indicate that at certain CNC‐PVA ratios, micron‐sized needle‐like crystals have formed. These crystalline structures correlate with the remarkable improvement in mechanical properties of the CNC‐PVA nanocomposite films, that is, enhanced tensile strain and toughness to 570% and 202 MJ m^?3, respectively, as compared to pristine PVA. BTCA enhances the tensile strain, ultimate tensile stress, toughness, and modulus of CNC films compared to pristine CNC films. Water absorption of crosslinked CNC and CNC‐PVA nanocomposite films is significantly reduced, while film transparency is significantly improved as a function of PVA and crosslinker content. The presented results indicate that CNC‐PVA nanocomposite films may find applications in packaging, and though materials applications.     

Thermal decomposition of metal nitrates

The paper presents a study regarding the preparation of 40 %M^IIFe₂O₄/60 %SiO₂ nanocomposites (M = Ni, Zn, Cu) by thermal decomposition of metal nitrates—poly(vinyl alcohol)–tetraethyl orthosilicate gels. Thermal analysis and FT-IR spectroscopy have evidenced that a redox reaction takes place between PVA and NO ₃ ^? ions in the pores of the formed hybrid gels. The result of this redox reaction is the formation of carboxylate-type coordination compounds that have the role of a precursor of the ferrite nanoparticles. By thermal decomposition of these precursors inside the silica matrix, the corresponding MFe₂O₄/SiO₂ nanocomposites are obtained starting with 600 °C, as resulting from XRD analysis. Elemental maps of the corresponding involved elements M (Ni, Zn, Cu), Fe, and Si have confirmed the homogenous distribution of the ferrite nanoparticles within the silica matrix. TEM images have shown that the nanocomposites were obtained as fine nanoparticles, with diameter up to 20 nm. All nanocomposites 40 %M^IIFe₂O₄/60 %SiO₂ obtained at 1000 °C presented magnetic properties characteristic to this type of nanocomposite.     

Facile synthesis of LDH nanoplates as reinforcing agents in PVA nanocomposites

In the present study, layered double hydroxide (LDH) nanoplates with high crystallinity and uniform size were facilely synthesized to act as reinforcing agents in polymer materials. The structure of the synthesized LDH nanoplates was characterized by X‐ray diffraction, Fourier transform infrared spectra, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy measurements. Subsequently, the LDH nanoplates were incorporated into poly(vinyl alcohol) (PVA) matrix as reinforcing agents based on a solution casting method. The LDH nanoplates were well dispersed in PVA matrix and formed strong interfacial interactions with PVA chains, leading to remarkable improvements of thermal stability, flame retardancy, and mechanical properties. With the incorporation of 1 wt% LDH nanoplates into PVA, the T_onset and T_50% increased by 11°C and 57°C, respectively. Moreover, the presence of LDH nanoplates decreases the decomposition rates of PVA and increases the amount of char residues. Compared with pure PVA, the peak heat release rate value of the PVA/5 wt% LDH nanocomposites is decreased by 52%. The tensile strength and the elongation at break increased by 71% and 187%, respectively, when incorporating with 3 wt% LDH nanoplates. Copyright © 2016 John Wiley & Sons, Ltd.     

Study of a highly durable low-humidification membrane electrode assembly using crosslinked polyvinyl alcohol for polymer electrolyte membrane fuel cells

A low-humidification membrane electrode assembly (MEA) for polymer electrolyte membrane fuel cells (PEMFCs) is prepared by adding the hydrophilic polymer: polyvinyl alcohol (PVA) to the anode catalyst layer. Glutaraldehyde (GA) is employed as a crosslinking agent for PVA to prevent washing from the anode during cell operation. This is confirmed by an immersion test in deionized water for 2 h. A single cell test is conducted at 80 °C, ambient pressure, and 50 % relative humidity. Although MEA containing 1 wt% non-crosslinked PVA shows the best initial performance (788 mA cm^?2 at 0.6 V), a considerable performance decrease of 41 % is observed following a 100-h durability test. However, MEA containing 5 wt% crosslinked PVA demonstrates enhanced durability, with little performance decline after 100 h of constant current operation. This strongly suggests that crosslinked PVA plays a crucial role in a low-humidification MEA at low humidity levels.     

Influence of the nanoparticle type on the thermal decomposition of the green starch/poly(vinyl alcohol)/montmorillonite nanocomposites

In this study, some aspects concerning the thermal decomposition of starch/poly(vinyl alcohol) (PVA)/montmorillonite (MMT) nanocomposites with 2 wt% nanoclay, prepared by melt mixing method, were studied. For these loadings, the inorganic fillers are well dispersed through the PVA/starch matrix, i.e., the nanocomposites formed are mostly intercalated hybrids. The aim of this article is to establish the effect of the nanofiller nature on the thermal decomposition of the starch/PVA/MMT nanocomposites. The thermal behavior of the 50 wt% starch/50 wt% PVA blend and its nanocomposites with 2 wt% nanoclay has been investigated by thermogravimetric analysis coupled with Fourier transform-infrared spectroscopy and mass spectrometry (MS). The volatile compounds resulting during the thermal degradation were studied by in situ vapor phase FT-IR spectroscopy and MS technique under a controlled temperature/time program. Apart from the identification of the volatile compounds, some conclusions on the nanoclays effect on the degradation mechanism and formation of the volatile compounds in accordance with the previously developed general mechanisms for PVA and starch degradation have been formulated. The clay–PVA/starch nanocomposites show completely different degradation product distribution patterns, which may be attributed to the presence of the head-to-head structures and Si–O–C linkages formed between clay and blend components.     

Nanocrystalline cellulose acetate (NCCA)/graphene oxide (GO) nanocomposites with enhanced mechanical properties and barrier against water vapor

Highly flexible nanocomposite films of nanocrystalline cellulose acetate (NCCA) and graphene oxide (GO) were synthesized by combining NCCA and GO sheets in a well-controlled manner. By adjusting the GO content, various NCCA/GO nanocomposites with 0.3–1 wt% GO were obtained. Films of these nanocomposites were prepared using the solvent casting method. Microscopic and X-ray diffraction (XRD) measurements demonstrated that the GO nanosheets were uniformly dispersed in the NCCA matrix. Mechanical properties of the composite films were also studied. The best GO composition of the samples tested was 0.8 wt%, giving tensile strength of 157.49 MPa, which represents a 61.92 % enhancement compared with NCCA. On the other hand, the composite films showed improved barrier properties against water vapor. This simple process for preparation of NCCA/GO films is attractive for potential development of high-performance films for electrical and electrochemical applications.     

Bacterial cellulose/gelatin composites: in situ preparation and glutaraldehyde treatment

Bacterial cellulose (BC)/GEL composites were prepared in situ by adding gelatin into BC-producing culture medium. The addition of gelatin interfered with the formation of the BC pellicle structure and thus made the BC yield and growth rate quite different from that of pure BC. Scanning electron microscope images showed that the width of cellulose ribbons became narrower than that of pure BC and the gelatin filled in the pores of BC to form a dense structure. The addition level of gelatin significantly influences the yield of BC/GEL composites. An optimum value of 0.5 wt/v% gelatin was attained, with which the highest yield of 0.0541 g/100 mL was achieved. Under this condition, the weight percentage of gelatin in BC/GEL composite was 65 wt%. BC/GEL composites were treated with glutaraldehyde to crosslink BC fibrils and gelatin. The crosslinking degree, determined by the concentration of glutaraldehyde and crosslinking time, could affect the swelling behavior, thermal stability and mechanical properties of composites. With increasing of the crosslinking degree, the crystallinity index and swelling behavior of the composites decreased. The increase in the crosslinking degree also descreased the composite’s strain at break in elongation but increased the compressive and tensile strength. Covalent bonding between BC and gelatin provides good strength retention to the glutaraldehyde-treated composites with a high crosslinking degree. Considering the cytocompatibility and properties of composites, the most appropriate concentration of glutaraldehyde and crosslinking time were 1.0 wt/v% and 24 h, respectively.     

Topochemical acetylation of cellulose nanopaper structures for biocomposites: mechanisms for reduced water vapour sorption

Moisture sorption decreases dimensional stability and mechanical properties of polymer matrix biocomposites based on plant fibers. Cellulose nanofiber reinforcement may offer advantages in this respect. Here, wood-based nanofibrillated cellulose (NFC) and bacterial cellulose (BC) nanopaper structures, with different specific surface area (SSA), ranging from 0.03 to 173.3 m²/g, were topochemically acetylated and characterized by ATR-FTIR, XRD, solid-state CP/MAS ¹³C-NMR and moisture sorption studies. Polymer matrix nanocomposites based on NFC were also prepared as demonstrators. The surface degree of substitution (surface-DS) of the acetylated cellulose nanofibers is a key parameter, which increased with increasing SSA. Successful topochemical acetylation was confirmed and significantly reduced the moisture sorption in nanopaper structures, especially at RH = 53 %. BC nanopaper sorbed less moisture than the NFC counterpart, and mechanisms are discussed. Topochemical NFC nanopaper acetylation can be used to prepare moisture-stable nanocellulose biocomposites.     

Study on the nonisothermal crystallization behavior of poly(vinyl alcohol)/attapulgite nanocomposites by DSC analysis

Attapulgite (AT)‐reinforced poly(vinyl alcohol) (PVA) nanocomposite films were prepared by solution‐casting technique. The nonisothermal crystallization behaviors of PVA bulk and PVA/AT nanocomposites have been investigated by differential scanning calorimetry (DSC). It has been found that the uniformly dispersed AT nanorods in the matrix have great influence on the glass transition temperature and crystallization behavior of PVA matrix. The Jeziorny method has been employed to analyze the DSC data. The results show that Jeziorny method could describe this system very well. Comparing with the PVA bulk, PVA/AT nanocomposites have higher crystallinity X_t, shorter semicrystallization time t_1/2, and higher crystallization rate constant Z_c. It can be concluded that AT can be used as an effective nucleating agent and has effects on the growth of crystallites in the crystallization process of PVA matrix. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 534–540, 2006     

聚乙烯醇/氟基蒙脱土纳米复合材料的合成及性能研究

采用水热方法,在493 K条件下反应72小时,合成了氟基蒙脱土(F-MMT),在这种F-MMT中,硅酸盐结构中的一些OH-被F-取代。采用溶液插层方法,制备了聚乙烯醇/F-MMT纳米复合材料(PVA/F-MMT)。采用X 射线衍射、扫描电镜和透射电镜对F-MMT 和 PVA/F-MMT纳米复合材料进行了表征;结果表明,片状结构的F-MMT均匀分散于PVA中,形成了层离结构的纳米复合材料。热重分析、力学性能和紫外可见光谱的测试结果表明,在没有牺牲光学性能情况下,PVA/F-MMT纳米复合材料的热稳定性和力学性能都得到了提高。力学和热学性能的提高归功于F-MMT均匀而好的分散于聚合物基体中,以及PVA中的 OH- 和F-MMT 中F-之间强的氢键作用。     

Control of properties of nanocomposites bio-based collagen and cellulose nanocrystals

Collagen is an important biomaterial because it has many applications in the biomedical sector. However, the high hydrophilicity of collagen (COL) leads to easy swelling. Thus, controlling this property is highly desirable. In this work, cellulose nanocrystals (CNCs) dispersed in glycerol (GLI) were incorporated in the matrix collagen to tailor the hydrophilicity and mechanical properties. Study of the hydrophilicity of the bio-based nanocomposite was evaluated by contact angle measurement and thermogravimetric analysis. Mechanical analyses showed that CNCs are excellent reinforcing fillers to the collagen matrix. Synchrotron small-angle X-ray scattering was employed to investigate the nanostructures of COL/GLI/CNC nanocomposites and CNC water dispersion. CNC in concentrations up to 1 wt% presents an intermediate shape between a rod and a plane with a 9.34-nm radius of gyration (R _g). Bio-based nanocomposites present two different structural levels with two types of particles with very different R _gs. At the intermediate power-law regime, a large-scale mass fractal aggregate is observed. In the high-power-law regime, it is observed scattering from primary particles smaller than 1 nm. As the CNC concentration increases, the original particle distorts from a rod to a plate. The cytotoxicity assay indicates that the collagen and nanocomposites did not affect the cell viability of rat calvarial cells in vitro.