Crosslinked poly(vinyl alcohol) composite films with cellulose nanocrystals: Mechanical and thermal properties

In this work, poly(vinyl alcohol) (PVA) and cellulose nanocrystals (CNCs) were crosslinked using sodium tetraborate decahydrate (borax) to improve the mechanical and thermal properties of the neat PVA. The results showed that the CNCs affected the crystallization behavior of the crosslinked PVA. The crystallization temperature of the crosslinked PVA with CNCs increased considerably from ～152 to ～187 °C. The continuous improvement of the thermal stability was observed with the increasing content of CNCs in the crosslinked PVA films. Additionally, the strong interaction between the CNCs and PVA was theoretically estimated from the Young's modulus values of the composites. Thermodynamic mechanical testing revealed that the crosslinked PVA composite films with CNCs could bear higher loads at high temperature compared to the films without the CNCs. At 60 °C, 2.7 GPa was reported for the storage modulus of the crosslinked composites with 3 wt % of CNCs, twice as high as that for the crosslinked films without CNCs. Moreover, creep results were improved when CNCs were added in the crosslinked nanocomposites. The materials prepared in this work could broaden the opportunities for applications in a wide range of temperatures. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45710.     

Reinforcement of polypropylene by cellulose microfibers modified with polydopamine and octadecylamine

Cellulose microfibers (CMFs) having surfaces modified with polydopamine (PDPA) and octadecylamine (ODA) were prepared, and their reinforcing abilities for polypropylene (PP) were investigated. The PDPA coating was made via self-polymerization of dopamine (P-CMF), and subsequent alkylation was conducted by the reaction with ODA (OP-CMF). The modified CMFs exhibited improved dispersibility in the PP matrix due to the reduced hydrophilicity. The OP-CMF/PP composite prepared by batch mixing had a higher tensile modulus compared to that for the pure PP and composites with unmodified CMFs. However, excess alkylation lowered the tensile modulus, and the presence of an optimal degree of alkylation was demonstrated. The CMF/PP-IM composites fabricated by injection molding exhibited improved tensile properties compared to those prepared by batch mixing. Both the tensile modulus and yield stress were increased by increasing the CMF content and improved by the surface modification of the CMFs.     

Preparation and characteristic of a sodium alginate/carboxymethylated bacterial cellulose composite with a crosslinking semi‐interpenetrating network

A novel ionic crosslinking sodium alginate (SA)/carboxymethylated bacterial cellulose (CM‐BC) composite with a semi‐interpenetrating polymer network (semi‐IPN) structure was developed in this study. The composite was prepared through the blending of an SA gel with CM‐BC then crosslinking by Ca²⁺ followed by a freeze‐drying process. Scanning electron microscopy showed the composite matrix organized in a three‐dimensional network of CM‐BC interpenetrated against SA molecular chains with a quantity of calcium alginate microspheres upon the surface. The swelling ratios of the composite were enhanced by 183, 198, and 212% with the supplementation of CM‐BC weight fractions of 25, 50, and 75%, respectively; the swelling ratios changed with changing pH. The tensile modulus, tensile strength, and elongation at break of SA were enhanced by 165, 152, and 188%, respectively, with the addition of 50 wt % CM‐BC. This study demonstrated that the semi‐IPN structure dramatically changed the swelling and mechanical properties of the composite, and the semi‐IPN will be a promising candidate for biomedical applications such as wound dressings and skin tissue engineering. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39848.     

Construction of thermoplastic cellulose esters matrix composites with enhanced flame retardancy and mechanical properties by embedding hydrophobic magnesium hydroxide

Biomass-based composites with renewability and biodegradability have attracted extensive researches, but their applications are hindered by poor mechanical properties and flame retardancy. Cellulose ester matrix composites (CEMC), a kind of biomass-based composites, were prepared with inorganic crystals as flame retardant and reinforcement. Cellulose acetate oleate (CAO) prepared by mechanical activation-assisted solid-phase reaction was used as thermoplastic matrix. Hydrophobic oleate-magnesium hydroxide (O-MH), which was surface-modified with oleic acid, was embedded into CAO to prepare O-MH/CAO composites by hot pressing. The introduction of oleoyl contributed to favorable thermoplasticity of cellulose ester, resulting in enhanced thermal stability and mechanical properties of CEMC. The uniform dispersion of O-MH in the CAO matrix via metal–organic coordination increased the mechanical properties and flame retardancy of O-MH/CAO composites, ascribing to the toughening effect and combustion inhibition effect induced by O-MH. This study provides a feasible technology for fabricating the CEMC with outstanding thermal stability and mechanical properties.     

Silicified microcrystalline cellulose based pellets and their physicochemical properties

Silicified microcrystalline cellulose (SMCC), Prosolv SMCC 50 was used as spheronization aid to manufacture pellets by extrusion and spheronization. Different ratios of SMCC to lactose were used to manufacture pellets using appropriate levels of water as liquid binder. Avicel PH101 based pellets were also manufactured for comparison of their physical properties. The ratio of liquid binder to spheronization aid was critical to produce pellets of desired size and shape. Extrudates composed of 20% aid could withstand only smaller spheronization force in order to be shaped into pellets. The successful products fulfilled the quality of pellets such as narrow size distribution and spherical in shape. The highest surface tensile strength was observed in pellets with equal ratio of lactose to SMCC while pellets having 20% aid disintegrated rapidly within 15 min. Furthermore, Prosolv SMCC 50 based pellets possessed a stronger surface tensile strength when compared with Avicel PH101 based pellets. In conclusion, Prosolv SMCC 50 has showed to be a good spheronization aid for extrusion and spheronization when used in the range of 20 to 80% content. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43829.     

Preparation and characterization of antimicrobial films based on nanocrystalline cellulose

Nanocrystalline cellulose (NCC) has great potential in applications in medical and food packaging due to its abundance, high specific surface area, biodegradability, biocompatibility, and reproducibility. N-Halamine is one of the most effective antibacterial agents, with broad-spectrum efficacy against microorganisms, good stability, and reproducibility. Due to the nanosize effect and high specific surface area of NCC, N-halamine-modified NCC is potentially an excellent biocidal compound. In this paper, an N-halamine precursor 1-hydroxymethyl-5,5-dimethylhydantoin (HDH) was used to modify NCC with cyanuric chloride (cych) as the bonding agent. After chlorination, the produced NCC-cych-HDH-Cl became antibacterial. The synthesized NCC-cych-HDH-Cl was added to a chitosan (CS) and polyvinyl alcohol (PVA) solution to prepare antibacterial films. The optimum mixing ratio of PVA and CS in the PVA/CS films and concentration of NCC-cych-HDH-Cl were investigated. The surface morphologies and mechanical properties of the antibacterial films were characterized with scanning electron microscopy, transmission electron microscopy, and mechanical strength tests. The results indicated that the film with 90/10 PVA/CS and 7.0% loading of NCC-cych-HDH-Cl exhibited excellent tensile strength. The antibacterial film with 5.91 × 10¹⁷ atoms/cm² of active chlorine displayed an excellent antibacterial property against Staphylococcus aureus (ATCC 6538) and Escherichia coli O157:H7 (ATCC 43895). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47101.     

Aramid nanofiber reinforced nitrile rubber assisted by cellulose nanocrystals

A fiber-reinforced rubber composite was prepared by mixing aramid nanofibers (ANF) suspension and nitrile rubber (NBR) latex. The effects of ANF content and corresponding surface modification on the microstructure, vulcanization performance, processing and mechanical properties of composite materials, were systematically investigated. We found that, compared with commonly used short-cut aramid fibers, ANF fillers tend to form a stronger filling network within NBR matrix, resulting in a pronounced Payne effect. By improving the interfacial adhesion via dopamine (DA) coating onto ANF surface, the tensile strength can be further enhanced as expected. Besides, to eliminate the detriment of mechanical performance due to residual sodium polyacrylate in the course of flocculation, cellulose nanocrystal (CNC) was adopted to serve as a thickener during solution mixing. The incorporation of CNC can significantly improve the mechanical properties, which identifies a synergistic reinforcement effect arising from the cooperation of two types of fillers.     

Melt processing of nanocomposites of cellulose nanocrystals with biobased thermoplastic polyurethane

Nanocomposites of thermoplastic polyurethane (TPU) with cellulose nanocrystals (CNC) without and with surface treatment are obtained by melt processing. Nanocomposites are obtained with nanofiller weight content near of the theoretical percolation threshold (3.9 wt%). Visual observation of CNC agglomerates is sufficient to prove the inefficiency of the mixing in systems with untreated CNC. The crystallization kinetics of the TPU changes with the addition of CNC and this is confirmed by differential scanning calorimetry analysis. Thermogravimetric analysis prove that the addition of CNC increases the thermal stability of the TPU. From the rheological analysis it is possible to verify the absence of percolation and an intermediate state of sol–gel transition in the nanocomposites. CNC/TPU nanocomposites with 5 wt% of treated CNC present better mechanical performance than de neat TPU and the other processed nanocomposites and display around 130% increase in Young's modulus while retaining significant values of toughness, tensile strength and elongation at break.     

Τhe effect of wood‐fiber type on the thermomechanical performance of a biodegradable polymer matrix

The effect of type and content of wood fibers on the thermal, mechanical and rheological behavior of the commercial biodegradable polyester product, Ecovio® (BASF) is analytically studied. Ecovio® is basically a blend of poly(butylene adipate‐terephthalate) copolyester (Ecoflex®, BASF) and polylactide. Three different types of wood fibers, based either on raw cellulose (Arbocel) or selected conifers (Lignocel), with varying fiber size at various weight fractions were used for this purpose. The role of these fibers on the thermomechanical performance of Ecovio® was investigated in terms of several experimental techniques including scanning electron microscopy, differential scanning calorimetry, dynamic mechanical analysis, creep, tensile testing, and water uptake at room temperature. At the low wood fiber content (20 wt %), Lignocel composite's properties are predominant compared with the Arbocel composites. It has been found, that at this wood content, an efficient compatibility between matrix and fibers is achieved, leading to superior reinforcement. This trend is completely reversed at higher filler loading, probably due to the poor interfacial adhesion between the matrix and Lignocel occurring at 30 wt %. This behavior was supported by all the experimental methods employed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42185.     

Comparison of the performance of copper oxide and yttrium oxide nanoparticle based hydroxylethyl cellulose electrolytes for supercapacitors

Biodegradable solid polymer electrolyte (SPE) systems composed of hydroxylethyl cellulose blended with copper(II) oxide (CuO) and yttrium(III) oxide (Y₂O₃) nanoparticles as fillers, magnesium trifluoromethane sulfonate salt, and 1‐ethyl‐3‐methylimidazolium trifluoromethane sulfonate ionic liquid were prepared, and the effects of the incorporation of CuO and Y₂O₃ nanoparticles on the performance of the SPEs for electric double‐layer capacitors (EDLCs) were compared. The X‐ray diffraction results reveal that the crystallinity of the SPE complex decreased upon inclusion of the Y₂O₃ nanoparticles compared to CuO nanoparticles; this led to a higher ionic conductivity of the Y₂O₃‐based SPE [(3.08 ± 0.01) × 10^?4 S/cm] as compared to CuO [(2.03 ± 0.01) × 10^?4 S/cm]. The EDLC performances demonstrated that the cell based on CuO nanoparticles had superior performance in terms of the specific capacitance, energy, and power density compared to the Y₂O₃‐nanoparticle‐based cell. However, Y₂O₃‐nanoparticle‐based cell displayed a high cyclic retention (91.32%) compared to the CuO‐nanoparticle‐based cell (80.46%) after 3000 charge–discharge cycles. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44636.     

Regenerated cellulose/layered double hydroxide nanocomposite films with improved mechanical property

Construction of environment-friendly biomass-based nanocomposites with high performance is in great demand for developing of a sustainable low-carbon society. Here, transparent and flexible regenerated cellulose (RC)/layered double hydroxide (LDH) nanocomposite films were prepared from aqueous NaOH/urea solutions. The obtained nanocomposite films were characterized using AFM, SEM, FTIR, XRD, tensile testing, water contact angle, and thermogravimetric analysis. The results show that LDH nanoplatelets were individually dispersed with a thickness of 1 nm and surface diameter of 100 nm after ultrasonic treatment. Strong interaction existed between LDH nanoplatelets and cellulose molecules, leading to the improved thermal stability and mechanical strength of RC together with the original good properties of LDH. In particular, the nanocomposite films with 10 wt% LDH showed a 135% and 234% increase in the tensile strength and Young's modulus than those of the neat RC film. Meanwhile, the nanocomposite films exhibited high transparency. Therefore, these RC/LDH nanocomposites are promising in the fields of high-performance packaging materials, flexible display panels, and high-temperature dielectric materials.     

The effects on mechanical properties and crystallization of poly (l‐lactic acid) reinforced by cellulosic fibers with different scales

Bacterial cellulose (BC), microcrystalline cellulose (MCC), and bamboo cellulosic fibers (BCFs) were used to reinforce poly(l ‐lactic acid) (PLLA) based bio‐composites. The mechanical properties and crystallization of the composites were studied through mechanical testing, differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, and polarizing microscope. The incorporation of all three kinds of cellulose increased the stiffness of the composites compared to pure PLLA. The reinforcing effect of the MCC in the composites is most significant. The Young's modulus and impact toughness of the MCC/PLLA composites were increased by 44.4% and 58.8%, respectively. The tensile strength of the MCC/PLLA composites was increased to 71 MPa from 61 MPa of PLLA. However, the tensile strength of the composites reinforced with BCF or BC was lower than PLLA. The three kinds of cellulosic fibers improved the crystallization of PLLA. The BC with smallest size provided the composites with smallest grain and highest crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41077.     

Preparation of SiC whisker and application in reinforce of polystyrene resin composite materials

A simple approach to fabricate silicon carbide (SiC) whisker is reported via using cellulose nanocrystal (CNC) as templates. The CNC with a length between 2 and 4 μm and a width about 40 nm is prepared by hydrolysis of microcrystalline cellulose (MCC) in strong sulfuric acid condition. The sol–gel reaction of tetraethyl orthosilicate (TEOS) is employed to coat the CNC in the presence of acetic acid as acid catalyst. The SiC whisker is obtained by calcination of CNC / SiO₂ hybrid at 1200°C. The obtained SiC whisker is found to have uniform size and shape with a length of ca. 2–4 μm and a width of 40 ± 5 nm. XRD, SEM, TEM (HRTEM), SAED, EDX and FTIR are used to characterize the samples. The obtained SiC whisker is used in polystyrene (PS) resin toughened. And mechanical properties of SiC / PS composites are tested by tensile impact experiments. The test results show that the 5 wt. % SiC whisker particles can disperse homogeneously in the PS resins which use a silane coupling agent (KF9701) as compatibilizer. Our results also show that the SiC whisker is excellent reinforcing material, which the tensile strength of SiC / PS composites attains 110 MPa and the Izod notched impact strength attains 5.00 KJ / m². Comparing the pure PS resin, the tensile impact of SiC(5) / PS(94.5) / KF9701(0.5) composites can be increased by about 3 times and the Izod notched impact strength can be increased about 8 times. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polypropylene reinforced with nanocrystalline cellulose: Coupling agent optimization

Five different grades of maleic anhydride polypropylene (MAPP) having different molecular weight and acid value (AV) were used as coupler in PP‐nanocrystalline cellulose (NCC) composites. The main objective was to study the effect of MAPP structure (Mw, AV) and filler/coupler (F/C) ratio on mechanical properties in order to find optimum mechanical properties in tension, flexion, and impact. Results showed that both Mw and AV have direct effect on mechanical properties and a balance between both must be achieved to get the best performance. However, regardless of MAPP structure, optimum improvement was obtained for F/C = 7.5/1. Shear rheological data showed that at high MAPP content, MAPP acts as lubricant. DSC and AFM analysis showed small reduction in the size of PP crystals in the presence of NCC. Rheological data under large amplitude oscillatory shear showed that the nanocomposites used here are under percolation. Using these analyses, possible reinforcement mechanisms were investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42438.     

Preparation and morphological,thermal, and physicomechanical properties of polypropylene‐potato peel biocomposites

Potato peel powder (POPL), which is biodegradable, has been used as filler material in polypropylene (PP) matrix in varying concentration from 10 to 40% by weight to prepare biocomposites and investigated water absorption, physicomechanical and thermal properties. Scanning electron microscopy and X‐ray diffraction has been used for morphological characterization and crystallization studies. Flexural modulus of biocomposites increased by 40% compared with neat PP at 30% loading of POPL. Flexural strength also increased with increasing filler loading. Tensile strength of biocomposites has been observed to be comparable with neat PP up to 20% filler loading and increase in tensile modulus up to 40% was seen in biocomposites with 20% filler loading. Impact strength of biocomposites up to 20% filler loading was found to be at par with neat PP. Use of MA‐g‐PP compatibilizer in the biocomposites yielded better physico‐mechanical and thermal properties than biocomposites without compatibilizer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42445.     

Effects of oxidant and dopants on the properties of cellulose/PPy conductive composite hydrogels

Cellulose/Polypyrrole (PPy) composite hydrogels were prepared by in situ chemically oxidative polymerization of pyrrole in the cellulose matrix. Ferric chloride (FeCl₃) was used as an oxidant and four sulfonic compounds were used as dopants in order to investigate the effects on the properties of cellulose/PPy conductive composite hydrogels. The extent of polymerization of PPy was determined by the amount of the oxidant and the composite hydrogels with oxidant at 0.3M?0.5M exhibited the higher conductivities for the intrachain and interchain conductivities of conductive polymers; the fracture stress of the composite hydrogels could be up to 26.25 MPa with a strain of 86.8% when the oxidant was at 0.5M. Doping is an efficient way to improve the conductivity of the composite hydrogels and four kinds of dopant were compared in this work. Long alkane chain and side group in dopants can increase the steric hindrance of PPy polymerization which resulted in the lower conductivity of the composite hydrogels compared to dopants with smaller steric hindrance. The conductivity of the composite hydrogel firstly increased and then decreased with the concentration of dopants from 0.1M to 1.0M in this work. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43759.     

Transparent,flexible, and high‐strength regenerated cellulose/saponite nanocomposite films with high gas barrier properties

Regenerated cellulose‐saponite nanocomposite films were prepared from LiOH/urea solutions, and exhibited high optical transparency and flexibility. The saponite platelets formed intercalated nanolayered structures in the composites. The longitudinal directions of both the cellulose II crystallites and the saponite platelets were preferentially oriented parallel to the film surface in the composites. The good nanodispersibility and high orientation of the saponite platelets in the composite films resulted in high mechanical strength, high Young's modulus, and good thermal dimensional stabilities, and gas barrier properties in the composites, compared with a reference cellulose film. Moreover, the tensile strength and Young's modulus of the composite film reached 241 MPa and 7.7 GPa, respectively, when a simple drawing process was applied to the wet composite film; this is probably owing to the improvement in the orientation of the cellulose II crystallites and saponite platelets in the composites. The composite films also showed high toughness and ductility. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3168–3174, 2013     

Lightweight investigation of long chain branching polypropylene/cellulose nanofiber composite foams

Long chain branching polypropylene (LCBPP)/cellulose nanofiber (CNF) composite foams were prepared by short shot foam injection molding method and their morphological, mechanical, and thermal properties were also investigated. The cellular structure of LCBPP/CNF composite foams was improved with weight reduction (WR) ratios increasing. The cell densities of LCBPP/CNF composite foams were dramatically increasing with WR ratios rising. More, the fine and uniform cellular structures were obtained due to the incorporation of CNF. The highest cell density, specific flexural strength, and modulus could achieved 20 × 10³ cell/cm², 65 MPa/(g/cm³) and 2.7 GPa/(g/cm³), respectively. Furthermore, the specific Charpy impact strengths were also higher than the ones of solid samples. At last, the thermal insulation properties were discussed accordingly.     

Preparation and characterization of transparent cellulose films using an improved cellulose dissolution process

Effective dissolution of cellulosic macromolecules is the first predominant step to prepare functional bio‐based materials with desirable properties. In this study, we developed an improved dissolution process using a freeze‐drying pretreatment to promote the dissolution of cellulose. Rheological measurements of cellulose solutions and physicochemical characterization of regenerated cellulose films (scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis) were performed. Cellulose solution prepared from 5% microcrystalline cellulose (w:v) in the solvent exhibits a Newtonian fluid character while cellulose solutions at higher concentrations show a pseudo‐plastic fluid behavior. Results from physicochemical characterization indicate that a freeze‐drying pretreatment step of cellulose leads to a complete dissolution at 5% concentration while only part of cellulose is dissolved at 10% and 15% concentrations. The results obtained indicated that the use of a freeze‐drying pretreatment step under mild conditions lead to a complete dissolution of cellulose at 5% concentration. The cellulose films prepared from 5% concentration exhibited desirable properties such as good optical transparency, crystallinity, and thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44871.     

Fabrication of elastic composite hydrogels using surface‐modified cellulose nanofiber as a multifunctional crosslinker

We fabricate composite hydrogels using surface‐modified cellulose nanofiber (CNF) and N‐isopropylacrylamide (NIPAm) as a multifunctional crosslinker and monomer, respectively. We expect to produce unique network structures that lead to elastomeric properties rarely reported for CNF‐based materials. The modification of CNF is performed to introduce polymerizable vinyl groups onto the surface of CNF via condensation between the surface hydroxyl groups and 3‐(trimethoxysilyl)propylmethacrylate. The modification and morphology of the surface‐modified CNF (mCNF) are confirmed by FTIR, solid‐state NMR, and FE‐SEM, respectively. We conduct in situ radical polymerization under various conditions using mixtures of the mCNF aqueous suspension, NIPAm monomer, radical initiator, and catalyst. The mechanical properties of the obtained hydrogels (water content = 90 wt %) are evaluated. The gels can be elastically stretched to more than 700 times their original lengths and exhibit an apparent shape recovery with a small permanent deformation (～1/5 of the applied deformation under the gravity field). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42906.