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Incompatibility of nanocellulose with non-polar polymer matrices disrupts the interfacial interaction and results in aggregation and phase separation. In this study a facile and environmentally friendly method was used to partially substitute the surface hydroxyl groups by attaching polysiloxane to impart hydrophobic properties. The silanization reaction proceeded with hydrolysis of triethoxyvinylsilane (TEVS) into reactive silanols followed by condensation to form the branched polymer. These polysiloxane oligomers were chemically grafted to form alkoxy silane bonds on the surface of CNCs. A suitable degree of hydrophilic-hydrophobic balance of the modified CNCs was achieved which improved their dispersion in hydrophobic matrix poly(butylene adipate-co-terephthalate) (PBAT). FTIR, NMR (13C and 29Si) and XPS demonstrated successful surface chemical modification and confirmed extent of silanization as a function of silane concentration. XRD showed successful grafting of the vinyl silane agent and confirmed polymorph structure of the nanocellulose was retained. The results from TEM and AFM demonstrated successful coating of nano whiskers at 5 wt% silane loading. The successful grafting of the silane agent with pendant vinyl groups improved surface hydrophobicity. These results show that this facile method produces adequately surface modified CNC which can be used as filler in hydrophobic matrices of bioplastics.
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CeluloseRESUMO
Plastic pollution is recognized as a major environmental problem in many countries. Over the last decade, academics have embraced research on bioplastics to discover newer high-end green materials. However, the end-of-life environmental fate of such materials is not adequately understood. Non-isocyanate polyhydroxyurethanes (PHUs) are green engineering materials with huge potential to replace traditional polyurethanes. Despite this immense potential, a number of questions about their environmental fate remain unanswered. The present study investigated the extent and mechanisms underlying soil biodegradation of PHUs and determined whether the deterioration of PHUs within starch bioplastics (ST) can improve the biodegradation of starch (ST)-PHU hybrids. Soil microbiomes managed to effectively and quickly digest not only PHUs but also ST-PHU hybrids. All ST-PHU hybrids were characterized by exceptional biodegradability with mass losses of up to ~88% following a soil burial time of only 120 days. The biodegradation of ST-alone bioplastics was 69% under identical conditions. The presence of cellulose nanocrystals (CNC) reduced the potential for the soil microbial community to degrade nanohybrids (ST-PHU-CNC). Microbially digested bioplastics with PHU presented less stages of thermal degradation, and reduced intensities of FTIR, NMR and XPS signals compared to the original films, indicating improvement of the biodegradation mechanism. These findings suggested the positive environmental implications of PHU in improving the bioplastic's degradation and their potential for future applications.
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Nanopartículas , Amido , Biodegradação Ambiental , Celulose , Plásticos , SoloRESUMO
Graphene oxide quantum dots (GOQDs) hold great promise as a new class of high-performance carbonaceous nanomaterials due to their numerous functional properties, such as tunable photoluminescence (PL), excellent thermal and chemical stability, and superior biocompatibility. In this study, we developed a facile, one-pot, and effective strategy to engineer the interface of GOQDs through covalent doping with silicon. The successful covalent attachment of the silane dopant with pendant vinyl groups to the edges of the GOQDs was confirmed by an in-depth investigation of the structural and morphological characteristics. The Si-GOQD nanoconjugates had an average dimension of â¼8 nm, with a graphite-structured core and amorphous carbon on their shell. We further used the infrared nanoimaging based on scattering-type scanning near-field optical microscopy to unveil the spectral near-field response of GOQD samples and to measure the nanoscale IR response of its network; we then demonstrated their distinct domains with strongly enhanced near fields. The doping of Si atoms into the sp2-hybridized graphitic framework of GOQDs also led to tailored PL emissions. We then sought to explore the potential applications of Si-GOQDs on the surface of plastic films where poly(dimethylsiloxane) (PDMS) served as a bridge to tightly anchor the Si-GOQDs to the surface. The bi-layered coated films which were built with co-assembly of Si-GOQDs and PDMS contributed to suppressing the transmission of water molecules due to the generation of compact and less accessible passing sites, achieving a nearly twofold reduction in water permeability compared to the single-layered coated films. The nanoindentation and PeakForce quantitative nanomechanical mapping showed that Si-GOQD-coated substrates were softer and more deformable than those coated only with PDMS. The co-assembly of PDMS and Si-GOQDs yielded films that were less stiff than those made from PDMS alone. Our findings provided conceptual insights into the importance of nanoscale surface engineering of GOQDs in conferring excellent dispersibility and enhancing the performance of nanocomposite films.
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Synthetic polymers, commonly referred to as plastics, are anthropogenic contaminants that adversely affect the natural ecosystems. The continuous disposal of long lifespan plastics has resulted in the accumulation of plastic waste, leading to significant pollution of both marine and terrestrial habitats. Scientific pursuit to seek environment-friendly materials from renewable resources has focused on cellulose, the primary reinforcement component of the cell wall of plants, as it is the most abundantly available biopolymer on earth. This paper provides an overview on the current state of science on nanocellulose research; highlighting its extraction procedures from lignocellulosic biomass. Literature shows that the process used to obtain nanocellulose from lignocellulosic biomass greatly influences its morphology, properties and surface chemistry. The efficacy of chemical methods that use alkali, acid, bleaching agents, ionic liquids, deep eutectic solvent for pre-treatment of biomass is discussed. There has been a continuous endeavour to optimize the pre-treatment protocol as it is specific to lignocellulosic biomass and also depends on factors such as nature of the biomass, process and environmental parameters and economic viability. Nanofibers are primarily isolated through mechanical fibrillation while nanocrystals are predominantly extracted using acid hydrolysis. A concise overview on the ways to improve the yield of nanocellulose from cellulosic biomass is also presented in this review. This work also reviews the techniques used to modify the surface properties of nanocellulose by functionalizing surface hydroxyl groups to impart desirable hydrophilic-hydrophobic balance. An assessment on the emerging application of nanocellulose with an emphasis on development of nanocomposite materials for designing environmentally sustainable products is incorporated. Finally, the status of the industrial production of nanocellulose presented, which indicates that there is a continuously increased demand for cellulose nanomaterials. The demand for cellulose is expected to increase further due to its increasing and broadening applications.
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Surface texturing is a common modification method for altering the surface properties of a material. Predicting the response of a textured surface to scratching is significant in surface texturing and material design. In this study, scratches on a thermoplastic material with textured surface are simulated and experimentally tested. The effect of texture on scratch resistance, surface visual appearance, surface deformation and material damage are investigated. Bruise spot scratches on textured surfaces are found at low scratch forces (<3 N) and their size at different scratch forces is approximately the same. There is a critical point between the bruise spot damage and the texture pattern damage caused by continuous scratching. Scratch resistance coefficients and an indentation depth-force pattern are revealed for two textured surfaces. A texture named "Texture CB" exhibits high effectiveness in enhancing scratch visibility resistance and can increase the scratch resistance by more than 40% at low scratch forces. The simulation method and the analysis of the power spectral density of the textured surface enable an accurate prediction of scratches.
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The use of superhydrophobic surfaces in a broad range of applications is receiving a great deal of attention due to their numerous functionalities. However, fabricating these surfaces using low-cost raw materials through green and fluorine-free routes has been a bottleneck in their industrial deployment. This work presents a facile and environmentally friendly strategy to prepare mechanically robust superhydrophobic surfaces with engineered lotus leaf mimetic multiscale hierarchical structures via a hybrid route combining soft imprinting and spin-coating. Direct soft-imprinting lithography onto starch/polyhydroxyurethane/cellulose nanocrystal (SPC) films formed micro-scaled features resembling the pillar architecture of lotus leaf. Spin-coating was then used to assemble a thin layer of low-surface-energy poly(dimethylsiloxane) (PDMS) over these microstructures. Silica nanoparticles (SNPs) were grafted with vinyltriethoxysilane (VTES) to form functional silica nanoparticles (V-SNPs) and subsequently used for the fabrication of superhydrophobic coatings. A further modification of PDMS@SPC film with V-SNPs enabled the interlocking of V-SNPs microparticles within the cross-linked PDMS network. The simultaneous introduction of hierarchical microscale surface topography, the low surface tension of the PDMS layer, and the nanoscale roughness induced by V-SNPs contributed to the fabrication of a superhydrophobic interface with a water contact angle (WCA) of â¼150° and a sliding angle (SA) of <10°. The PDMS/V-SNP@SPC films showed an â¼52% reduction in water vapor transmission rate compared to that of uncoated films. These results indicated that the coating served as an excellent moisture barrier and imparted good hydrophobicity to the film substrate. The coated film surfaces were able to withstand extensive knife scratches, finger-rubbing, jet-water impact, a sandpaper-abrasion test for 20 cycles, and a tape-peeling test for â¼10 repetitions without losing superhydrophobicity, suggesting superior mechanical durability. Self-cleaning behavior was also demonstrated when the surfaces were cleared of artificial dust and various food liquids. The green and innovative approach presented in the current study can potentially serve as an attractive new tool for the development of robust superhydrophobic surfaces without adverse environmental consequences.
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Green and environment-friendly polymers with comparable thermal and mechanical performance can be suitable alternatives of synthetic polymers. This paper documents the synthesis of crystallizable polyhydroxyurethanes (PHUs) through a facile, non-isocyanate and catalyst-free route with step growth polymerization of ethylene carbonate and three different diamines (1,2-ethanediamine, 1,4-butanediamine and 1,6-hexanediamine). The PHU monomers were interacted with gelatinized starch (HAGS) to synthesize HAGS/PHU hybrid materials. Both PHU monomers and hybrid materials were characterized by FT-IR, 1H NMR, 13C NMR, DSC and XRD. Hydroxyl groups of HAGS and PHUs were found to predominantly contribute to the intermolecular hydrogen bonding. The films produced using HAGS/PHU hybrid materials exhibited tuneable mechanical properties with tensile strength ranging between 1.7â¯MPa and 3.2â¯MPa and a breaking strain varying between 45% and 121%. These findings underscore the potential of non-isocyanate polyurethanes as environmentally sustainable materials and provide facile route for synthesis of HAGS/PHU hybrid materials.
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Graphene-polyamide-6 (PA6) composites with up to 17.0%·w/w graphene content were prepared via melt mixing. Oscillatory rheometry revealed that the dynamic viscoelastic properties of PA6 decreased with the addition of 0.1%·w/w graphene but increased when the graphene content was increased to 6.0%·w/w and higher. Further analysis indicated that the rheological percolation threshold was between 6.0 and 10.0%·w/w graphene. The Carreau-Yasuda model was used to describe the complex viscosity of the materials. Capillary rheometry was applied to assess the steady shear rheology of neat PA6 and the 17.0%·w/w graphene-PA6 composite. High material viscosity at low shear rates coupled with intense shear-thinning in the composite highlighted the importance of selecting the appropriate rheological characterisation methods, shear rates and rheological models when assessing the 3D printability of percolated graphene-polymer composites for material extrusion (ME). A method to predict the printability of an ME filament feedstock, based on fundamental equations describing material flow through the printer nozzle, in the form of a printing envelope, was developed and verified experimentally. It was found that designing filaments with steady shear viscosities of approximately 15% of the maximum printable viscosity for the desired printing conditions will be advantageous for easy ME processing.
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Materials based on petroleum-based resources have aroused widespread concern because of their environmental and healthcare footprints. Cellulose nanocrystals (CNCs) are at the cutting edge of current research because of their great promise in developing sustainable and high-performance materials. To establish a comprehensive understanding of the synergistic reinforcement effect of CNCs, we introduced a new method to fabricate all-green, transparent, and mechanically robust nanohybrid materials using CNCs in conjunction with gelatinized starch (GS) and polyhydroxyurethanes (PHUs). The synergistic interaction between the CNC skeleton and the GS/PHU network enabled us to span exceptionally stiff nanohybrids that could withstand up to 8.5 MPa tensile strength. The tunable mechanical properties and enhanced thermal stability in these nanohybrids primarily arise from the presence of dense hydroxyl groups on the CNCs' surface, which offer a robust scaffold for fortified hydrogen bonds to form with GS/PHU domains. The multiple intramolecular hydrogen bonds synergistically served as highly stable associations and concurrently facilitated energy dissipation and transferred the stress across the interfacial region. The rational design of the molecular interactions presented in this work provided increased opportunities to build nanohybrids with outstanding mechanical performance. More broadly, the insights afforded by this study not only delivered a better understanding on the molecular-level interactions in the CNC/GS/PHU system but also enriched the potential for the commercial exploration of tunable cellulosic nanohybrid materials.
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Manufacturing of multifunctional materials through blending is a promising route for improving performance of biopolymers including starch. Non-isocyanate polyurethanes (NIPUs) are an emerging group of green materials. Understanding the mechanism of interaction between starch and NIPU not only highlights underlying chemistry but also offers an opportunity to tailor the properties and functions of starch-NIPU hybrids. We investigated the interfacial interactions between starch and NIPU to pave the way towards development of high-performance green materials. Multiple analyses revealed that NIPU interacted effectively with starch chains via intermolecular hydrogen bonds. We showed that NIPU domains can efficiently interact with the small portion of starch skeleton at interfacial region and they are only moderately miscible. Incorporation of either component above certain ratio resulted in a phase separation. This work contributes towards understanding of interfacial chemistry between starch and NIPUs and enables tailoring the interface for facile engineering of starch-NIPU hybrids.
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Dioxolanos/química , Química Verde , Poliuretanos/síntese química , Amido/química , Engenharia Química , Técnicas de Química Sintética , Etilenodiaminas , Humanos , Ligação de Hidrogênio , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The colonization of undesired bacteria on the surface of devices used in biomedical and clinical applications has become a persistent problem. Different types of single-function (cell resistance or bactericidal) bioresponsive materials have been developed to cope with this problem. Even though these materials meet the basic requirements of many biomedical and clinical applications, dual-function (cell resistance and biocidal) bioresponsive materials with superior design and function could be better suited for these applications. The past few years have witnessed the emergence of a new class of dual-function materials that can reversibly switch between cell-resistance and biocidal functions in response to external stimuli. These materials are finding increased applications in biomedical devices, tissue engineering, and drug-delivery systems. This review highlights the recent advances in design, structure, and fabrication of dual-function bioresponsive materials and discusses translational challenges and future prospects for research involving these materials.
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Antibacterianos/uso terapêutico , Bactérias/patogenicidade , Infecções Bacterianas/prevenção & controle , Materiais Biocompatíveis/uso terapêutico , Antibacterianos/química , Bactérias/efeitos dos fármacos , Infecções Bacterianas/microbiologia , Materiais Biocompatíveis/química , Humanos , Polímeros/química , Polímeros/uso terapêutico , Propriedades de Superfície , Engenharia TecidualRESUMO
Nanocomposite application in automotive engineering materials is subject to continual stress fields together with recovery periods, under extremes of temperature variations. The aim is to prepare and characterize polyolefin-rubber nanocomposites developed for additive manufacturing in terms of their time-dependent deformation behaviour as revealed in creep-recovery experiments. The composites consisted of linear low density polyethylene and functionalized rubber particles. Maleic anhydride compatibilizer grafted to polyethylene was used to enhance adhesion between the polyethylene and rubber; and multi-walled carbon nanotubes were introduced to impart electrical conductivity. Various compositions of nanocomposites were tested under constant stress in creep and recovery. A four-element mechanistic Burger model was employed to model the creep phase of the composites, while a Weibull distribution function was employed to model the recovery phase of the composites. Finite element analysis using Abaqus enabled numerical modelling of the creep phase of the composites. Both analytical and numerical solutions were found to be consistent with the experimental results. Creep and recovery were dependent on: (i) composite composition; (ii) compatibilizers content; (iii) carbon nanotubes that formed a percolation network.