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Lignin-containing cellulose nanofibrils (LCNFs) have attracted great attention because the presence of lignin brought additional merits to cellulose nanofibrils including hydrophobicity, ultraviolet (UV)-shielding capacity, and reduced water sensitivity. In the present work, LCNFs with lignin content up to 21 wt % were prepared with a high yield exceeding 70 wt %, from neat date palm waste, by a hydrothermal treatment (HTT) at 120-150 °C in the presence of 20-30 wt % maleic acid, followed by high-pressure homogenization. The chemical composition, degree of polymerization, morphology, and colloidal and rheological properties of the LCNFs were investigated to understand how the HTT in the presence of MA affected the properties of the resulting LCNFs. Nanopapers prepared from the LCNF suspensions exhibited mechanical properties lower than those from lignin-free CNF-based nanopapers, yet with decreased hydrophilicity. A mechanism explaining how the HTT in the presence of MA facilitated the disintegration of the biomass into nanoscale material was proposed. Overall, the present work demonstrated a feasible and scalable approach for the sustainable production of LCNF suspensions from neat agricultural residues, with a high yield and a high lignin content, without any need to perform a preliminary partial delignification.
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Nanofibras , Phoeniceae , Celulose/química , Lignina/química , Suspensões , Nanofibras/químicaRESUMO
Due to its intrinsic electrical conductivity, polyaniline (PANI) is one of the most promising conducting polymers for high-performance applications in a wide range of technological fields. However, its poor dispersibility in water and organic solvents markedly imparts its processability and electrical conductivity. Herein, we report a green and one-step approach to preparing stable colloidal dispersions of highly dispersible hybrid nanoparticles by polymerizing PANI onto chitin nanocrystals (ChNCs) as biotemplates, via initiation through the surface amino groups of ChNCs. Evidence of the grafting of PANI onto ChNCs was supported by transmission electron microscopy (TEM), as well as Raman and Fourier transform infrared (FTIR) spectroscopies. Nanocomposite films were prepared by mixing the PANI-g-ChNCs with a waterborne poly(vinyl acetate) latex dispersion followed by casting and film formation at room temperature. The mechanical properties were tested as a function of the PANI-g-ChNC content. In addition, it was shown that at a proper content of PANI in ChNCs, and over a critical loading in the PANI-g-ChNCs, a conductive film was obtained, without sacrificing the reinforcing effect of the rodlike nanofiller. As a potential application, conductive waterborne adhesives for wood were prepared and the performance of the adhesives was tested. This research provides a facile route to fabricating a new class of hybrid nanofiller from a biobased origin, stable in water and easy to mix with waterborne dispersions, combining the merits of the ChNC nanofiller with the conductivity of PANI.
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Nanopartículas , Polímeros , Compostos de Anilina , Quitina/química , Condutividade Elétrica , Látex , Nanopartículas/química , Polímeros/química , Solventes , ÁguaRESUMO
In the present work, the nucleating aptitude for poly-L-(lactic acid) (PLLA) of several biobased nanoparticles (NPs) with different morphologies and surface properties, including cellulose nanofibrils with and without lignin (LCNFs and CNFs) as well as cellulose, chitin and starch nanocrystals (CNCs, ChNCs and SNCs), was investigated. A single melt-processing step using a small amount of poly(ethylene glycol) (PEG) as carrier for the NPs was adopted to prepare films with the same nanofiller content of 1 wt%. The nucleation efficiency was investigated by differential scanning calorimetry using Avrami's and Lauritzen-Hoffman's secondary nucleation theory. The crystallization half-time was found to change considerably according to the morphology and surface properties of the NPs, with the lowest time observed for CNFs and CNCs, followed by ChNCs, SNCs and LCNFs. Comparing the surface energy components of the different nucleating agents, it was found that the nanofiller with the highest γp had the lowest t1/2 and demonstrated the most effective nucleating aptitude. The evolution of the melt rheological properties of the different compositions, and the mechanical and optical properties of the films with and without a short annealing treatment were also studied.
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Celulose , Nanopartículas , Celulose/química , Cristalização , Ácido Láctico/química , Nanopartículas/química , ReologiaRESUMO
Twin-screw extrusion (TSE) is a recent strategy used to prepare nanocelluloses at high solid contents. However, various aspects of the mechanism of disintegration and the role of fiber pretreatment remain to be elucidated. Oxidized cellulose fibers with carboxyl contents between 300 and 700 µmol·g-1 were extruded in the presence of polyvinyl alcohol (PVA) at a 80/20 (w/w) ratio, to produce high-consistency nanocellulose gels at 15 wt% solid content, ready for use in multiple applications. The influence of the origin of the pulps and the oxidation treatment on the efficiency of fiber disintegration was evaluated by porosity measurement. The rheological properties of the nanocellulose-PVA gels and the mechanical properties and transparency of the resulting nanopapers were studied as well. Combining TSE and rotor-stator dispersion or short sonication homogenization contributed to enhancing the fibrillation during extrusion, providing a method to increase the fraction of nanocellulose in a much less energy-consuming manner.
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Lignin-containing cellulose nanofibrils (LCNFs) have emerged as a new class of nanocelluloses where the presence of residual lignin is expected to impart additional attributes such as hydrophobicity or UV-absorption. In the present work, LCNFs with a lignin content between 7 and 15 wt% were prepared via a TEMPO-mediated oxidation as chemical pretreatment followed by high-pressure homogenization. The impact of the carboxyl content (CC) on the properties of the resulting LCNF gel, in terms of lignin content, colloidal properties, morphology, crystallinity, and thermal stability, were investigated. It was found that lignin content was significantly decreased at increasing CC. In addition, CC had a positive effect on colloidal stability and water contact angle, as well as resulting in smaller fibrils. This lower size, together with the lower lignin content, resulted in a slightly lower thermal stability. The reinforcing potential of the LCNFs when incorporated into a ductile polymer matrix was also explored by preparing nanocomposite films with different LCNF contents that were mechanically tested under linear and non-linear regimes by dynamic mechanical analysis (DMA) and tensile tests. For comparison purposes, the reinforcing effect of the LCNFs with lignin-free CNFs was also reported based on literature data. It was found that lignin hinders the network-forming capacity of LCNFs, as literature data shows a higher reinforcing potential of lignin-free CNFs. Nonetheless, the tensile strength of the acrylic matrix was enhanced by 10-fold at 10 wt% of LCNF content.
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Mater-Bi® is one of the most commercialized starch-based blends used in biodegradable flexible packaging. However, the high ductility and low stiffness of Mater-Bi® might limit its application and developing a solution to tailor the stiffness and mechanical strength is highly desirable. In the present work, blends based on Mater-Bi® and poly-L-(lactic acid) (PLLA) at a different ratio from 70/30 to 50/50 wt% were prepared via melt-extrusion and the effect of the PLLA content and Joncryl ADR® as a reactive compatibilizing agent, on the mechanical properties, melts rheology, morphology and disintegration aptitude were investigated. The inclusion of PLLA in Mater-Bi® has a marked beneficial effect on the tensile strength and stiffness of the blend while maintaining acceptable ductility. The addition of the reactive compatibilizing agent contributed to improving the strength and elongation at the break of the blend. The melt rheology of the blend was also affected by the ratio of the two components, mostly when the Joncryl ADR® was present. The disintegration by biodegradation of the blend was preserved in the presence of PLLA, and it takes less than 30 days for the films to completely decompose and disintegrate under controlled composting conditions. Interestingly, a thin film from Mater-Bi®/PLLA 60/40 was successfully prepared by blown film extrusion, demonstrating a good balance between stretchability (elongation at break exceeding 100%) and stiffness (1.8 GPa). This work opened to broadening the use of starch-based biodegradable plastic toward more demanding applications such as mulching films.
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Despite advances in diabetes care, impaired diabetic wound healing remains a significant clinical problem. The present study was aimed at developing a novel cream based on Ginkgo biloba extract and investigating its wound healing effect on full-thickness wounds in diabetic rats. The topical formulated oil-in-water emulsion-based cream contains Ginkgo biloba aqueous extract in an amount of about 1% to 5% as an active agent. The prepared formula was subjected to physicochemical assessment and pharmacotechnical characterization. Eighteen alloxan-induced diabetic rats completing full-thickness excisional skin wounds were randomly divided into three groups topically treated with either a normal saline (control group), the reference drug ("Cytol Centella cream®"), and cream based on the Ginkgo biloba extract. The response to treatment was assessed by macroscopic, qualitative, and quantitative histopathological analysis. The prepared formula showed good physicochemical properties. The rheological behavior of the prepared cream followed a non-Newtonian pseudoplastic pattern at different storage temperatures. The cream, which is a macroemulsion with uniform size distribution, remained stable for 6 months. Skin tolerance studies confirmed the compatibility of the cream with the skin. During the experimental trial, the cream based on the Ginkgo biloba-treated group showed significant improvements over the control and reference groups for both general wound appearance and healing dynamics. This increased rate of closure of wounds in diabetic rats was associated with increased collagen synthesis. Our findings showed that the cream could be a promising and innovative topical treatment with Ginkgo biloba extract for the management of acute diabetic wounds.
Assuntos
Diabetes Mellitus Experimental/tratamento farmacológico , Ginkgo biloba/química , Extratos Vegetais/farmacologia , Creme para a Pele/farmacologia , Pele/efeitos dos fármacos , Cicatrização/efeitos dos fármacos , Administração Tópica , Animais , Diabetes Mellitus Experimental/complicações , Diabetes Mellitus Experimental/patologia , Modelos Animais de Doenças , Masculino , Ratos , Ratos Wistar , Pele/patologiaRESUMO
Stable biobased waterborne Pickering dispersions of acrylated epoxidized soybean oil (AESO) were developed using chitin nanocrystals (ChNCs) as sole emulsifier without any additives. Thin AESO-ChNC nanocomposite films were produced by UV-curing thin-coated layers of the AESO emulsion after water evaporation. The kinetics of photopolymerization were assessed by monitoring the consumption of the AESO acrylate groups by infrared spectroscopy (Fourier transform infrared (FTIR)). The curing was faster in the presence of ChNCs, with a disappearance of the induction period observed for neat AESO. The coating of AESO droplets with a thin layer of ChNCs was confirmed by scanning electron microscopy (SEM) observation. SEM and transmission electron microscopy (TEM) images revealed the honeycomb organization of ChNCs inside the cured AESO-ChNC films. The mechanical, thermal, and optical properties of the nanocomposite films were studied by dynamic mechanical analysis (DMA), tensile testing, differential scanning calorimetry (DSC), and transmittance measurement, as a function of ChNC content. The inclusion of ChNCs is strongly beneficial to increase the stiffness and strength of the cured films, without compromising its optical transparency. The ability of ChNCs to act as an emulsifier for AESO in replacement of synthetic surfactants and their strong reinforcing effect in UV-cured films offer new opportunities to produce waterborne stable dispersions from AESO for application in biobased coatings and adhesives.
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Nanocompostos , Nanopartículas , Quitina , Óleo de SojaRESUMO
In this work, date palm waste (DPW) stemming from the annual pruning of date palm was used as a reinforcing filler in polypropylene matrix at 20-60 wt.%. Only a grinding process of the DPW has been performed to ensure no residue generation and full utilization. The present work investigates how the DPW use affects mechanical properties and water absorption of the ensuing composite. The effect of the addition of maleated polypropylene (MAPP) as a coupling agent on the composite properties was also studied. It was shown that the reinforcing potential of DPW was strongly dependent on aspect ratio and interface quality. The MAPP addition resulted in a composite with higher strength and stiffness than the neat PP, meaning that DPW behaves as reinforcement. The difference in the reinforcing effect was explained by the change in the quality of the interface between date palm waste and the polypropylene polymeric chain.
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Date palm waste is an abundant agricultural residue in Tunisia and can be used for plastic reinforcement. Moreover, its use in plastic composites can help to reduce dependence on fossil resources for material production. In this work, the valorization of date palm residues was studied by employing high-yield processes following mechanical, chemical, and enzymatical treatments. Fibers obtained by soft chemical treatment with sodium hydroxide and enzymatic treatment with xylanases and pectinases were evaluated for their use in the reinforcement of plastic materials. The flexural strength property, truly relevant for structural, construction, automotive, or other market sectors, was adopted to assess the reinforcing potential of the fibers. Polypropylene was effectively reinforced with date palm fibers (60 wt.%), exhibiting a flexural strength increases of 80% (73.1 MPa), 93% (78.5 MPa), and 106% (83.9 MPa) for mechanical, chemical, and enzymatic fibers, respectively. The different treatments had an impact on the chemical composition of the fibers, and by extension on the final properties of the composites. The holocellulose content could provide good interfacial adhesion using a coupling agent, whereas the lignin content improved the dispersion of the phases. Two interesting outcomes were that the flexural performance of enzymatic fibers was like that of wood composites, whereas the specific flexural strength was comparable to that of glass fiber composites. Overall, the present work has shown the potential behind date palm waste in the composite sector when a specific property or application is desired. Novel treatments have been used for greater fiber compatibility, increasing the sustainability of the process, and improving the applicability of the palm residue.
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Paper-TiO2-Ag2O floating photocatalysts were produced under mild condition and their photocatalytic activity for the degradation of aromatic amine under sunlight stimulant was investigated. Characterizations by Raman, XRD, XPS, DRS and PL confirmed the presence of TiO2 and Ag2O, and the morphology of the appended TiO2/Ag2O layer was probed by FE-SEM. The photocatalytic activity of the prepared samples was investigated by the degradation of aniline (AN) in water under simulated sun-light illumination and constrained conditions, i.e. non-stirring and non-oxygenation. The presence of Ag2O combined with TiO2 was shown to improve the resistance of paper to bacteria attack, thus increasing the durability of the photocatalyst. Thanks to its hydrophobic character, the paper-TiO2-Ag2O NPs can be employed as useful floating photocatalyst and can be reused in continuous cycles.
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Celulose , Prata , Antibacterianos/farmacologia , Catálise , TitânioRESUMO
Poly(butylene adipate-Co-terephthalate)/thermoplasticized starch PBAT/TPS blends are among the most produced biodegradable plastic for wide application packaging, sharing more than 20% of the global production capacity of bioplastics. However, this class of material suffers from poor mechanical strength in comparison of neat PBAT, especially when the TPS content exceeds 30 wt%. Aiming at enhancing the mechanical performance of PBAT/TPS blends while maintaining relatively high TPS content, cellulose nanofibrils (CNFs) was incorporated into the TPS phase using twin screw extrusion. The effects of CNFs content on the microstructure, mechanical properties, melt-rheology and humidity absorption were investigated. An enhancement in the tensile strength and modulus was noted with the inclusion of CNFs, with optimal performance attained at 8 wt% of CNFs. A narrowing in the distribution of the TPS nodules within the PBAT matrix was also observed with the addition of CNFs, which is expected to be on the origin of the main evolution in the mechanical, rheological and humidity observed. Because of the availability of CNFs, biodegradability and facile processability, the ternary PBAT-TPS-CNFs blends might contribute to improve the performance of this class of biodegradable bioplastic.
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Celulose/química , Polímeros/química , Nanofibras/química , Reologia , Resistência à TraçãoRESUMO
Cotton fabrics decorated with Cu2O-Ag and Cu2O-Ag-AgBr NPs have been prepared using chemically immobilized Cu2O NPs as sacrificial templates. The objective is to prepare Cu2O-Ag heterostructures with Ag being intimately in contact with Cu2O NPs by galvanic replacement reactions without addition of any external reducing agent. Field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) analysis were used to study the morphology and the chemical composition of the nanocomposites formed on the fabrics. The morphology of the ensuing nanostructures was shown to be dependent on the Ag precursor, AgNO3, concentration. The antimicrobial activity of the treated fabrics was evaluated against Staphylococcus aureus and Escherichia coli as model strains of gram-negative and gram-positive, respectively. The results showed that the fabrics loaded with Cu2O-Ag and Cu2O-Ag-AgBr nanocomposites exhibited enhanced sterilization activity compared to the Cu2O treated fabric.
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Nanopartículas Metálicas , Prata , Antibacterianos/farmacologia , Fibra de Algodão , Prata/farmacologia , Staphylococcus aureus , TêxteisRESUMO
Chitin nanocrystals (ChNCs) produced by hydrochloric acid hydrolysis of chitin were used as stabilizing agent for oil-in-water (O/W) emulsification of soybean oil (SO), acrylated soybean oil (ASO), and epoxidized soybean oil (ESO). The emulsion stability, droplet size, and rheology of the emulsion were found to be significantly affected by the oil chemical structure. Strong interaction between ChNCs and the oil droplets enhanced the stabilizing efficiency of ChNCs through a Pickering effect, resulting in emulsions with low droplet size and long-term stability. The use of ChNCs as stabilizer for O/W emulsions in replacement of synthetic surfactants opens new avenues to produce emulsions for a wide variety of applications, including cosmetic products, coating, inks and adhesives.
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Quitina , Nanopartículas , Emulsões , Hidrólise , Reologia , ÁguaRESUMO
Foodborne diseases caused by resistance of microorganisms to multiple antimicrobial agents have emerged as a major public health concern around the world. The search for potential antimicrobials has resulted in the emergence of metal nanoparticles for protection against these infections. In this study an eco-friendly and green approach was used to biosynthesize hybrid Ag/AgCl nanoparticles (NPs), using levan from Bacillus mojavensis as a stabilizing/reducing agent, with a high efficiency against a broad spectrum of foodborne bacteria as well as biofilm formations. The morphology and physicochemical characteristics of levan-Ag/AgCl NPs were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-vis spectroscopy (UV), dynamic light scattering (DLS) and thermogravimetric analysis (TGA). The hybrid levan-Ag/AgCl was evaluated for antibacterial activity against foodborne pathogenic bacteria (Escherichia coli, Klebsiella pneumoniae, Salmonella enterica, Pseudomonas aeruginosa, Staphylococcus aureus, Micrococcus luteus, Listeria monocytogenes, Enterococcus faecalis, Bacillus subtilis and Bacillus thuringiensis). The study demonstrated the strong efficiency of hybrid levan-Ag/AgCl NPs as a potent inhibitor against all tested strains, with much higher activity against Gram-negative than Gram-positive bacteria. Furthermore, bacterial strains were found to be highly sensitive to hybrid levan-Ag/AgCl NPs in comparison to the tested antibiotics. As a possible application of levan-Ag/AgCl NPs as an additive in packaging, PVA films with different amounts of hybrid levan-Ag/AgCl NPs were prepared by casting and their antibacterial, mechanical, and optical properties and ability to expand the shelf life of beef meat were explored. Interestingly, the amount of Ag leached out from films was below the permissible limit. This work demonstrates the strong antibacterial action of hybrid levan-Ag/AgCl NPs and their potential use in bioactive packaging material.
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In this study, cotton fabrics decorated with Ag/AgCl and Ag/AgBr NPs were produced by a simple hydrothermal treatment using AgCl and AgBr as precursors. Their morphological features as well as, chemical composition and structural and luminescence properties were compared. Their water disinfection aptitude against E. coli and S. aureus was also investigated under solar illumination in batch as well asin dynamic conditions. The highest activity was observed for Cot-Ag/AgCl with a quasi-complete inactivation of E. coli and S. aureus(1.5 × 107cfu mL-1) within 15 min illumination. Disinfection efficiency under continuous flow was also tested using a home-made photoreactor and the cotton fabrics with the most efficient photocatalyst (Ag/AgCl). It has shown to be efficient at least for 10 cycles revealing the robustness of the functionalization. The mechanism of photocatalytic disinfection was explained in terms of the surface plasmon resonance (SPR) induced by the presence of Ag NPs, the resulting holes, h+, being one of the most intervenient species in the disinfection mechanism. The difference in the photocatalytic efficiency between AgCl and AgBr functionalized cotton was attributed to differences in the carriers (h+and e-) lifetime. This work provides a proof of concept for the potential applicability of Cot-Ag/AgCl or Cot-Ag/AgBr for in-flow potabilization of water under solar illumination.
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Compostos de Prata , Prata , Catálise , Escherichia coli , Luz , Staphylococcus aureusRESUMO
The present work aims at determining the potential of date palm wastes to be applied as reinforcement in polypropylene. For this, fibers were separated from the raw biomass via mechanical defibration in Sprout Waldron equipment. Then, three different treatment strategies were adopted on the fibers, being (i) mechanical, (ii) chemical with NaOH, and (iii) enzymatical with xylanases and pectinases. Fibers were characterized in terms of chemical composition, morphology and SEM. Additionally, PP was reinforced with date palm fibers and the composites' stiffness was evaluated. The analysis was performed from a macro and micro mechanical viewpoint. The incorporation of 40 and 60 wt.% of DPF-E enhanced the Young's modulus of PP by 205 and 308%, respectively. The potential of enzymatically treated fibers to replace glass fibers in composites was studied, exhibiting similar stiffening abilities at 60 wt.% of date palm fiber (6.48 GPa) and 40% of glass fibers (6.85 GPa). The intrinsic Young's modulus of the fibers was set at values around 16, 20 and 24 GPa for mechanical, chemical and enzymatic fibers. From the micromechanical analysis, the efficiency of the reinforcement as well as the contribution of the length and orientation to the Young's modulus of the composite was evaluated.
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In this work, date palm waste (DPW) stemming from the annual pruning of date palm was used as reinforcing filler in polypropylene (PP) matrix at 40% w/w. Three pre-treatment routes were performed for the DPW, namely (i) defibration, (ii) soft alkali treatment, and (iii) enzymatic treatment, to obtain date palm fibers (DPF) and to investigate the effect of each process on their chemical composition, which will ultimately affect the mechanical properties of the resulting composites. The enzymatic and alkali treatment, combined with maleated polypropylene (MAPP) as a coupling agent, resulted in a composite with higher strength and stiffness than the neat PP. The differences in the reinforcing effect were explained by the change in the morphology of DPF and their chemical surface composition according to the selected treatment of DPW. Enzymatic treatment maximized the tensile strength of the compound as a consequence of an improvement in the interfacial shear strength and the intrinsic resistance of the fibers.
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Twin-screw extrusion (TSE) is a rather recent method to produce cellulose nanofibrils (CNFs) at a high solid content under continuous feeding. Here, never-dried commercial eucalyptus pulp was used as starting material to produce CNFs by TSE after a chemical pretreatment to introduce carboxylic groups via TEMPO-mediated oxidation and carboxymethylation. Five samples with a carboxyl content ranging from 800 to 1300 µmol.g-1 were produced to explore how the carboxyl content affects the aptitude of cellulose fibers to be broken down to nanoscale. The properties of the resulting CNFs in terms of nanosized fraction, morphology and rheological properties were investigated. A critical carboxyl content of 700 µmol.g-1was a prerequisite for the successful conversion of cellulose fibers into a CNF gel by TSE, regardless the pretreatment method. The degree of swelling of the fibers was put forward to account for this critical parameter.
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Celulose/síntese química , Nanofibras/química , Celulose/química , Tamanho da Partícula , Propriedades de SuperfícieRESUMO
Emulsion polymerization provides a sustainable way to produce latex polymers for coatings and adhesives thanks to the use of water as a dispersion medium. This synthesis approach can be even more attractive if synthetic surfactant can be replaced by biobased solid particles as a stabilizer, through what is known as a "Pickering effect". Herein, latex dispersions with solid content up to 35 wt% were successfully produced by emulsion polymerization using starch nanocrystals (SNCs) as a sole stabilizer and H2O2/citric acid as a redox-initiator. The effect of the SNC modification with vinyltriethoxysilane (VTES) on the colloidal properties of the polymer dispersion and performance of the resulting nanocomposite film were investigated. As an application of this approach, pressure-sensitive adhesive (PSA) dispersions have been prepared via Pickering emulsion polymerization in the presence of 8 wt% SNCs. The use of VTES-SNCs has a beneficial impact on the performance of PSAs with improved peel strength and wettability. The possibility to use SNCs as a stabilizer to replace synthetic surfactants in emulsion polymerization opens new avenues for the application of SNCs as biobased Pickering stabilizers to produce latex for coatings, adhesives, inks, and textiles.