Microbial cellulose as a support for photocatalytic oxidation of toluene using TiO2 nanoparticles

The aim of this study was to investigate the feasibility of toluene degradation using impregnated microbial cellulose (MC) with titanium dioxide (TiO₂) nanoparticles (MC/TiO₂). The effects of the initial toluene concentration and ultraviolet (UV) source on the degradation efficiency of toluene have been evaluated. The experimental results showed that the rate of toluene degradation decreased with an increasing of the inlet toluene concentration. After 40 min reaction time, the decomposition rate (%) of toluene decreased from 72.3% to 36.02% for experiments conducted at 100 and 500 ppm, respectively. The degradation efficiency of toluene decreased with application of UVA source instead of UVC source. The toluene degradation efficiency (%) reached to 87.79% and 76.87% for UVC and UVA irradiation, respectively. At initial toluene concentration of 100 mg/L, toluene degradation efficiency for photocatalysis and photolysis processes were 70.2% and 10.65%, respectively; indicating that the photocatalytic degradation efficiency is significantly higher than that of photolytic degradation efficiency. Furthermore, photocatalytic degradation kinetics of toluene was studied and the rates of degradation were found to conform to pseudo‐second‐order kinetic. As shown in the present study, impregnation of TiO₂ nanoparticles on MC/TiO₂ significantly increases toluene removal for short exposure time. It can be concluded that the MC acted as a local toluene concentrator by adsorbing pollutants from the air stream, and thereby diffusing them to the TiO₂ nanoparticles for photodegradation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43051.     

Effect of metal-oxide nanoparticle presence and alginate cross-linking on cellulose nanocrystal-based aerogels

In a context where environmentally friendly materials development is becoming essential, cellulose is achieving a great importance. Cellulose nanocrystal (CNC) hierarchical and nanostructured porous network is a versatile nanoparticle support to fabricate nanocomposites for different solutions. In this work, CNC-based aerogels loaded with copper and palladium-oxide nanoparticles have been synthesized by nitrate precursor reduction followed by freeze-drying, after a scalable, surfactantless and room temperature process. The in situ produced nanoparticles are entrapped by CNC due to ionic interactions and aerogels show an uniformly colored macroscopic appearance. Metal oxide nanoparticle (MOx) mediated hybridization promotes remarkable changes in CNC wettability, free surface energy and thermal stability. These modifications are dependent on the type of metal precursor and concentration and have been analyzed by different techniques. Overall, obtained CNC hybrid aerogels are lightweight (12–30 mg^.cm⁻³) and highly porous (98%–99%). Finally, more mechanically resistant hybrid aerogels have been synthesized through the incorporation of sodium alginate and tested by compressive stress measurements.     

Synthesis of poly(butyl acrylate)—laponite nanocomposite nanoparticles for improving the impact strength of poly(lactic acid)

This work aims at preparing and characterizing poly(butyl acrylate) (PBA)—laponite (LRD) nanocomposite nanoparticles and nanocomposite core (PBA‐LRD)‐shell poly(methyl methacrylate) (PMMA) nanoparticles, on the one hand, and the morphology and properties of poly(lactic acid) (PLA)‐based blends containing PBA‐LRD nanocomposite nanoparticles or (PBA‐LRD)/PMMA core–shell nanoparticles as the dispersed phase, on the other hand. The PBA and (PBA‐LRD)/PMMA nanoparticles were synthesized by miniemulsion or emulsion polymerization using LRD platelets modified by 3‐methacryloxypropyltrimethoxysilane (MPTMS). The grafting of MPTMS onto the LRD surfaces was characterized qualitatively using FTIR and quantitatively using thermogravimetric analysis (TGA). The amounts of LRD in the PBA‐LRD nanocomposites were characterized by TGA. The PBA/PMMA core–shell particles were analyzed by ¹H‐NMR. Their morphology was confirmed by SEM and TEM. Mechanical properties of (PBA‐LRD)/PLA blends and (PBA‐LRD)/PMMA/PLA ones were tested and compared with those of the pure PLA, showing that core–shell particles allowed increasing impact strength of the PLA while minimizing loss in Young modulus and tensile strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Increasing the elongation at break of polyhydroxybutyrate biopolymer: Effect of cellulose nanowhiskers on mechanical and thermal properties

Bionanocomposites based on polyhydroxybutyrate (PHB) and cellulose nanowhiskers (CNWs) were prepared by dispersing CNWs in poly(ethylene glycol) (PEG) plasticizer subsequently incorporating the CNWs/PEG suspensions in the matrix. The thermal properties of the nanocomposites indicate an enlargement in the processing window in comparison to the neat PHB. The nanocomposites showed a remarkable increase in the strain level (50 times related to the neat PHB), without a significant loss of the tensile strength with the incorporation of small concentrations of CNWs in the final nanocomposite (up to 0.45 wt %). This behavior was explained in terms of a considerable chain orientation promoted by the presence of CNWs in the same direction of the applied load, which activated shear flow of the polymer matrix. The results described here can be explored to extend the applications of this biopolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Chitosan/P3HT biohybrid films as polymer matrices for the in-situ synthesis of CdSe quantum dots. Experimental and theoretical studies

Biohybrid nanocomposite films were obtained through a simple two-step methodology. Films of chitosan/poly(3-hexylthiophene) (CS/P3HT) were used as polymer matrices for the in-situ synthesis and stabilization of CdSe quantum dots. The biohybrid materials were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), Raman spectroscopy, UV–visible spectroscopy, thermogravimetric analysis (TGA), field emission scanning electron microscope (FESEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence spectroscopy (PL). The effects of the P3HT composition on the properties of the QDs in the films were analyzed. The results confirmed that CS/P3HT films provided an adequately confining matrix for the growth of CdSe QDs with a fairly uniform size and revealed that the interactions between the CdSe nanoparticles and the CS/P3HT matrix mainly involved the  OH and  NH₂ groups. The optical band gaps of the biohybrid nanocomposite films were estimated. The results of photoluminescence revealed that a charge transfer phenomenon occurred in the polymer system. Finally, theoretical analyses suggest that the CdSe QDs would be preferentially located onto the chitosan domains.     

Assessment of ball milling methodology to develop polylactide‐bacterial cellulose nanocrystals nanocomposites

In this work, ball milling is evaluated as a methodology to develop polylactide (PLA)‐bacterial cellulose nanocrystals (BCNC) nanocomposites. This technique, widely used for clay‐based nanocomposites, is effective in breaking up to a very large extent the freeze‐dried nanocellulose aggregates, giving raise to transparent films similar to the neat PLA films. Incorporation of the nanofiller through this methodology enhances the polymer crystallinity index. An increase in the onset degradation temperature and a significant reinforcing effect in terms of an increase in the storage modulus and in the tan delta peak are also observed. Improved barrier to oxygen at high relative humidity (80%) is also noticed, reaching the best performance at the lowest BCNC loading (0.5 wt %). These improvements are related to the relatively good nanocellulose dispersion and distribution attained for low loadings of the nanofiller. Thus, the ball milling methodology appears as a feasible processing methodology for developing PLA‐BCNC nanocomposites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41605.     

Fabrication of regenerated cellulose nanoparticles/waterborne polyurethane nanocomposites

Regenerated cellulose nanoparticles (RCNs) are ideal materials for new biomass polymer composites industries. RCNs and composites of RCNs and water‐borne polyurethane (RCN/WPU) were prepared using a facile and environmentally friendly approach without the use of any harmful chemicals. The morphological, thermal, and mechanical properties of the RCN/WPU nanocomposite were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), rheometer, wide‐angle X‐ray diffraction, and enzymatic hydrolysis. RCNs exhibited low crystallinity upon regeneration with an NaOH‐based aqueous solution, and were identified by SEM and TEM to consist of the more thermodynamically stable cellulose form. TGA showed that the thermal stability of RCN/WPU nanocomposites was increased by the addition of RCNs. Finally, enzymatic hydrolysis using cellulase indicated that the biodegradability of RCN/WPU nanocomposites was also improved. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46633.     

PLA/sepiolite and PLA/calcium carbonate nanocomposites: A comparison study

Polylactic acid (PLA)‐based nanocomposites comprising two different types of nanofillers, i.e. sepiolite (SEP) and nano calcium carbonate (NCC), were prepared by internal mixing and injection molding. Because of the different aspect ratio, surface area, and surface property of the nanofillers, their effects on the morphological, mechanical, dynamic mechanical, rheological, and thermal properties of the nanocomposites were shown to be very different. NCC demonstrated more uniform particle dispersion and matrix compatibility than did SEP because of the former's surface treatment, thus leading to higher strength and strain‐at‐failure of PLA/NCC composites. On the other hand, larger aspect ratio and surface area of SEP caused higher melt viscosity, stronger shear thinning, and better thermal resistance of PLA/SEP composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Biocomposite membranes of sodium alginate and silk fibroin fibers for biomedical applications

Biocomposite membranes from biodegradable and biocompatible natural polymers were prepared from sodium alginate solution reinforced with silk fibroin fibers in several fiber content by casting and solvent evaporation. The properties of these biocomposites were investigated by scanning electron microscopy, swelling test, water vapor transmission, mechanical and thermal analyses, and cytotoxicity test. A biocomposite with uniform fiber dispersion and good fiber–matrix interaction was obtained through the incorporation of fibroin fibers in the alginate membrane, even though the fibers were used without any surface treatment to enhance the interfacial adhesion. The incorporation of fibroin fibers improved the tensile strength and also provided a new property to the alginate, that is, the resistance to tear. Moreover, the use of silk fibroin fibers in polymeric composites can result in a material with adequate characteristics for application in the biomaterial field, especially as wound dressings, because of its nontoxic effect to cells, flexibility, and resistance to tear. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3451–3457, 2013     

MWCNTs reinforced conductive,self-healing polyvinyl alcohol/carboxymethyl chitosan/oxidized sodium alginate hydrogel as the strain sensor

The preparation and application of hydrogel has been a hot research field in recent years. Here in, a composite hydrogel based on poly(vinyl alcohol) (PVA), carboxymethyl chitosan (CMCS), oxidized sodium alginate (OSA), and oxidized multiwall carbon nanotubes (OMWCNTs) was successfully prepared. Hydrogen and imine bonds of the hydrogel endowed the composite hydrogel with self-healing property and pH sensitivity. The fracture strength of the hydrogel was enhanced to about 0.8 MPa with the help of OMWCNTs, which was about 2.5 times compared with the one without OMWCNTs. Meanwhile, a new conductive network inside the hydrogel was constructed by OMWCNTs, which improved the conductivity of the hydrogel from 1.75 × 10⁻⁴ to 7.02 × 10⁻⁴ S/cm. The sensing test of the hydrogel showed that it could produce profound feedback signals for the deformation caused by external force and response to human body movements, such as finger bending, swallowing, and speaking.     

Hydrogels of starch/carboxymethyl cellulose crosslinked with sodium trimetaphosphate via reactive extrusion

Hydrogels are materials with advantages in specific applications, such as, retention of food active compounds. This work aims to develop starch (S)/carboxymethyl cellulose (CMC) hydrogels with porous structure, using reactive extrusion to promote crosslinking with sodium trimetaphosphate (STMP). The expansion, porosity, degree of substitution, gel fraction, swelling properties, and FTIR are studied, comparing S, S/CMC, S/STMP, and S/CMC/STMP formulations. Samples containing STMP present the same degree of substitution (0.050 ± 0.001). Higher porosity and percentage of open pores are observed in the mixed hydrogel (S/CMC/STMP). Crosslinking increase the swelling capacity at pH 7, and this property, just like the gel fraction, are sensitive to pH variations. The hydrogel S/CMC present the highest swelling rate compared with the other samples, suggesting strong interaction between components. The reactive extrusion process is efficient to produce starch and starch/CMC hydrogels crosslinked with STMP and the overall results demonstrate the advantages of the mixed hydrogel.     

Optimized synthesis,characterization, and antibacterial activity of an alginate–cupric oxide bionanocomposite

In this research, the structural features and optimal conditions for the synthesis of an alginate–CuO nanocomposite with the highest antibacterial activity were investigated. CuO nanoparticles (NPs) and the alginate biopolymer were synthesized chemically and biologically, respectively. Nine nanocomposite compounds were produced on the basis of the Taguchi method with different levels of CuO NPs and the alginate biopolymer nanocomposite with different stirring times. Fourier transform infrared spectroscopy, high‐resolution field emission scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy analysis confirmed the formation of the nanocomposites. The nanocomposite synthesized with 8 mg/mL copper oxide NPs and 2 mg/mL alginate biopolymer with 60 min of stirring time showed the highest antibacterial activity. The results of two colony forming units and disk‐diffusion methods indicated a stronger antibacterial activity of the alginate–CuO nanocomposite compared with those of its components. The alginate–CuO nanocomposite showed the potential ability to act as an antimicrobial agent against Gram‐negative and Gram‐positive bacteria. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45682.     

Electrorheological behavior of low filled suspensions of highly anisometric montmorillonite particles

The electrorheological (ER) behavior of modified montmorillonite (MMT) suspensions in polydimethylsiloxane is studied. As established by rotational viscometry, the samples with a dispersed phase concentration from 1 to 8 wt % reveal viscous Newtonian behavior and dramatically change their properties to elastic when electric field is applied. The rheological characteristics of the suspensions over 0–7 kV mm⁻¹ range of electric field strengths are also studied. Novel X-ray diffraction method is developed to evaluate the suspension of the filler in a siloxane medium and to calculate the degree of its exfoliation. The dependence of exfoliation degree, dielectric, and ER characteristics on the type of modifier in the MMT structure is considered. Based on the obtained data, a new model of system behavior with the various types of fillers is proposed and the prospects of utilizing MMT as a filler for ER fluids are demonstrated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47678.     

Increased thermal stability of nanocellulose composites by functionalization of the sulfate groups on cellulose nanocrystals with azetidinium ions

Cellulose nanocrystals (CNCs) prepared via sulfuric acid hydrolysis are decorated with sulfate groups that yield a stable water suspension. To make the CNCs adaptable for use in composites, the hydroxyl groups on the surface are usually hydrophobized. In this article, an alternative hydrophobization method is described in which the sulfate groups are conjugated with azetidinium salts. The results of this study show that the sulfate groups can be functionalized with azetidinium salts and from thermal studies, it was discovered that the functionalization led to a 100 °C increase in thermal stability, compared with unmodified CNCs. The nanocomposites prepared by extrusion of CNC‐coated low‐density polyethylene powder displayed similar mechanical properties as the CNC‐reference sample, but without the discoloration, due to the increased thermal stability. In conclusion, the azetidinium reagent reacts preferentially with sulfate groups, and this new type of chemical conversion of sulfate groups on polysaccharides will be beneficial in nanocomposite manufacturing. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45963.     

Poly(vinylidene fluoride‐co‐hexafluoropropylene) nanocomposites incorporating cellulose nanocrystals with potential applications in lithium ion batteries

Cellulose nanocrystals (CNCs) have received considerable attention recently because CNCs can be produced from renewable materials such as straw, wood, cotton, and sea animals (tunicates). CNCs are one of the stiffest organic materials, with an estimated tensile modulus (E) of 80–160 GPa depending on the starting material. In addition, composites incorporating CNCs have been fabricated from a variety of polymer matrices and CNCs have been shown to increase the E significantly and to a lesser extent the tensile strength (TS). A copolymer of poly(vinylidene fluoride) (PVDF), PVDF‐co‐hexafluoropropylene) (PVDFHFP), has received interest over the years in the area of lithium ion battery separator technology. However, the mechanical properties of neat PVDFHFP do not meet the necessary requirements for commercial separators, especially the low E. In this work, novel PVDHFHFP/CNC nanocomposite films were fabricated and characterized. It was found that incorporation of CNCs improves the E and TS. The improvement in mechanical properties of PVDFHFP upon addition of CNCs makes PVDFHFP a more suitable candidate for polymer separators in lithium ion batteries. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Self‐aggregated nanoparticles of N‐dodecyl,N′‐glycidyl(chitosan) as pH‐responsive drug delivery systems for quercetin

In this study, pH‐responsive amphiphilic chitosan (CS) nanoparticles were used to encapsulate quercetin (QCT) for sustained release in cancer therapy. The novel CS derivatives were obtained by synthesis with 2,3‐epoxy‐1‐propanol, also known as glycidol, followed by acylation with dodecyl aldehyde. Characterization was performed by spectroscopic, viscosimetric, and size‐determination methods. Critical aggregation concentration, morphology, entrapment efficiency, drug release profile, cytotoxicity, and hemocompatibility studies were also carried out. The average size distribution of the self‐assembling nanoparticles measured by dynamic light scattering ranged from 140 to 300 nm. In vitro QCT release and Korsmeyer–Peppas model indicated that pH had a major role in drug release. Cytotoxicity assessments indicated that the nanoparticles were non‐cytotoxic. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide assay further revealed that QCT‐loaded nanoparticles could inhibit MCF‐7 cell growth. In vitro erythrocyte‐induced hemolysis indicated the good hemocompatibility of the nanoparticles. These results suggest that the synthesized copolymers might be potential carriers for hydrophobic drugs in cancer therapy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45678.     

A comparative study for the behavior of 3D-printed and compression molded PLA/POSS nanocomposites

Because of the biocompatible and nontoxic character of both PLA (polylactide) and POSS (Polyhedral Oligomeric Silsesquioxane) nanoparticles, recently being a significant alternative for biomedical parts; the main purpose of this study was to investigate performance of the 3D-printed PLA/POSS nanocomposites with respect to the compression molded PLA/POSS specimens. Due to the higher uniformity and higher homogeneity in the distribution of POSS nanoparticles in each PLA matrix layer, mechanical tests (tensile, flexural, and toughness) revealed that the improvements in the strength, elastic modulus and fracture toughness values of the 3D-printed specimens were much higher compared to their compression molded counterparts, the benefits starting from 13% increasing up to 78%. It was also observed that there was almost no deterioration in the physical structure and mechanical properties of the 3D-printed specimens, even after keeping them 120 days at 37°C in a physiological solution prepared by using the standard PBS (phosphate buffered saline) tablet.     

Development and characterization of chitosan bionanocomposites containing oxidized cellulose nanocrystals

In this research, cellulose nanocrystals (CNs) were extracted from corn cobs by 2,2,6,6,‐tetramethylpiperidine‐1‐oxyl radical‐mediated oxidation combined with ultrasonic treatment for the first time. These CNs were then used as a mechanical reinforcement agent and barrier in chitosan‐based bionanocomposite films. Birefringence analyses under crossed polarizers indicated the presence of isolated nanocrystals in suspension, which was later confirmed by TEM analysis. The crystallinity index obtained from X‐ray diffraction was 92.4%. The incorporation of these nanoparticles into a filmogenic matrix of chitosan made it possible to obtain bionanocomposite films with improved properties. The water‐vapor permeability was reduced by 70%, whereas the tensile strength and Young's modulus increased by up to 136 and 224% respectively. The developed films were applied as interleaving of sliced cheese, and the efficiency was assessed by investigation of adhesion between the surfaces and by comparing its properties with two commercial interleaving products (polyethylene (PE), and Greasepel paper (GP)). Concluding, the developed films showed a substantial potential to be exploited as an interleaving film, owing to its excellent mechanical properties, permeability, hydrophobicity, and low surface adhesion compared to pure chitosan, PE, and GP films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43033.     

Prodegradant effect of titanium dioxide nanoparticulates on polypropylene–polyhydroxybutyrate blends

Polymers are gradually replacing conventional materials in various sectors of the economy because of their low cost and broad functionality. However, the high stability of polymers under most environmental conditions can lead to their accumulation in the form of waste. Polyhydroxybutyrate (PHB) is an alternative because of its biodegradability, but it is usually expensive and brittle. These aspects can be improved through the formation of blends, such as with polypropylene (PP). The objective of this study was to investigate the possibility of using titanium dioxide (TiO₂) nanoparticles as a prodegradant agent in the PP–PHB–TiO₂ system through the evaluation of the effects of these nanoparticles under UV light on the structure and properties of the materials. Samples were produced through extrusion and injection molding and were characterized by their mechanical and thermal properties and structural analyses. The results show that the TiO₂ nanoparticles were able to act as a prodegradant agent for the PP–PHB blend; they also successfully improved some of the mechanical and dynamic mechanical properties of the blend. However, a TiO₂ nanoparticle content higher than 7.5 wt % was not able to extend the photodegradation process further, possibly as a consequence of the agglomeration of nanoparticles during the processing of these more concentrated blends. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46636.     

Poly(butylene succinate)/layered double hydroxide bionanocomposites: Relationships between chemical structure of LDH anion,delamination strategy,and final properties

A series of poly(butylene succinate) (PBS) containing organo‐modified layered double hydroxide (LDH) are prepared by melt compounding and by in situ polymerization of succinic ester and 1,4‐butanediol. Various LDHs intercalated with renewable organic anions are used. More specifically, lauryl sulfate, stearate, succinate, adipate, sebacate, citrate, and ricinoleate ions are used as LDHs organo‐modifiers. The thermal, rheological, and dynamic mechanical properties of the samples are investigated. The results reveal a general mechanical reinforcement imparted by the clays. Significant changes are observed for the in situ polymerized nanocomposites, especially for LDH stearate which improves the properties of PBS nanostructure, whereas very few differences are observed for the other samples. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1931–1940, 2013