Polymers

Cellulose crystallinity can be described according to the crystal size and the crystallinity index (CI). In this research, using Fourier-transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) methods, we studied the crystallinity of three different types of cellulose: banana rachis (BR), commercial cellulose (CS), and bacterial cellulose (BC). For each type of cellulose, we analyzed three different crystallization grades. These variations were obtained using three milling conditions: 6.5 h, 10 min, and unmilled (films). We developed a code in MATLAB software to perform deconvolution of the XRD data to estimate CI and full width at half-maximum (FWHM). For deconvolution, crystalline peaks were represented with Voigt functions, and a Fourier series fitted to the amorphous profile was used as the amorphous contribution, which allowed the contribution of the amorphous profile to be more effectively modeled. Comparisons based on the FTIR spectra and XRD results showed there were no compositional differences between the amorphous samples. However, changes associated with crystallinity were observed when the milling time was 10 min. The obtained CI (%) values show agreement with values reported in the literature and confirm the effectiveness of the method used in this work in predicting the crystallization aspects of cellulose samples. Full article

The main advantages of the three-dimensional (3D) printing process are flexible design, rapid prototyping, multi-component structures, and minimal waste. For stereolithography (SLA) 3D printing, common photocurable polymers, such as bisphenol-A glycidyl methacrylate (Bis-EMA), trimethylolpropane triacrylate (TMPTMA), as well as urethane oligomers, have been widely used. For a successful 3D printing process, these photocurable polymers must satisfy several requirements, including transparency, a low viscosity, good mechanical strength, and low shrinkage post-ultraviolet curing process. Herein, we investigated SLA-type photocurable resins prepared using Bis-EMA, TMPTMA, and urethane oligomers. The flexural strength, hardness, conversion rate, output resolution, water absorption, and solubility of the printed materials were investigated. The degree of conversion of the printed specimens measured by infrared spectroscopy ranged from 30 to 60%. We also observed that 64–80 MPa of the flexural strength, 40–60 HV of the surface hardness, 15.6–29.1 MPa of the compression strength, and 3.3–14.5 MPa of the tensile strength. The output resolution was tested using three different structures comprising a series of columns (5–50 mm), circles (0.6–6 mm), and lines (0.2–5 mm). In addition, we used five different pigments to create colored resins and successfully printed complex models of the Eiffel Tower. The research on resins, according to the characteristics of these materials, will help in the design of new materials. These results suggests that acrylate-based resins have the potential for 3D printing. Full article

In this study, CNCs were extracted from durian rind. Modification to CNCs with saponin was conducted at 50 °C for one h. CNCs and CNCs-saponin were employed as dexamethasone carriers. Modification to CNCs using saponin did not change the relative crystallinity of CNCs. CNCs’ molecular structure and surface chemistry did not alter significantly after modification. Both nanoparticles have surface charges independently of pH. Dexamethasone-released kinetics were studied at two different pH (7.4 and 5.8). Higuchi, Ritger–Peppas, first-order kinetic and sigmoidal equations were used to represent the released kinetic data. The sigmoidal equation was found to be superior to other models. The CNCs and CNCs-saponin showed burst release at 30 min. The study indicated that cell viability decreased by 30% after modification with saponin. Full article

Currently, the requirements for adsorbent materials are based on their environmentally friendly production and biodegradability. However, they are also related to the design of materials to sustain many cycles in pursuit of low cost and profitable devices for water treatments. In this regard, a chitosan reinforced with poly-ε-caprolactone thermoplastic composite was prepared and characterized by scanning electron microscopy; Fourier transforms infrared spectroscopy, X-ray diffraction analysis, mechanical properties, as well as erosion and swelling assays. The isotherm and kinetic data were fitted with Freundlich and pseudo-second-order models, respectively. The adsorption equilibrium capacities at pH 6 of Zn(II), Cu(II), Fe(II), and Al(III) were 165.59 ± 3.41 mg/g, 3.91 ± 0.02 mg/g, 10.72 ± 0.11 mg/g, and 1.99 ± 0.22 mg/g, respectively. The adsorbent material lost approximately 6% of the initial mass in the adsorption-desorption processes. Full article

The development of scaffold-based nanofilms for the acceleration of wound healing and for maintaining the high level of the healthcare system is still a challenge. The use of naturally sourced polymers as binders to deliver nanoparticles to sites of injury has been highly suggested. To this end, chitosan (CS) was embedded with different nanoparticles and examined for its potential usage in wound dressing. In detail, chitosan (CS)-containing zinc sulfide (ZnS)/zirconium dioxide (ZrO₂)/graphene oxide (GO) nanocomposite films were successfully fabricated with the aim of achieving promising biological behavior in the wound healing process. Morphological examination by SEM showed the formation of porous films with a good scattering of ZnS and ZrO₂ nanograins, especially amongst ZnS/ZrO₂/[email protected] film. In addition, ZnS/ZrO₂/[email protected] displayed the lowest contact angle of 67.1 ± 0.9°. Optically, the absorption edge records 2.35 eV for pure chitosan, while it declines to 1.8:1.9 scope with the addition of ZnS, ZrO₂, and GO. Normal lung cell (WI-38) proliferation inspection demonstrated that the usage of 2.4 µg/mL ZnS/ZrO₂/[email protected] led to a cell viability % of 142.79%, while the usage of 5000 µg/ mL led to a viability of 113.82%. However, the fibroblast malignant cell line exposed to 2.4 µg/mL ZnS/ZrO₂/[email protected] showed a viability % of 92.81%, while this percentage showed a steep decline with the usage of 5000 µg/ mL and 2500 µg/mL, reaching 23.28% and 27.81%, respectively. Further biological assessment should be executed with a three-dimensional film scaffold by choosing surrounding media characteristics (normal/malignant) that enhance the selectivity potential. The fabricated scaffolds show promising selective performance, biologically. Full article

Potato waste, such as peels, broken or spoiled potatoes and grape bagasse residues from the winery industry, can be used for the biotechnological production of high-value products. In this study, green, sustainable and highly productive technology was developed for the production of antioxidant bacterial cellulose (BC). The aim of this work was to evaluate the feasibility of a low-cost culture medium based on wine bagasse and potato waste to synthesize BC. Results show that the production of BC by Komagateibacter xylinus in the GP culture medium was five-fold higher than that in the control culture medium, reaching 4.0 g/L BC in 6 days. The compounds of the GP culture medium improved BC production yield. The mechanical, permeability, swelling capacity, antioxidant capacity and optical properties of the BC films from the GP medium were determined. The values obtained for the tensile and puncture properties were 22.77 MPa for tensile strength, 1.65% for elongation at break, 910.46 MPa for Young’s modulus, 159.31 g for burst strength and 0.70 mm for distance to burst. The obtained films showed lower permeability values (3.40 × 10⁻¹² g/m·s·Pa) than those of other polysaccharide-based films. The BC samples showed an outstanding antioxidant capacity (0.31–1.32 mg GAE/g dried film for total phenolic content, %DPPH^• 57.24–78.00% and %ABTS^•+ 89.49–86.94%) and excellent UV-barrier capacity with a transmittance range of 0.02–0.38%. Therefore, a new process for the production of BC films with antioxidant properties was successfully developed. Full article

The amphiphilic block copolymer poly(N-isopropylacrylamide)–Ge(C₆F₅)₂–poly(2,2,3,3-tetrafluoropropyl methacrylate) was prepared by the reaction of chain transfer to bis-(pentafluorophenyl)germane during the polymerization of N-isopropylacrylamide and the subsequent postpolymerization of isolated functional polymers in 2,2,3,3–tetrafluoropropyl methacrylate. The conversion of the block copolymer was 68% and the molecular weight of the sample was 490,000 g/mol. The colloidal chemical properties of Langmuir monolayers and Langmuir–Blodgett films of synthesized block copolymer have been studied. For comparison, a functional polymer, namely, poly-N-isopropylacrylamide with terminal –Ge(C₆F₅)₂H group, was synthesized and studied. The concentrations of spreading solutions were selected and the effect of subphase acidity on the formation of monolayers of macromolecules of the block copolymer was studied. It was found that regardless of the acidity of the subphase, high pressure of fracture of films are characteristic of monolayers of collapse pressures π_max = (48–61) mN/m. The morphology of the Langmuir–Blodgett films of functional polymer exhibit isolated elongated micelles with high densities in the form of “octopus” on the periphery of which there are terminal hydrophobic groups. For the Langmuir–Blodgett film of block copolymer, a comb-like structure is observed with characteristic protrusions. Full article

This study explored the synergistic effects of simultaneously using calcium and gallium cations in the cross-linking of alginate, detailing its effects on the characteristics of alginate compared to its single cation counterparts. The primary goal is to determine if there are any synergistic effects associated with the utilisation of multiple multivalent cations in polymer cross-linking and whether or not it could therefore be used in pharmaceutical applications such as wound healing. Given the fact divalent and trivalent cations have never been utilised together for cross-linking, an explanation for the mode of binding that occurs between the alginate and the cations during the cross-linking process and how it may affect the future applications of the polymer has been investigated. The calcium gallium alginate polymers were able to retain the antibacterial effects of gallium within the confines of the polymer matrix, possessing superior rheological properties, 6 times that of pure calcium and pure gallium, coupled with an improved swelling capacity that is 4 times higher than that of gallium alginate. Full article

At present, achieving good storability and water damage resistance remains challenging for cold-patching asphalt mixtures (CAMs). To address this issue, this study selects styrene–ethylene–butadiene–styrene copolymer (SEBS) and diesel as a modifier and diluent, respectively, to improve the water stability and storability of CAMs. The diesel oil content is determined through the Brookfield rotational viscosity test, and the modifier content is obtained through the Marshall stability test. With the empirical formula method, paper trail test, and modified Marshall test, mixed designs of CAMs modified with and without SEBS are established to determine the best cold-patching asphalt content. On this basis, the modification effect of SEBS is verified by comparing the test results of the modified and unmodified CAMs, and the water stability and Marshall stability tests are conducted before and after CAM storage, respectively. Results show that the optimum contents of SEBS and diesel oil are 7.5% and 40% of the base asphalt weight, respectively, and the best modified asphalt content is 4.6% of the mineral material weight in CAM. The Marshall residual stability and freeze–thaw splitting strength ratio of the 7.5% SEBS-modified CAM are increased by 20.1% and 15.7%, respectively, relative to the unmodified CAM, and the storage performance requirement of at least two months can be guaranteed. Full article

The properties of solvent-based pressure-sensitive adhesive (PSA) acrylics, especially shrinkage, are mostly determined by the type and amount of the crosslinking agent added to the prepolymer or by the crosslinking method. The shrinkage profiles of the selected solvent-based acrylic PSA coated on PVC film were investigated using metal chelates (between 0 and 0.55 wt.%), N-methylol acrylamide (up to 8 wt.%), polycarbodiimide and amino resins (up to 6 wt.%), diisocyanate (up to 1 wt.%), multi-functional propylene imines (up to 0.9 wt.%), conventional photoinitiators (up to 3 wt.%) and copolymerizable photoinitiators (up to 2 wt.%). These chemicals were both crosslinking agents that react after the solvent has been evaporated or at higher temperatures, and to the crosslinking agents that react under UV radiation. Some of them were copolymerizable, and others were added to the prepolymer before crosslinking. The best results of shrinkage (0.2%) were obtained by using the UV-crosslinking method and copolymerizable photoinitiators ZLI 3331 and ABP, as well as metal chelates AlACA and TiACA and multifunctional propylene imine Neocryl CX-100 (0.2%). Acceptable results were also achieved for amide BPIA (0.3%), benzophenone derivative PCB (0.4%), N-methylol acrylamide (0.35%) and benzoguanamine resin Cymel 1123 (0.45%). Full article

Magnetic extraction offers a rapid and low-cost solution to microplastic (MP) separation, in which we magnetize the hydrophobic surface of MPs to separate them from complex environmental matrices using magnets. We synthesized a hydrophobic Fe-silane based nanocomposite ([email protected]₂/MDOS) to separate MPs from freshwater. Pristine and weathered, polyethylene (PE) and tire wear particles (TWP) of different sizes were used in the study. The weathering of MPs was performed in an accelerated weathering chamber according to ISO 4892-2:2013 standards that mimic natural weathering conditions. The chemical properties and morphology of the [email protected]₂/MDOS, PE and TWP were confirmed by Fourier transform infrared spectroscopy and Scanning electron microscopy, respectively. The thermal properties of PE and TWP were evaluated by Thermogravimetric analysis. Using 1.00 mg of [email protected]₂/MDOS nanocomposite, 2.00 mg of pristine and weathered PE were extracted from freshwater; whereas, using the same amount of the nanocomposite, 7.92 mg of pristine TWP and 6.87 mg of weathered TWP were extracted. The retrieval of weathered TWP was 13% less than that of pristine TWP, which can be attributed to the increasing hydrophilicity of weathered TWP. The results reveal that the effectiveness of the magnetic separation technique varies among different polymer types and their sizes; the weathering of MPs also influences the magnetic separation efficiency. Full article

Oregano essential oil was encapsulated in poly-ϵ-caprolactone nanoparticles by a nanoprecipitation method using glycerin as a moisturizer. Nanocapsule characterization was performed by measuring the particle size, colloidal stability and encapsulation efficiency using dynamic light scattering, UV–Vis spectrophotometry and scanning electron microscopy (SEM). The nanoparticles had a mean particle size of 235 nm with a monomodal distribution. In addition, a low polydispersity index was obtained, as well as a negative zeta potential of −36.3 mV and an encapsulation efficiency of 75.54%. Nanocapsules were applied to polyester textiles through bath exhaustion and foulard processing. Citric acid and a resin were applied as crosslinking agents to improve the nanocapsules’ adhesion to the fabric. The adsorption, desorption, moisture content and essential oil extraction were evaluated to determine the affinity between the nanocapsules and the polyester. The adsorption was higher when the citric acid and the resin were applied. When standard oregano nanocapsules were used, almost all of the impregnated nanoparticles were removed when washed with water. The moisture content was evaluated for treated and non-treated textiles. There was a significant increase in the moisture content of the treated polyester compared to the non-treated polyester, which indicates that the polyester hydrophilicity increased with an important absorption of the essential oil nanocapsules; this can improve fabric comfort and probably promote antibacterial properties. Full article

Kaolinite supported cerium oxide (CeOx/Kaol) was successfully prepared via a deposition method and used to improve the mechanical and aging properties of styrene–butadiene rubber (SBR) composite. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results showed that cerium oxide has a successfully loading and fine distribution on the edge and surface of kaolinite. Fourier transform infrared (FT-IR) spectroscopy indicated that cerium oxide may interact with the surface hydroxyls of kaolinite. The CeOx/Kaol material had a uniform dispersion in the resulting SBR composite. The loading of cerium oxide on Kaol increases the scorch time (t₁₀) and curing time (t₉₀) of the filled SBR composites relative to the pure SBR. The mechanical parameters of the filled SBR composites were increased significantly. The tensible strength and tear strength at 40 phr content with 4% CeOx loading reached 12.85 Mpa and 51.16 kN/m, which were increases of 35.9% and 38.3%, respectively, relative to that of the SBR filled with raw Kaol. The anti-ageing characteristic of the resulting composite showed an obvious improvement with the loading of CeOx. Meanwhile, the reinforcement and anti-ageing mechanisms of the CeOx/Kaol were proposed. These results were attributed to the complexation between Ce elements on the surface of Kaol and rubber chains through a double bond. This could improve the incorporation between rubber molecules and filler particles, and restrict rubber chain motion via trapping rubber chains. Full article

The electrostatic complexation between double hydrophilic block copolymers (DHBCs) and a model porphyrin was explored as a means for the development of polyion complex micelles (PICs) that can be utilized as photosensitive porphyrin-loaded nanoparticles. Specifically, we employed a poly(2-(dimethylamino) ethyl methacrylate)-b-poly[(oligo ethylene glycol) methyl ether methacrylate] (PDMAEMA-b-POEGMA) diblock copolymer, along with its quaternized polyelectrolyte copolymer counterpart (QPDMAEMA-b-POEGMA) and 5,10,15,20-tetraphenyl-21H,23H-porphine-p,p′,p″,p′′′-tetrasulfonic acid tetrasodium hydrate (TPPS) porphyrin. The (Q)PDMAEMA blocks enable electrostatic binding with TPPS, thus forming the micellar core, while the POEGMA blocks act as the corona of the micelles and impart solubility, biocompatibility, and stealth properties to the formed nanoparticles. Different mixing charge ratios were examined aiming to produce stable nanocarriers. The mass, size, size distribution and effective charge of the resulting nanoparticles, as well as their response to changes in their environment (i.e., pH and temperature) were investigated by dynamic and electrophoretic light scattering (DLS and ELS). Moreover, the photophysical properties of the complexed porphyrin along with further structural insight were obtained through UV-vis (200-800 nm) and fluorescence spectroscopy measurements. Full article

Textile-reinforced concrete (TRC) is a cement-based composite material that uses textile as a reinforcement material. The weft-direction fiber bundles in the traditional orthogonally arranged warp–weft textile hardly bear force, and its bonding strength with the weft fiber bundle is not ideal. Under the action of force, a small included angle between the stressed fiber bundle and the stressed direction can effectively increase the anchoring effect of their fibers in the matrix, resulting in higher bonding and reinforcement efficiency. To improve the utilization rate of fibers and the bonding strength between the textile and the concrete matrix, an arrangement along the diagonal of the grids was proposed in this paper. The flexural properties of basalt TRC plates with orthogonal grids (OG-BTRC) and plates with nonorthogonal grids (NOG-BTRC) with different grid angles and grid sizes with different laying methods, namely, a side layout (SL) and diagonal layout (DL), were studied through four-point bending tests. A comparative analysis was carried out with an ABAQUS simulation and the test results. The results showed that with a decrease in the grid angle, the BTRC specimens gradually showed a failure mode of multiple cracks, and most of the cracks appeared in the pure bending area; as the grid angle decreased, the BTRC specimens exhibited excellent flexural bearing capacity, good ductility, and high toughness. The total number of cracks on the specimen increased when it failed, while the spacing of the cracks decreased, and the fracture morphology appeared as fine and uniform features. The toughness of the specimen with a small grid angle using the DL laying method was greater than that using the SL laying method. The software simulation value matched the test data well, which proved that the test result was reliable. Full article

In oral administration systems, mucoadhesive polymers are crucial for drug localization and target-specific activities. The current work focuses on the application of thiolated xanthan gum (TXG) to develop and characterize a novel mucoadhesive nanocrystal (NC) system of simvastatin (SIM). Preparation of SIM-NC was optimized using response surface methodology (RSM) coupled with statistical applications. The concentration of Pluronic F-127 and vacuum pressure were optimized by central composite design. Based on this desirable approach, the prerequisites of the optimum formulation can be achieved by a formulation having 92.568 mg of F-127 and 77.85 mbar vacuum pressure to result in EE of 88.8747% and PS of 0.137.835 nm. An optimized formulation was prepared with the above conditions along with xanthan gum (XG) and TXG and various parameters were evaluated. A formulation containing TXG showed 98.25% of SIM at the end of 96 h. Regarding the mucoadhesion potential evaluated by measuring zeta potential, TXG-SIM-NC shoed the maximum zeta potential of 16,455.8± 869 mV at the end of 6 h. The cell viability percentage of TXG-SIM-NC (52.54 ± 3.4% with concentration of 50µg/mL) was less than the plain SIM, with XG-SIM-NC showing the highest cytotoxicity on HSC-3 cells. In vivo pharmacokinetic studies confirm the enhanced bioavailability of formulated mucoadhesive systems of SIM-NC, with TXG-SIM-NC exhibiting the maximum. Full article

This paper provides a study of the liquid-phase polypropylene polymerization on a heterogeneous titanium–magnesium Ziegler–Natta-type catalyst. A kinetic model was developed that included the activation of potential active centers, chain growth, transferring the chains to hydrogen and monomer, and the deactivation of active centers. The model was created to predict the polymerization rate, polymer yield, and average molecular weights of polymer chains where the polymerization temperature changes from 40 to 90 °C. In developing polycentric kinetic models, there is a difficulty associated with evaluating the kinetic constants of the rates of elementary reactions/stages in polymerization. Each heterogeneous titanium–magnesium catalyst (TMC), including a co-catalyst, as well as an internal and an external electron donor, has its own set of kinetic parameters. Therefore, its kinetic parameters must be defined for each new catalyst. The presented algorithm for identifying the kinetic constants of rates starts with a kinetic model that considers one type of active centers. At the second stage, a deconvolutional analysis is used for the molecular weight distribution (MWD) of the gel permeation chromatography (GPC) data of the polypropylene samples and the most probable distribution of Flory chain lengths is found for each type of active centers. At the third stage, the single-center model is transformed into a polycentric kinetic model. For the catalyst system, five types of active centers were identified, together with a mass fraction and a number-average molecular weight for each active center type of the catalyst, which is consistent with the published results for similar Ti-based Ziegler–Natta catalysts. Full article

The limited number of materials and mechanical weakness of fused deposition modeling (FDM) parts are deficiencies of FDM technology. The preparation of polymer composites parts with suitable filler is a promising method to improve the properties of the 3D printed parts. However, the agglomerate of filler makes its difficult disperse in the matrix. In this work, graphene nanoplatelets (GnPs) were surface modified with chemical, low-temperature plasma and in situ methods, in order to apply them as fillers for thermoplastic polyurethane (TPU). Following its modification, the surface chemical composition of GnPs was analyzed. Three w% of surface-modified GnPs were incorporated into TPU to produce FDM filaments using a melting compounding process. Their effects on rheology properties and electrical conductivity on TPU/GnPs composites, as well as the dimensional accuracy and mechanical properties of FDM parts, are compared. The images of sample facture surfaces were examined by scanning electron microscope (SEM) to determine the dispersion of GnPs. Results indicate that chemical treatment of GnPs with zwitterionic surfactant is a good candidate to significantly enhance TPU filaments, when considering the FDM parts demonstrated the highest mechanical properties and lowest dimensional accuracy. Full article

Polymeric coating materials (PCMs) are promising candidates for developing next-generation flexible displays. However, PCMs are frequently subjected to external stimuli, making them highly susceptible to repeated damage. Therefore, in this study, a highly self-healing PCM based on a charge transfer complex (CTC) was developed, and its thermal, self-healing, and mechanical properties were examined. The self-healing material demonstrated improved thermal stability, fast self-healing kinetics (1 min), and a high self-healing efficiency (98.1%) via CTC-induced multiple interactions between the polymeric chains. In addition, it eliminated the trade-off between the mechanical strength and self-healing capability that is experienced by typical self-healing materials. The developed PCM achieved excellent self-healing and superior bulk (in-plane) and surface (out-of-plane) mechanical strengths compared to those of conventional engineering plastics such as polyether ether ketone (PEEK), polysulfone (PSU), and polyethersulfone (PES). These remarkable properties are attributed to the unique intermolecular structure resulting from strong CTC interactions. A mechanism for the improved self-healing and mechanical properties was also proposed by comparing the CTC-based self-healing PCMs with a non-CTC-based PCM. Full article