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1.
Polymers (Basel) ; 16(17)2024 Aug 29.
Artículo en Inglés | MEDLINE | ID: mdl-39274091

RESUMEN

The progress in polymer science and nanotechnology yields new colloidal and macromolecular objects and their combinations, which can be defined as complex polymer materials. The complexity may include a complicated composition and architecture of macromolecular chains, specific intermolecular interactions, an unusual phase behavior, and a structure of a multi-component polymer-containing material. Determination of a relation between the structure of a complex material, the structure and properties of its constituent elements, and the rheological properties of the material as a whole is the subject of structural rheology-a valuable tool for the development and study of novel materials. This work summarizes the author's structural-rheological studies of complex polymer materials for determining the conditions and rheo-manifestations of their micro- and nanostructuring. The complicated chemical composition of macromolecular chains and its role in polymer structuring via block segregation and cooperative hydrogen bonds in melt and solutions is considered using tri- and multiblock styrene/isoprene and vinyl acetate/vinyl alcohol copolymers. Specific molecular interactions are analyzed in solutions of cellulose; its acetate butyrate; a gelatin/carrageenan combination; and different acrylonitrile, oxadiazole, and benzimidazole copolymers. A homogeneous structuring may result from a conformational transition, a mesophase formation, or a macromolecular association caused by a complex chain composition or specific inter- and supramolecular interactions, which, however, may be masked by macromolecular entanglements when determining a rheological behavior. A heterogeneous structure formation implies a microscopic phase separation upon non-solvent addition, temperature change, or intense shear up to a macroscopic decomposition. Specific polymer/particle interactions have been examined using polyethylene oxide solutions, polyisobutylene melts, and cellulose gels containing solid particles of different nature, demonstrating the competition of macromolecular entanglements, interparticle interactions, and adsorption polymer/particle bonds in governing the rheological properties. Complex chain architecture has been considered using long-chain branched polybutylene-adipate-terephthalate and polyethylene melts, cross-linked sodium hyaluronate hydrogels, asphaltene solutions, and linear/highly-branched polydimethylsiloxane blends, showing that branching raises the viscosity and elasticity and can result in limited miscibility with linear isomonomer chains. Finally, some examples of composite adhesives, membranes, and greases as structured polymeric functional materials have been presented with the demonstration of the relation between their rheological and performance properties.

2.
Polymers (Basel) ; 16(17)2024 Sep 05.
Artículo en Inglés | MEDLINE | ID: mdl-39274155

RESUMEN

This study aims to examine the 50/50 polypropylene/polyamide 6 (iPP/PA6) system molded under confined flow conditions, both in its original state and after being modified by two different interfacial agents. This study provides two main insights. Firstly, it focuses on a polymer blend close to phase inversion. Secondly, it investigates the impact of using two different types of interfacial agents (derived from polymer waste) to enhance the compatibility between iPP and PA6. Dynamic Mechanical Analysis (DMA) has been employed to achieve these objectives. It is important to note that the investigation of the 50/50 iPP/PA6 system is a crucial focus predicted in previous studies, where a series of mechanical properties were evaluated using Box-Wilson design of experiments (DOEs) over the whole compositional range on the iPP/PA6 binary system. Thus, two interfacial modifiers, namely succinic anhydride (SA)-grafted atactic polypropylene with terminal, side, and bridge SA grafts (aPP-SASA) and succinyl-fluoresceine (SF) with bridge succinic anhydride grafting atactic polypropylene (aPP-SFSA), were employed. The authors obtained and characterized these agents. The quantity of these agents used in the blend was identified as a critical coordinate in prior studies conducted by the authors. The processing method used, compression molding under confined conditions, was chosen to minimize any orientation effect on the emerging morphology. All characterization procedures were performed on samples processed by contour machining to retain the blend morphologies as they emerged from the processing stage. Results from WAXS and SAXS synchrotron tests concluded there were no changes in the crystal morphology of the iPP or the PA6 in the blends nor any co-crystallization process throughout the compositional range. These findings, and the long period fits on the PP crystalline phase for the fifty/fifty blends we are discussing, will support the present DMA study. Finally, the efficiency of these interfacial modifiers has been concluded, even in this unfavorable scenario.

3.
Macromol Rapid Commun ; : e2400551, 2024 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-39183577

RESUMEN

Binary blends of polyterpenes are employed comprising cis-1,4-polyfarnesene (PF) with a bottlebrush architecture, and linear cis-1,4-polyisoprene (PI) as model systems toward supersoft polymer melts. The bottlebrush PF results in a low plateau modulus ( G N 0 ≈ 3.5 × 10 4 ${G}_{N}^{0}\approx 3.5\ensuremath{\times{}}{10}^{4}$ Pa) that can further be reduced with the addition of PI. Depending on the fraction of short PI chains in the athermal and nearly isofrictional blends, plateau moduli in the range from 1 to 10 kPa can be achieved. Tube dilation is very efficient in the present binary blends as compared to more common blends comprising long/short or linear/star chains of identical polymer structure.

4.
ACS Appl Mater Interfaces ; 16(34): 45487-45496, 2024 Aug 28.
Artículo en Inglés | MEDLINE | ID: mdl-39140627

RESUMEN

Maintaining a high modulus to simultaneously withstand deformation and increase fatigue resistance to restrict crack propagation in a material presents a significant challenge. In this work, a straightforward strategy was developed to address this issue in polymers. A dynamic network was incorporated into a permanent one prior to the formation of the latter, and two incompatible polymer networks were created to prevent common phase separation. The mechanical and fatigue resistance properties were substantially enhanced by the exact modulation of the soft and hard phase distribution by precise control over the densities of dynamic and permanent networks as well as the number of reprocessing steps. The experimental results demonstrated a nearly 9-fold increase in the fatigue life of polyurethane compared with traditional design methods and a 2.5 times increase in modulus. This strategy shows potential for the design of fatigue-resistant thermosetting and thermoplastic materials. The results offer new insight into the development of durable, high-performance materials that are reprocessable and compatible.

5.
ACS Biomater Sci Eng ; 10(9): 5807-5821, 2024 Sep 09.
Artículo en Inglés | MEDLINE | ID: mdl-39177293

RESUMEN

In this study, the synthesis of poly(AVGVP) [where A-Alanine, V-Valine, G-Glycine, and P-Proline] is executed by the stepwise solution phase method. The interaction between Chitosan and synthetic polypentapeptide in blends was examined in the liquid and solid phases. Viscosity criteria that establish the total miscibility with Chitosan are the Δ[η]m, the intrinsic viscosity [η], Huggins coefficient [KH], by Garcia ΔB, α by Sun, and µ suggested by Chee, ΔK, and ß buttressed by Jiang and Han. Besides, the results are corroborated in the solid phase by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD). Miscibility in the blends led to higher thermal stability than that of pure polymers, according to thermogravimetric analysis (TGA). In vitro, studies offered the absence of cytotoxicity, and in vivo histopathological results advocated that the blend shows less inflammation and is more compact as against cotton gauge, evincing an enhanced healing environment and promising the possibility of use in wound therapeutic applications.


Asunto(s)
Quitosano , Péptidos , Ratas Sprague-Dawley , Cicatrización de Heridas , Quitosano/química , Animales , Cicatrización de Heridas/efectos de los fármacos , Ratas , Péptidos/química , Péptidos/farmacología , Viscosidad , Materiales Biocompatibles/química , Materiales Biocompatibles/farmacología , Masculino
6.
Environ Sci Pollut Res Int ; 31(39): 51504-51520, 2024 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-39112900

RESUMEN

This study aims to use beeswax, a readily available and cost-effective organic material, as a novel phase change material (PCM) within blends of low-density polyethylene (LDPE) and styrene-b-(ethylene-co-butylene)-b-styrene (SEBS). LDPE and SEBS act as support materials to prevent beeswax leakage. The physicochemical properties of new blended phase change materials (B-PCM) were determined using an X-ray diffractometer and an infrared spectrometer, confirming the absence of a chemical reaction within the materials. A scanning electron microscope was used for microstructural analysis, indicating that the interconnection of the structure allowed better thermal conductivity. Thermal gravimetric analysis revealed enhanced thermal stability for the B-PCM when combined with SEBS, especially within its operating temperature range. Analysis of phase change temperature and latent heat with differential scanning calorimetry showed no major difference in the melting point of the various PCM blends created. During the melting/solidification process, the B-PCMs possess excellent performance as characterized by W70/P30 (112.45 J.g-1) > W70/P20/S10 (94.28 J.g-1) > W70/P10/S20 (96.21 J.g-1) of latent heat storage. Additionally, the blends tend to reduce supercooling compared to pure beeswax. During heating and cooling cycles, the B-PCM exhibited minimal leakage and degradation, especially in blends containing SEBS. In comparison to the rapid temperature drop observed during the cooling process of W70/P30, the temperature decline of W70/P30 was slower and longer, as demonstrated by infrared thermography. The addition of LDPE to the PCM reduced melting time, indicating an improvement in the thermal energy storage reaction time to the demand. According to the obtained findings, increasing the SEBS concentration in the composite increased the thermal stability of the resulting PCM blends significantly. Despite the challenges mentioned earlier, SEBS proved to be an effective encapsulating material for beeswax, whereas LDPE served well as a supporting material. Leak tests were performed to find the ideal mass ratio, and weight loss was analyzed after multiple cycles of cooling and heating at 70 °C. The morphology, thermal characteristics, and chemical composition of the beeswax/LDPE/SEBS composite were all examined. Beeswax proves to be a highly effective phase change material for storing thermal energy within LDPE/SEBS blends.


Asunto(s)
Ceras , Ceras/química , Polietileno/química
7.
Molecules ; 29(16)2024 Aug 12.
Artículo en Inglés | MEDLINE | ID: mdl-39202905

RESUMEN

Bone tissue exhibits self-healing properties; however, not all defects can be repaired without surgical intervention. Bone tissue engineering offers artificial scaffolds, which can act as a temporary matrix for bone regeneration. The aim of this study was to manufacture scaffolds made of poly(lactic acid), poly(ε-caprolactone), poly(propylene fumarate), and poly(ethylene glycol) modified with bioglass, beta tricalcium phosphate (TCP), and/or wollastonite (W) particles. The scaffolds were fabricated using a gel-casting method and observed with optical and scanning electron microscopes. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetry (TG), wettability, and degradation tests were conducted. The highest content of TCP without W in the composition caused the highest hydrophilicity (water contact angle of 61.9 ± 6.3°), the fastest degradation rate (7% mass loss within 28 days), moderate ability to precipitate CaP after incubation in PBS, and no cytotoxicity for L929 cells. The highest content of W without TCP caused the highest hydrophobicity (water contact angle of 83.4 ± 1.7°), the lowest thermal stability, slower degradation (3% mass loss within 28 days), and did not evoke CaP precipitation. Moreover, some signs of cytotoxicity on day 1 were observed. The samples with both TCP and W showed moderate properties and the best cytocompatibility on day 4. Interestingly, they were covered with typical cauliflower-like hydroxyapatite deposits after incubation in phosphate-buffered saline (PBS), which might be a sign of their excellent bioactivity.


Asunto(s)
Ingeniería de Tejidos , Andamios del Tejido , Ingeniería de Tejidos/métodos , Andamios del Tejido/química , Animales , Materiales Biocompatibles/química , Huesos/efectos de los fármacos , Ratones , Polímeros/química , Línea Celular , Poliésteres/química , Ensayo de Materiales , Cerámica/química , Fosfatos de Calcio/química , Regeneración Ósea/efectos de los fármacos , Espectroscopía Infrarroja por Transformada de Fourier , Termogravimetría , Fumaratos/química
8.
Polymers (Basel) ; 16(14)2024 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-39065395

RESUMEN

Polymer blends of poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide) (PLLA-PEG-PLLA) and high-density polyethylene (HDPE) with different blend ratios were prepared by a melt blending method. The thermal, morphological, mechanical, opacity, and biodegradation properties of the PLLA-PEG-PLLA/HDPE blends were investigated and compared to the PLLA/HDPE blends. The blending of HDPE improved the crystallization ability and thermal stability of the PLLA-PEG-PLLA; however, these properties were not improved for the PLLA. The morphology of the blended films showed that the PLLA-PEG-PLLA/HDPE blends had smaller dispersed phases compared to the PLLA/HDPE blends. The PLLA-PEG-PLLA/HDPE blends exhibited higher flexibility, lower opacity, and faster biodegradation and bioerosion in soil than the PLLA/HDPE blends. Therefore, these PLLA-PEG-PLLA/HDPE blends have a good potential for use as flexible and partially biodegradable materials.

9.
Eur J Pharm Sci ; 200: 106850, 2024 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-38996850

RESUMEN

Additive manufacturing (AM) enables the production of complex, lightweight, and customized components with superior quality. Selecting the right materials considering their thermal properties, printability, and layer adhesion is crucial in melting-based AM techniques. This study investigates Droplet Deposition Modelling (DDM), an innovative material extrusion process that utilizes thermoplastic granules. DDM is distinguished by its shorter manufacturing times and a wider range of materials, setting it apart from traditional material extrusion methods such as fused filament fabrication. We investigated the printability and part quality in DDM using two common pharmaceutical excipients: Polyvinylpyrrolidone/vinyl acetate 6:4 (PVP/VA), which is highly brittle, and Polycaprolactone (PCL), known for its low solubility and role in controlled drug release. Different ratios of PVP/VA and PCL were compounded via hot melt extrusion (HME) and used in DDM to study the impact of ingredient content on printability and part quality, employing geometrical models to assess material compatibility and printability. The study revealed that increasing PVP/VA content leads to higher viscosity, reduced flowability, and uneven deposition, with formulations of 80 % and 100 % PVP/VA showing poor processability. In contrast, formulations with 60 % and 40 % PVP/VA exhibited smooth processing and compatibility with DDM. We identified processing temperature and Drop Aspect Ratio (DAR) as key factors influencing material printability and part quality. Elevated processing temperatures and reduced DAR were found to increase interface temperatures, reduce diffusion, and potentially cause the 'elephant feet' issue. Additionally, smaller droplet sizes and material characteristics, such as higher interfacial tension in PCL, could lead to coalescence. Our findings highlight the complexities in optimizing DDM processing parameters and material blends, underscoring the need for careful formulation design to achieve high-quality 3D printed products.


Asunto(s)
Excipientes , Poliésteres , Povidona , Poliésteres/química , Excipientes/química , Povidona/química , Compuestos de Vinilo/química , Composición de Medicamentos/métodos
10.
Polymers (Basel) ; 16(13)2024 Jun 23.
Artículo en Inglés | MEDLINE | ID: mdl-39000632

RESUMEN

Poly(L-Lactide) (PLA), a fully biobased aliphatic polyester, has attracted significant attention in the last decade due to its exceptional set of properties, such as high tensile modulus/strength, biocompatibility, (bio)degradability in various media, easy recyclability and good melt-state processability by the conventional processes of the plastic/textile industry. Blending PLA with other polymers represents one of the most cost-effective and efficient approaches to develop a next-generation of PLA-based materials with superior properties. In particular, intensive research has been carried out on PLA-based blends with engineering polymers such as polycarbonate (PC), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT) and various polyamides (PA). This overview, consequently, aims to gather recent works over the last 10 years on these immiscible PLA-based blends processed by melt extrusion, such as twin screw compounding. Furthermore, for a better scientific understanding of various ultimate properties, processing by internal mixers has also been ventured. A specific emphasis on blend morphologies, compatibilization strategies and final (thermo)mechanical properties (tensile/impact strength, ductility and heat deflection temperature) for potential durable and high-performance applications, such as electronic parts (3C parts, electronic cases) to replace PC/ABS blends, has been made.

11.
ACS Appl Mater Interfaces ; 16(26): 34192-34212, 2024 Jul 03.
Artículo en Inglés | MEDLINE | ID: mdl-38915136

RESUMEN

Two dynamic covalent networks based on the Diels-Alder reaction were blended to exploit the properties of the dissimilar polymer backbones. Furan-functionalized polyether amines based on poly(propylene oxide) (PPO) FD4000 and polydimethylsiloxane (PDMS) FS5000 were mixed in a common solvent and reversibly cross-linked with the same bismaleimide DPBM. The morphology of the phase-separated blends is primarily controlled by the concentration of backbones. Increasing the PDMS content of the blends results in a dilute droplet morphology at 25 wt %, with a growing size and concentration of droplets and the formation of two separate PPO- and PDMS-rich layers at 50 wt %. Further increasing the PDMS content to 75 wt % leads to larger droplets and a thicker layer of the secondary phase. The hydrophobic PDMS phase creates a barrier against water, while the more hydrophilic PPO phase enhances the resistance against oxygen diffusion. Lowering the maleimide-to-furan stoichiometric ratio resulted in a decrease in cross-link density and thus more flexible and stretchable encapsulants. Changes in the stoichiometric ratio also affected the phase morphology due to resulting changes in phase separation and network formation kinetics. Lowering the stoichiometric ratio also resulted in enhanced self-healing properties of 96% at room temperature as a consequence of the increased chain mobility in the blended networks. The self-healing blends were used to encapsulate liquid metal circuits to create stretchable strain sensors with a linear electro-mechanical response without much drift or hysteresis, which could be efficiently recovered by 90% after the damage-healing cycles.

12.
Polymers (Basel) ; 16(12)2024 Jun 08.
Artículo en Inglés | MEDLINE | ID: mdl-38931976

RESUMEN

A Monte Carlo study of the compatibilization of A/B polymer blends has been performed using the bond fluctuation model. The considered compatibilizers are copolymer molecules composed of A and B blocks. Different types of copolymer structures have been included, namely, linear diblock and 4-block alternating copolymers, star block copolymers, miktoarm stars, and zipper stars. Zipper stars are composed of two arms of diblock copolymers arranged in alternate order (AB and BA) from the central unit, along with two homogeneous arms of A and B units. The compatibilization performance has been characterized by analyzing the equilibration of repulsion energy, the simulated scattering intensity obtained with opposite refractive indices for A and B, the profiles along a coordinate axis, the radial distribution functions, and the compatibilizer aggregation numbers. According to the results, linear alternate block copolymers, star block copolymers, and zipper stars exhibit significantly better compatibilization, with zipper stars showing slightly but consistently better performance.

13.
Heliyon ; 10(7): e28379, 2024 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-38689987

RESUMEN

In our pursuit of a flexible energy storage solution, we have developed biocompatible (bc)-NG/PVA composite polymers by combining neem tree gum (NG) with polyvinyl alcohol (PVA). This innovative bio-inspired approach harnesses NG's unique properties for both the bio-electrolyte and bio-electrode components. The resulting bc-NG/PVA composites exhibit superior dielectric strength and versatility, surpassing traditional inorganic ceramic dielectrics in advanced electronics and pulsed power systems. Our study investigates the dielectric characteristics, conductivities, electric modulus, and impedance parameters of Pure PVA and NG-doped PVA composites. Adding 5 % NG to PVA significantly boosts its conductivity from 10-8 S cm-1 to 10-4 S cm-1, while the dielectric constant of PVA/5 % NG composite jumps to 104.5 compared to pure PVA. These improvements position the composite films of 5 % NG added PVA as promising materials for diverse applications. The heightened performance of these NG-blended PVA composite materials underscores their potential as a valuable resource for flexible energy storage solutions.

14.
Polymers (Basel) ; 16(9)2024 Apr 29.
Artículo en Inglés | MEDLINE | ID: mdl-38732710

RESUMEN

Bio-fillers are intensively studied for advanced polymer composite circular design and production. In this context, the algal biomass may be considered an important and relatively low-cost resource, when harvested as a by-product from wastewater treatment plants. The biomass of the algal species Chlorella vulgaris is frequently used in this type of environmental process, and its macro constituents' composition ranges from around 15-25% carbohydrates, 10-20% lipids, and 50-60% proteins. Poly (styrene-butadiene-styrene) (SBS) copolymers have a matrix composed of glassy polystyrene domains connected by flexible polybutadiene segments. Although the physical-mechanical properties of SBS copolymers recommend them for many industrial applications, they have the drawback of low biodegradability. This study aimed to assess the aerobic biodegradability of polymer composites by integrating biomass from Chlorella vulgaris at varying mass percentages of 5, 10, and 20% into SBS copolymer composites. Biodegradation tests were conducted under industrial composting conditions (58 °C and 50% relative humidity) for 180 days. The biodegradability of materials was evaluated by measuring the CO2 produced in each vessel during the study period. Potential correlations between the amount of carbon dioxide released and the percentage of biomass added to the polymer matrix were examined. Structural and morphological changes were assessed using Fourier Transform infrared spectroscopy (FTIR), thermal analysis (DSC), and scanning electron microscopy (SEM). Physical and chemical testing revealed a decrease in sample density after the industrial composting test, along with noticeable changes in melt flow index (MFI). The observed physical and chemical changes, coupled with FTIR, SEM, and DSC data, indicate increased cross-linking and higher porosity in biodegraded polymer structures with higher biomass content. This behavior is likely due to the formation of cross-linked connections between polymer chains and polypeptide chains resulting from protein degradation, enhancing connections between polystyrene units facilitated by peptide bonds with the benzene units of the styrene blocks within the polymer matrix.

15.
Appl Spectrosc ; : 37028241247823, 2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38651333

RESUMEN

In the processing of polymer blends and composites, in-line near-infrared (NIR) spectroscopy enables monitoring of the composition and its composite uniformity and contributes to rapid process development and quality control. However, in the injection molding process, the study of the composition of polymer materials has been delayed due to high-pressure conditions. Our research group developed NIR probes for transmission and diffuse reflectance measurements that can withstand high-pressure and temperature conditions up to 130 MPa and 200 °C. In this research, transmission and diffuse reflectance spectra were measured inline during the injection molding process of polymer blends of poly(lactic acid) and polybutylene succinate adipate. The intensity of each polymer band in the second-derivative spectra exhibited a monotonic increase or decrease in response to changes in the blend ratio. Using transmission and diffuse reflectance spectra as explanatory variables of the partial least squares regression model simultaneously, the model showed high estimation accuracy for the entire region of the blend ratio. Finally, this model was applied to monitor the polymer changeover operation, and the change in the blend ratio in the molded product was successfully estimated in line.

16.
Polymers (Basel) ; 16(8)2024 Apr 14.
Artículo en Inglés | MEDLINE | ID: mdl-38675011

RESUMEN

Over the past few years, polymer nanocomposites have garnered a significant amount of interest from both the scientific community and industry due to their remarkable versatility and wide range of potential uses in various fields, including automotive, electronics, medicine, textiles and environmental applications. In this regard, this study focuses on the influence of a compatibilizer rubber on a nanocomposite incorporating graphene nanoparticles (GNPs), with a polymer matrix based on a blend of polypropylene (PP) and polyethylene terephthalate (PET). This effect has been investigated on both isotropic samples and on anisotropic/spun fiber samples. The influence of the compatibilizer rubber on morphological, rheological and mechanical properties was analysed and discussed. Mechanical and morphological properties were evaluated on both isotropic samples obtained by compression moulding and melt-spun fibers. The addition of the rubbery compatibilizer increased the viscosity, improving interfacial adhesion, and the same effect was observed for the melt strength and breaking stretching ratios. Mechanical properties, including the elastic modulus, tensile strength and elongation at break, improved in both types of samples but more significantly in the fibers. These improvements were attributed to the orientation of the matrix, the formation of PET microfibrils, and the reduction in the size of graphene nanoparticles due to the action of the elongational flow. This reduction, facilitated by the elongation flow and the action of the compatibilizer, improved matrix-nanofiller adhesion due to the increased contact area between the two polymeric phases and between the filler and matrix. Finally, a transition from brittle to ductile behaviour was observed, particularly in the system with the compatibilizer, attributed to defect reduction and improved stress transmission.

17.
Polymers (Basel) ; 16(8)2024 Apr 16.
Artículo en Inglés | MEDLINE | ID: mdl-38675026

RESUMEN

Biodegradable blends based on plasticized poly(lactic acid) PLA and thermoplastic starch (TPS) have been obtained. The influence of the PLA plasticizer as a compatibility agent has been studied by using two different plasticizers such as neat oligomeric lactic acid (OLA) and functionalized with maleic acid (mOLA). In particular, the morphological, thermal, and mechanical properties have been studied as well as the shape memory ability of the melt-processed materials. Therefore, the influence of the interaction between different plasticizers and the PLA matrix as well as the compatibility between the two polymeric phases on the thermally-activated shape memory properties have been studied. It is very interesting to use the same additive able to act as both plasticizer and compatibilizer, decreasing the glass transition temperature of PLA to a temperature close to the physiological one, obtaining a material suitable for potential biomedical applications. In particular, we obtain that OLA-plasticized blend (oPLA/TPS) show very good thermally-activated capability at 45 °C and 50% deformation, while the blend obtained by using maleic OLA (moPLA/TPS) did not show shape memory behavior at 45 °C and 50% deformation. This fact is due to their morphological changes and the loss of two well-distinguished phases, one acting as fixed phase and the other one acting as switching phase to typically obtain shape memory response. Therefore, the thermally-activated shape memory results show that it is very important to make a balance between plasticizer and compatibilizer, considering the need of two well-established phases to obtain shape memory response.

18.
J Funct Biomater ; 15(3)2024 Feb 26.
Artículo en Inglés | MEDLINE | ID: mdl-38535250

RESUMEN

Bone tissue is one of the most transplanted tissues. The ageing population and bone diseases are the main causes of the growing need for novel treatments offered by bone tissue engineering. Three-dimensional (3D) scaffolds, as artificial structures that fulfil certain characteristics, can be used as a temporary matrix for bone regeneration. In this study, we aimed to fabricate 3D porous polymer scaffolds functionalized with tricalcium phosphate (TCP) particles for applications in bone tissue regeneration. Different combinations of poly(lactic acid) (PLA), poly(ethylene glycol) (PEG with molecular weight of 600 or 2000 Da) and poly(ε-caprolactone) (PCL) with TCP were blended by a gel-casting method combined with rapid heating. Porous composite scaffolds with pore sizes from 100 to 1500 µm were obtained. ATR-FTIR, DSC, and wettability tests were performed to study scaffold composition, thermal properties, and hydrophilicity, respectively. The samples were observed with the use of optical and scanning electron microscopes. The addition of PCL to PLA increased the hydrophobicity of the composite scaffolds and reduced their susceptibility to degradation, whereas the addition of PEG increased the hydrophilicity and degradation rates but concomitantly resulted in enhanced creation of rounded mineral deposits. The scaffolds were not cytotoxic according to an indirect test in L929 fibroblasts, and they supported adhesion and growth of MG-63 cells when cultured in direct contact.

19.
Materials (Basel) ; 17(5)2024 Feb 27.
Artículo en Inglés | MEDLINE | ID: mdl-38473555

RESUMEN

The polymer foil industry is one of the leading producers of plastic waste. The development of new recycling methods for packaging products is one of the biggest demands in today's engineering. The subject of this research was the melt processing of multilayered PET-based foil waste with PETG copolymer. The resulting blends were intended for additive manufacturing processing using the fused deposition modeling (FDM) method. In order to improve the properties of the developed materials, the blends compounding procedure was conducted with the addition of a reactive chain extender (CE) and elastomeric copolymer used as an impact modifier (IM). The samples were manufactured using the 3D printing technique and, for comparison, using the traditional injection molding method. The obtained samples were subjected to a detailed characterization procedure, including mechanical performance evaluation, thermal analysis, and rheological measurements. This research confirms that PET-based film waste can be successfully used for the production of filament, and for most samples, the FDM printing process can be conducted without any difficulties. Unfortunately, the unmodified blends are characterized by brittleness, which makes it necessary to use an elastomer additive (IM). The presence of a semicrystalline PET phase improves the thermal resistance of the prepared blends; however, an annealing procedure is required for this purpose.

20.
Macromol Rapid Commun ; 45(11): e2400036, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38453138

RESUMEN

Preparation of materials that possess highly strong and tough properties simultaneously is a great challenge. Thermosetting resins as a type of widely used polymeric materials without synergistic strength and toughness limit their applications in some special fields. In this report, an effective strategy to prepare thermosetting resins with synergistic strength and toughness, is presented. In this method, the soft and rigid microspheres with dynamic hemiaminal bonds are fabricated first, followed by hot-pressing to crosslink at the interfaces. Specifically, the rigid or soft microspheres are prepared via precipitation polymerization. After hot-pressing, the resulting rigid-soft blending materials exhibit superior strength and toughness, simultaneously. As compared with the precursor rigid or soft materials, the toughness of the rigid-soft blending films (RSBFs) is improved to 240% and 2100%, respectively, while the strength is comparable to the rigid precursor. As compared with the traditional crushing, blending, and hot-pressing of rigid or soft materials to get the nonuniform materials, the strength and toughness of the RSBFs are improved to 168% and 255%, respectively. This approach holds significant promise for the fabrication of polymer thermosets with a unique combination of strength and toughness.


Asunto(s)
Polimerizacion , Resinas Sintéticas/química , Microesferas , Polímeros/química , Temperatura , Ensayo de Materiales , Propiedades de Superficie , Tamaño de la Partícula
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