Search Results (20)

Halloysite nanoclay (HNC) and as-polymerized polytetrafluoroethylene powder (PTFE) were introduced into biodegradable polylactic acid (PLA) via a melt mixing technique to enhance its mechanical, rheological properties and foaming ability. The synergetic effects of these fillers on the morphological, mechanical, thermal, and foaming properties of PLA were investigated. Results indicated that the tensile properties were improved in comparison to neat PLA. Differential Scanning Calorimetry (DSC) revealed a decrease in PLA crystallization time with increasing filler concentration, indicating a strong nucleating effect on PLA crystallization. Extensional flow tests showed that strain hardening in PLA composites is influenced by fillers, with PTFE particularly exhibiting a more pronounced effect, attributed to nanofibrillation and entanglement during melt processing. The addition of a dual-filler system improved the melt strength and viscosity of PLA, resulting in foams with decreased cell size and increased cell density. Full article

Modern tissue engineering requires not only degradable materials promoting cell growth and differentiation, but also vascularization of the engineered tissue. Porous polylactide/polycaprolactone (PLA/PCL, ratio 3/5) foam scaffolds were prepared by a combined porogen leaching and freeze-drying technique using NaCl (crystal size 250–500 µm) and a water-soluble cellulose derivative (Klucel^TM E; 10–100% w/w relative to the total PLA/PCL concentration) as porogens. Scanning electron microscopy, micro-CT, and Brunauer–Emmett–Teller analysis showed that all scaffolds contained a trimodal range of pore sizes, i.e., macropores (average diameter 298–539 μm), micropores (100 nm to 10 μm), and nanopores (mostly around 3.0 nm). All scaffolds had an open porosity of about 90%, and the pores were interconnected. The size of the macropores and the nanoporosity were higher in the scaffolds prepared with Klucel. Nanoporosity increased water uptake by the scaffolds, while macroporosity promoted cell ingrowth, which was most evident in scaffolds prepared with 25% Klucel. Human adipose-derived stem cells co-cultured with endothelial cells formed pre-vascular structures in the scaffolds, which was further enhanced in a dynamic cell culture system. The scaffolds are promising for the engineering of pre-vascularized soft tissues (relatively pliable 10% Klucel scaffolds) and hard tissues (mechanically stronger 25% and 50% Klucel scaffolds). Full article

This paper presents the novel development of a shape memory polymer foam based on polymer–polymer nanocomposites. Herein, polylactide (PLA)/biosourced polyamide (PA) foams are fabricated by in situ fibrillation of polymer blends and a subsequent supercritical CO₂ foaming technique. In this system, PLA serves as a shape memory polymer to endow this foam with a shape memory effect (SME), and in situ generated PA nanofibers are employed to reinforce the PLA cell walls and provide an additional permanent phase. A concentration of PA, 5 wt.%, was chosen to form an entangled nanofibrillar network. Foams of PLA/PA nanoblends with the same content of constituents were fabricated to reveal the effect of minor phase morphology on the cell structure and shape memory behavior of polymer foams. Profiting from the reinforcing effect of PA nanofibers, the PLA/PA nanocomposite foam exhibits smaller foam cells, a narrower cell size distribution and a comparable cell concentration than the PLA/PA nanoblend foam. In addition, PA nanofibers, unlike PA nanodroplets, favor the shape fixation ratio and recovery ratio and shorten the shape recovery time. Full article

Biodegradable polylactic acid (PLA) foams with open-cell structures are good candidates for oil–water separation. However, the foaming of PLA with high-expansion and uniform cell morphology by the traditional supercritical carbon dioxide microcellular foaming method remains a big challenge due to its low melting strength. Herein, a green facile strategy for the fabrication of open-cell fully biodegradable PLA-based foams is proposed by introducing the unique stereocomplexation mechanism between PLLA and synthesized star-shaped PDLA for the first time. A series of star-shaped PDLA with eight arms (8-s-PDLA) was synthesized with different molecular weights and added into the PLLA as modifiers. PLLA/8-s-PDLA foams with open-cells structure and high expansion ratios were fabricated by microcellular foaming with green supercritical carbon dioxide. In detail, the influences of induced 8-s-PDLA on the crystallization behavior, rheological properties, cell morphology and consequential oil–water separation performance of PLA-based foam were investigated systemically. The addition of 8-s-PDLA induced the formation of SC-PLA, enhancing crystallization by acting as nucleation sites and improving the melting strength through acting as physical cross-linking points. The further microcellular foaming of PLLA/8-s-PDLA resulted in open-cell foams of high porosity and high expansion ratios. With an optimized foaming condition, the PLLA/8-s-PDLA-13K foam exhibited an average cell size of about 61.7 μm and expansion ratio of 24. Furthermore, due to the high porosity of the interconnected open cells, the high-absorption performance of the carbon tetrachloride was up to 37 g/g. This work provides a facile green fabrication strategy for the development of environmentally friendly PLA foams with stable open-cell structures and high expansion ratios for oil–water separation. Full article

Polylactide foaming as the key stage in laboratory preparation of highly porous biocompatible matrices used as scaffold prototypes was monitored based the effect of dynamic light scattering in expanding polylactide foams. Intensity fluctuations of scattered laser radiation in the course of foam expansion were analyzed using ensemble-averaged estimates of the speckle lifetime within a running window in the time domain. It was found that, in contrast to the commonly used correlation time of intensity fluctuations, the values of the average speckle lifetime are invariant with respect to the type of dynamics of phase fluctuations of partial components in scattered radiation. This makes it possible to relate this parameter to microscopic mobility of interphase boundaries in the foam in the absence of a priori information on the law of motion relating these boundaries at the microscopic level. The proposed approach in combination with the developed phenomenological model describing the relationship between the average speckle lifetime and the current values of the foam volume, as well as its first-time derivative made it possible to interpret the features of foam structure formation. Full article

Microscopic structural rearrangements in expanding polylactide foams were probed using multiple dynamic scattering of laser radiation in the foam volume. Formation and subsequent expansion of polylactide foams was provided by a rapid or slow depressurization of the “plasticized polylactide–supercritical carbon dioxide” system. Dynamic speckles induced by a multiple scattering of laser radiation in the expanding foam were analyzed using the stacked speckle history technique, which is based on a joint mapping of spatial–temporal dynamics of evolving speckle patterns. A significant decrease in the depressurization rate in the case of transition from a rapid to slow foaming (from 0.03 MPa/s to 0.006 MPa/s) causes dramatic changes in the texture of the synthesized stacked speckle history maps. These changes are associated with transition from the boiling dynamics of time-varying speckles to their pronounced translational motions and are manifested as significant slopes of individual speckle traces on the recovered stacked speckle history maps. This feature is interpreted in terms of the actual absence of a new cell nucleation effect in the expanding foam upon slow depressurization on the dynamic scattering of laser radiation. Full article

Fabricating polymeric scaffolds using cost-effective manufacturing processes is still challenging. Gas foaming techniques using supercritical carbon dioxide (scCO₂) have attracted attention for producing synthetic polymer matrices; however, the high-pressure requirements are often a technological barrier for its widespread use. Compressed 1,1,1,2-tetrafluoroethane, known as Freon R134a, offers advantages over CO₂ in manufacturing processes in terms of lower pressure and temperature conditions and the use of low-cost equipment. Here, we report for the first time the use of Freon R134a for generating porous polymer matrices, specifically polylactide (PLA). PLA scaffolds processed with Freon R134a exhibited larger pore sizes, and total porosity, and appropriate mechanical properties compared with those achieved by scCO₂ processing. PLGA scaffolds processed with Freon R134a were highly porous and showed a relatively fragile structure. Human mesenchymal stem cells (MSCs) attached to PLA scaffolds processed with Freon R134a, and their metabolic activity increased during culturing. In addition, MSCs displayed spread morphology on the PLA scaffolds processed with Freon R134a, with a well-organized actin cytoskeleton and a dense matrix of fibronectin fibrils. Functionalization of Freon R134a-processed PLA scaffolds with protein nanoparticles, used as bioactive factors, enhanced the scaffolds’ cytocompatibility. These findings indicate that gas foaming using compressed Freon R134a could represent a cost-effective and environmentally friendly fabrication technology to produce polymeric scaffolds for tissue engineering approaches. Full article

The aim of the presented research was to obtain two new eco-polyols based on waste polylactide (PLA) and to check the effect on the properties of rigid polyurethane (RPU) foams and, based on these, rigid polyurethane/polyisocyanurate (RPU/PIR) foams. The synthesis of eco-polyols was based on the transesterification reaction of melted PLA with diethylene glycol in the presence of an organometallic catalyst. Properties of the obtained eco-polyols were examined for their potential as raw materials for synthesis of rigid polyurethane and polyisocyanurate foams, i.e., hydroxyl value, acid value, density, viscosity, pH, water content. Spectroscopic studies (FTIR, ¹H NMR and ¹³C NMR) were also carried out. Results of these tests confirmed the assumed chemical structure of the new polyols. RPU and RPU/PIR foam formulations were developed based on the obtained analytical results. Partial replacement of petrochemical polyol by eco-polyols in RPU and RPU/PIR foams decreased the value of apparent density, compressive strength, brittleness and water absorption. Moreover, all foams modified by eco-polyols showed higher resistance to aging. All RPU/PIR foams and most PRU foams modified by eco-polyols from waste PLA had better functional properties than the reference foams based on petrochemical polyol. Full article

Polylactide (PLA) is one of the most important bioplastics worldwide and thus represents a good potential substitute for bead foams made of the fossil-based Polystyrene (PS). However, foaming of PLA comes with a few challenges. One disadvantage of commercially available PLA is its low melt strength and elongation properties, which play an important role in foaming. As a polyester, PLA is also very sensitive to thermal and hydrolytic degradation. Possibilities to overcome these disadvantages can be found in literature, but improving the properties for foaming of PLA as well as the degradation behavior during foaming have not been investigated yet. In this study, reactive extrusion on a twin-screw extruder is used to modify PLA in order to increase the melt strength and to protect it against thermal degradation and hydrolysis. PLA foams are produced in an already known process from the literature and the influence of the modifiers on the properties is estimated. The results show that it is possible to enhance the foaming properties of PLA and to protect it against hydrolysis at the same time. Full article

Anterior cruciate ligament (ACL) cell sheets combined with biomechanically competent scaffolds might facilitate ACL tissue engineering. Since thermoresponsive polymers allow a rapid enzyme-free detachment of cell sheets, we evaluated the applicability of a thermoresponsive poly(glycidyl ether) (PGE) coating for cruciate ligamentocyte sheet formation and its influence on ligamentocyte phenotype during sheet-mediated colonization of embroidered scaffolds. Ligamentocytes were seeded on surfaces either coated with PGE or without coating. Detached ligamentocyte sheets were cultured separately or wrapped around an embroidered scaffold made of polylactide acid (PLA) and poly(lactic-co-ε-caprolactone) (P(LA-CL)) threads functionalized by gas-phase fluorination and with collagen foam. Ligamentocyte viability, protein and gene expression were determined in sheets detached from surfaces with or without PGE coating, scaffolds seeded with sheets from PGE-coated plates and the respective monolayers. Stable and vital ligamentocyte sheets could be produced within 24 h with both surfaces, but more rapidly with PGE coating. PGE did not affect ligamentocyte phenotype. Scaffolds could be colonized with sheets associated with high cell survival, stable gene expression of ligament-related type I collagen, decorin, tenascin C and Mohawk after 14 d and extracellular matrix (ECM) deposition. PGE coating facilitates ligamentocyte sheet formation, and sheets colonizing the scaffolds displayed a ligament-related phenotype. Full article

Polylactide foaming materials with promising biocompatibility balance the lightweight and mechanical properties well, and thus they can be desirable candidates for biological scaffolds used in tissue engineering. However, the cells are likely to coalesce and collapse during the foaming process of polylactide (PLA) due to its intrinsic low melt strength. This work introduces a unique PLA stereocomplexation into the microcellular foaming of poly (l-lactide)/poly (butylene succinate) (PLLA/PBS) based on supercritical carbon dioxide. The rheological properties of PLA/PBS with 5 wt% or 10 wt% poly (d-lactide) (PDLA) present enhanced melt strength owing to the formation of PLA stereocomplex crystals (sc-PLA), which act as physical pseudo-cross-link points in the molten blends by virtue of the strong intermolecular interaction between PLLA and the added PDLA. Notably, the introduction of either PBS or PDLA into the PLLA matrix could enhance its crystallization, while introducing both in the blend triggers a decreasing trend in the PLA crystallinity, which it is believed occurs due to the constrained molecular chain mobility by formed sc-PLA. Nevertheless, the enhanced melt strength and decreased crystallinity of PLA/PBS/PDLA blends are favorable for the microcellular foaming behavior, which enhanced the cell stability and provided amorphous regions for gas adsorption and homogeneous nucleation of PLLA cells, respectively. Furthermore, although the microstructure of PLA/PBS presents immiscible sea-island morphology, the miscibility was improved while the PBS domains were also refined by the introduction of PDLA. Overall, with the addition of PDLA into PLA/10PBS blends, the microcellular average cell size decreased from 3.21 to 0.66 μm with highest cell density of 2.23 × 10¹⁰ cells cm⁻³ achieved, confirming a stable growth of cells was achieved and more cell nucleation sites were initiated on the heterogeneous interface. Full article

For the preparation of polylactide (PLA)-based foams, it is commonly necessary to increase the melt strength of the polymer. Additives such as chain extenders (CE) or peroxides are often used to build up the molecular weight by branching or even crosslinking during reactive extrusion. Furthermore, a blowing agent with a low molecular weight, such as carbon dioxide (CO₂), is introduced in the foaming process, which might affect the reactivity during extrusion. Offline rheological tests can help to measure and better understand the kinetics of the reaction, especially the reaction between the polymer and the chemical modifier. However, rheological measurements are mostly done in an inert nitrogen atmosphere without an equivalent gas loading of the polymer melt, like during the corresponding reactive extrusion process. Therefore, the influence of the blowing agent itself is not considered within these standard rheological measurements. Thus, in this study, a rheometer equipped with a pressure cell is used to conduct rheological measurements of neat and chemical-modified polymers in the presence of CO₂ at pressures up to 40 bar. The specific effects of CO₂ at elevated pressure on the reactivity between the polymer and the chemical modifiers (an organic peroxide and as second choice, an epoxy-based CE) were investigated and compared. It could be shown in the rheological experiments that the reactivity of the chain extender is reduced in the presence of CO₂, while the peroxide is less affected. Finally, it was possible to detect the recrystallization temperature T_rc of the unmodified and unbranched sample by the torque maximum in the rheometer, representing the tear off of the stamp from the sample. T_rc was about 13 K lower in the CO₂-loaded sample. Furthermore, it was possible to detect the influences of branching and gas loading simultaneously. Here the influence of the branching on T_rc was much higher in comparison to a gas loading. Full article

The experimental evidence on depressurization foaming of the amorphous D,L-polylactide, which is plasticized by subcritical (initial pressures below the critical value) or supercritical (initial pressures above the critical value) carbon dioxide at a temperature above the critical value, relates to two extreme cases: a slow quasi-isothermal foam expansion, and a rapid quasi-adiabatic expansion. Under certain conditions, the quasi-isothermal mode is characterized by the non-monotonic dependencies of the foam volume on the external pressure that are associated with the expansion-to-shrinkage transition. The quasi-adiabatic and quasi-isothermal expansions are characterized by a significant increase in the degree of foam expansion under conditions where the CO₂ initial pressure approaches the critical value. The observed features are interpreted in terms of the energy balance in the foam volume and the phenomenological model based on the equation of the foam state. The expansion-to-shrinkage condition is based on the relationship between the average bubble radius and the pressure derivative of the surface tension for the plasticized polylactide. The maximum expansion ratio of the rapidly foamed polylactide in the vicinity of the critical point is interpreted in terms of the maximum decrement of the specific internal energy of the foaming agent (carbon dioxide) in the course of depressurization. Full article

In this comprehensive study, the influence of (i) material specific properties (e.g., molecular weight, zero shear viscosity, D-content) and (ii) process parameters (e.g., saturation temperature, -time, -pressure, and pressure drop rate) on the expansion behavior during the autoclave foaming process were investigated on linear Polylactide (PLA) grades, to identify and evaluate the foam relevant parameters. Its poor rheological behavior is often stated as a drawback of PLA, that limits its foamability. Therefore, nine PLA grades with different melt strength and zero shear viscosity were systematically chosen to identify whether these are the main factors governing the foam expansion and whether there is a critical value for these rheological parameters to be exceeded, to achieve low density foams with fine cells. With pressure drop induced batch foaming experiments, it could be shown that all of the investigated PLA grades could be foamed without the often used chemical modifications, although with different degrees of expansion. Interestingly, PLAs foaming behavior is rather complex and can be influenced by many other factors due to its special nature. A low molecular weight combined with a high ability to crystallize only lead to intermediate density reduction. In contrast, a higher molecular weight (i.e., increased zero shear viscosity) leads to significant increased expandability independent from the D-content. However, the D-content plays a crucial role in terms of foaming temperature and crystallization. Furthermore, the applied process parameters govern foam expansion, cell size and crystallization. Full article

The article presents the results of research on the synthesis of a new eco-polyol based on polylactide (PLA) waste and its use for the production of rigid polyurethane-polyisocyanurate (RPU/PIR) foams. The obtained recycling-based polyol was subjected to analytical, physicochemical and spectroscopic tests (FTIR, ¹H NMR, ¹³C NMR) to confirm its suitability for the synthesis of polyurethane materials. Then, it was used to partially replace petrochemical polyol in polyurethane formulation. The obtained RPU/PIR foams were characterized by lower apparent density, brittleness, and water absorption. In addition, foams modified by eco-polyol had higher flame retardancy, as compared to reference foam. The results of the research show that the use of PLA polyol based on plastic waste may be an alternative to petrochemical polyols. This research matches with the current trends of sustainable development and green chemistry. Full article