Search Results (92)

This study proposes a continuous preparation strategy for poly (l-lactic acid) (PLLA) scaffolds with oriented hierarchical microporous structures for bone repair. A PLLA-oriented multi-stage microporous bone repair scaffold (hereafter referred to as the oriented multi-stage microporous scaffold) was designed using a novel extrusion foaming technology that integrates fused deposition modeling (FDM) 3D printing with supercritical carbon dioxide (SC-CO₂) microcellular foaming technology. The influence of the 3D-printed structure on the microcellular morphology of the oriented multi-stage microporous scaffold was investigated and optimized. The combination of FDM and SC-CO₂ foaming technology enables a continuous extrusion foaming process for preparing oriented multi-stage microporous scaffolds. The mechanical strength of the scaffold reached 15.27 MPa, meeting the requirements for bone repair in a low-load environment. Notably, the formation of open pores on the surface of the oriented multi-stage microporous scaffold positively affected cell proliferation, differentiation, and activity, as well as the expression of anti-inflammatory and pro-inflammatory factors. In vitro cell experiments (such as CCK-8) showed that the cell proliferation rate in the oriented multi-stage microporous scaffold reached 100–300% after many days of cultivation. This work provides a strategy for the design and manufacture of PLLA scaffolds with hierarchical microcellular structures and biocompatibility for bone repair. Full article

This study explored the innovative foaming behavior of a novel biodegradable polymer blend consisting of polylactic acid/poly(butylene succinate)/poly(butylene adipate-co-terephthalate) (PLA/PBS/PBAT) enhanced with nanohydroxyapatite (nHA), using supercritical carbon dioxide (SCCO₂) as an environmentally friendly physical foaming agent. The aim was to investigate the effects of various foaming strategies on the resulting cell structure, aiming for potential applications in tissue engineering. Eight foaming strategies were examined, starting with a basic saturation process at high temperature and pressure, followed by rapid decompression to ambient conditions, referred to as the (1T-1P) strategy. Intermediate temperature and pressure variations were introduced before the final decompression to evaluate the impact of operating parameters further. These strategies included intermediate-temperature cooling (2T-1P), intermediate-temperature cooling with rapid intermediate decompression (2T-2P), and intermediate-temperature cooling with gradual intermediate decompression (2T-2P, stepwise ΔP). SEM imaging revealed that the (2T-2P, stepwise ΔP) strategy produced a bimodal cell structure featuring small cells ranging from 105 to 164 μm and large cells between 476 and 889 μm. This study demonstrated that cell size was influenced by the regulation of intermediate pressure reduction and the change in intermediate temperature. The results were interpreted based on classical nucleation theory, the gas solubility principle, and the effect of polymer melt strength. Foaming results of average cell size, cell density, expansion ratio, porosity, and opening cell content are reported. The hydrophilicity of various foamed polymer blends was evaluated by measuring the water contact angle. Typical compressive stress–strain curves obtained using DMA showed a consistent trend reflecting the effect of foam stiffness. Full article

Expanded graphite (EG) with high infrared (IR) absorption is incorporated at low concentrations (≤2 wt%) into polystyrene (PS) foams to reduce radiative thermal conductivity and solid thermal conductivity, which account for 20~40% and 10~30% of total thermal conductivity, respectively. After systematically and quantitatively investigating thermal insulation behavior in PS/EG foams, it was found that the inclusion of 1 wt% EG in 25-fold expanded PS/EG foam blocks over 90% of the radiative thermal conductivity, with only a marginal increase in heat conduction. A great reduction in total thermal conductivity from 36.5 to 30.2 mW·m⁻¹·K⁻¹ was then achieved. By further optimization using a co-blowing agent in the supercritical CO₂ foaming process, superthermal insulating PS/EG foam with a total thermal conductivity of 19.6 mW·m⁻¹·K⁻¹ was achieved for the first time. This significant result implies that the composite material design together with the foaming process design is capable of obtaining a superthermal insulating composite foam by using the following strategy: using additives with high IR absorption efficiency, a foam with a large expansion ratio, and a co-blowing agent with low gas conductivity. Full article

Conventional techniques for incorporating active ingredients into polymeric matrices are accompanied by certain disadvantages, primarily attributable to the inherent characteristics of the active ingredient itself, including its sensitivity to temperature. A potential solution to these challenges lies in the utilization of supercritical carbon dioxide (scCO₂) for the formation of polymeric foam and the incorporation of active ingredients, in conjunction with the encapsulation of inclusion complexes (ICs), to ensure physical stability and augmented bioactivity. The objective of this study was to assess the impact of IC impregnation and subsequent foam formation on PLA films and PLA/PBAT blends that had been previously impregnated. The study’s methodology encompassed the formation and characterization of ICs with caffeic acid (CA) and β-cyclodextrin (β-CD), along with the thermal, structural, and morphological properties of the resulting materials. Higher incorporation of impregnated IC into the PLA(42)/PBAT(58) blend was observed at 12 MPa pressure and a depressurization rate of 1 MPa/min. The presence of IC, in addition to a lower rate of expansion, contributed to the formation of homogeneous cells with a size range of 4–44 um. On the other hand, the incorporation of IC caused a decrease in the crystallinity of the PLA fraction due to the interaction of the complex with the polymer. This study makes a significant contribution to the advancement of knowledge on the incorporation of compounds encapsulated in β-CD by scCO₂, as well as to the development of active materials with potential applications in food packaging. Full article

Poly (butylene adipate-co-terephthalate) (PBAT) foam sheets prepared by foaming supercritical fluids are characterized by high resilience, homogeneous cellular structure, and well-defined biodegradability. However, the inert chemical structure and the rigid hard segments restrict the diffusion of CO₂ within the PBAT matrix, resulting in extremely long gas saturation times as long as 9 h at a thickness of 12 mm. In this study, microporous structures were pre-introduced into the PBAT matrix to provide a fast gas diffusion pathway during the saturation process. After 2 h of saturation, PBAT foam sheets with expansion ratio of 10 to 13.8 times were prepared. The interaction of CO₂ with PBAT was systematically investigated, and the CO₂ sorption process was evaluated kinetically and thermodynamically using the Fickian diffusion theory. The solubility and diffusion rate of CO₂ in pretreated PBAT sheets with different microporous sizes and densities were investigated, and the effects of pretreatment strategies on the foaming behavior and cell structure of PBAT foam sheets were discussed. The introduction of a microporous structure not only reduces saturation time but also enhances solubility, enabling the successful preparation of soft foams with high expansion ratios and resilience. After undergoing foaming treatment, the PBAT pretreated sheets with a 10 μm microporous structure and a density of 0.45 g/cm³ demonstrated improved mechanical properties: their hardness decreased to 35 C while resilience increased to 58%, reflecting enhanced elastic recovery capabilities. The pretreatment method, which increases the diffusion rate of CO₂ in PBAT sheets, offers a straightforward approach that provides valuable insights into achieving rapid and efficient foaming of thick PBAT sheets in industrial applications. Full article

Fruit seeds are often an underutilized side-stream of fruit processing. The most common approach to seed valorization is oil extraction due to the relative simplicity of the process. The partially or fully defatted seed meal is rarely further processed, even though seeds generally contain more protein and fiber than oil. The present study used single-screw extrusion (oil press), supercritical CO₂ extraction, and a combination of the two, to defat Japanese quince (Chaenomeles japonica) seeds, and evaluated the defatted meals as sources of functional protein. Defatting with oil press and CO₂ extraction proved similarly effective (reduced seed flour fat content from 11.75% to 6.40% and 5.32%, respectively); combining the two methods reduced fat content to 0.90%. The yield was minimally affected, but protein extract purity was defined by defatting efficiency (65.05% protein from non-defatted versus 82.29% protein from a combination-defatted meal). Defatting did not significantly affect amino acid composition but had a significant effect on every tested functional property (solubility, water, and oil binding capacity, apparent viscosity, foaming capacity, and emulsifying activity index). Of the tested defatting methods, supercritical CO₂ extraction and the combination provided the best results from most aspects. Full article

In this manuscript, an efficient self-reinforcing technology—solid hot drawing (SHD) technology—was combined with green processing supercritical carbon dioxide (SC-CO₂) foaming technology to promote poly (l-lactic acid) (PLLA) to form an oriented micropore structure. In addition, Polydimethylsiloxane (PDMS), with a high affinity of CO₂ and biological safety, was introduced to enhance the nucleation effect in SC-CO₂ foaming and co-regulate the uniformity of oriented micropores’ structure. The results showed that orientation induced PLLA crystallization, so the tensile strength was improved; the maximum tensile strength of the oriented micropores’ PLLA reached 151.2 MPa. Furthermore, the micropores mainly improved the toughness; the maximum elongation at break reached 148.3%. It is worth mentioning that PDMS can form an antibacterial film on the surface of the material, so that the material has a continuous antibacterial effect. 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

This study investigates the modeling and experimental validation of cell morphology in microcellular-foamed polycaprolactone (PCL) using supercritical carbon dioxide (scCO₂) as the blowing agent. The microcellular foaming process (MCP) was conducted using a solid-state batch foaming process, where PCL was saturated with scCO₂ at 6 to 9 MPa and 313 K, followed by depressurization at a rate of −0.3 and −1 MPa/s. This study utilized the Sanchez–Lacombe equation of state and the Peng–Robinson–Stryjek–Vera equation of state to model the solubility and density of the PCL-CO₂ mixture. Classical nucleation theory was modified and combined with numerical analysis to predict cell density, incorporating factors such as gas absorption kinetics, the role of scCO₂ in promoting nucleation, and the impact of depressurization rate and saturation pressure on cell growth. The validity of the model was confirmed by comparing the theoretical predictions with experimental and reference data, with the cell density determined through field-emission scanning electron microscopy analysis of foamed PCL samples. This study proposes a method for predicting cell density that can be applied to various polymers, with the potential for wide-ranging applications in biomaterials and industrial settings. This research also introduces a Python-based numerical analysis tool that allows for easy calculation of solubility and cell density based on the material properties of polymers and penetrant gases, offering a practical solution for optimizing MCP conditions in different contexts. Full article

Microcellular injection molding (MuCell^®) using supercritical fluid (SCF) as a foaming agent to achieve weight reduction has become popular in carbon emission reduction. In the typical MuCell® process, SCF N₂ is commonly used. Although SCF CO₂ exhibits high solubility and can achieve a high weight reduction, controlling the foaming is not easy, and its foaming cells are usually larger and less uniform, which limits its industrial application. Our previous studies have shown that gas counter pressure (GCP) can improve the foaming quality effectively. Here, we investigated whether or not the CO₂ SCF foaming quality could be improved, and weight reduction was achieved for polycarbonate (PC) material. This is quite important for the electronics industry, in which most of the housing for devices is made of PC materials. MuCell^® was subjected to molding experiments using the parameters of the SCF dosage, melt temperature, mold temperature, and injection speed. The results revealed that using CO₂ gas for the PC material can reduce the size of microcellular cells to 40 µm and increase the cell densities to 3.97 × 10⁶ cells/cm³. Using GCP significantly improved the microcellular injection-molded parts by reducing the cell size to 20.9 µm (a 45.41% improvement) and increasing the cell density to 8.04 × 10⁶ cells/cm³ (a 102.48% improvement). However, implementing GCP may slightly decrease the target weight reduction. This study reveals that microcellular injection molding of PC parts using SCF CO₂ can achieve high-quality foaming and reduce the weight by about 30%. Full article

Supercritical carbon dioxide (SCCO₂) is a non-toxic and environmentally friendly fluid and has been used in polymerization reactions, processing, foaming, and plasticizing of polymers. Exploring the behavior and data of SCCO₂ sorption and dissolution in polymers provides essential information for polymer applications. This study investigated the sorption and diffusion of SCCO₂ into polyetherimide (PEI). The sorption and desorption processes of SCCO₂ in PEI samples were measured in the temperature range from 40 to 60 °C, the pressure range from 20 to 40 MPa, and the sorption time from 0.25 to 52 h. This study used the ex situ gravimetric method under different operating conditions and applied the Fickian diffusion model to determine the mass diffusivity of SCCO₂ during sorption and desorption processes into and out of PEI. The equilibrium mass gain fraction of SCCO₂ into PEI was reported from 9.0 wt% (at 60 °C and 20 MPa) to 12.8 wt% (at 40 °C and 40 MPa). The sorption amount increased with the increasing SCCO₂ pressure and decreased with the increasing SCCO₂ temperature. This study showed the crossover phenomenon of equilibrium mass gain fraction isotherms with respect to SCCO₂ density. Changes in the sorption mechanism in PEI were observed when the SCCO₂ density was at approximately 840 kg/m³. This study qualitatively performed FTIR analysis during the SCCO₂ desorption process. A CO₂ antisymmetric stretching mode was observed near a wavenumber of 2340 cm⁻¹. A comparison of loss modulus measurements of pure and SCCO₂-treated PEI specimens showed the shifting of loss maxima. This result showed that the plasticization of PEI was achieved through the sorption process of SCCO₂. Full article

Since reservoirs with permeability less than 10 mD are characterized by high injection difficulty, high-pressure drop loss, and low pore throat mobilization during the water drive process, CO₂ is often used for development in actual production to reduce the injection difficulty and carbon emission simultaneously. However, microfractures are usually developed in low-permeability reservoirs, which further reduces the injection difficulty of the driving medium. At the same time, this makes the injected gas flow very fast, while the gas utilization rate is low, resulting in a low degree of recovery. This paper conducted a series of studies on the displacement effect of CO₂-soluble foaming systems in low-permeability fractured reservoirs (the permeability of the core matrix is about 0.25 mD). For the two CO₂-soluble blowing agents CG-1 and CG-2, the effects of the CO₂ phase state, water content, and oil content on static foaming performance were first investigated; then, a more effective blowing agent was preferred for the replacement experiments according to the foaming results; and finally, the effects of the blowing agents on sealing and improving the recovery degree of a fully open fractured core were investigated at different injection rates and concentrations, and the injection parameters were optimized. The results show that CG-1 still has good foaming performance under low water volume and various oil contents and can be used in subsequent fractured core replacement experiments. After selecting the injection rate and concentration, the blowing agent can be used in subsequent fractured cores under injection conditions of 0.6 mL/min and 2.80%. In injection conditions, the foaming agent can achieve an 83.7% blocking rate and improve the extraction degree by 12.02%. The research content of this paper can provide data support for the application effect of a CO₂-soluble blowing agent in a fractured core. Full article

In this study, a twin-screw extruder was used to fabricate poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) blends and blend-based nanocomposites with carbon nanotube (CNT) or nanocarbon black (CB) as nanofillers. The fabricated samples were subsequently treated with supercritical carbon dioxide (scCO₂) to fabricate the corresponding foams. Bi-phasic morphology and selective distribution of CNTs or CBs in the PBAT phase were observed in the blends/composites through scanning electron microscopy. After the scCO₂ treatment, the selective foaming of the PBAT phase in the prepared blends/composites was confirmed. The cellular structure of PBAT phase in scCO₂-treated blends is similar to the size/shape of PBAT domains in untreated blends or treated neat PBAT foam. The addition of CNTs or CBs in the blends led to a slight reduction in cell size of the foamed PBAT phase, demonstrating CNT/CB-induced cell nucleation. Differential scanning calorimetry (DSC) results showed that CNTs and CBs played as nucleating agents and increased the initial crystallization temperature up to 14 °C compared with neat PBAT for PBAT in different composites during cooling. The scCO₂ treatment induced the bimodal stability of PBAT crystals in different samples, which melted mainly in two temperature regions in DSC studies. Thermogravimetric analyses revealed that compared with parent blends, the addition of CNTs or CBs increased the temperature at 80 wt.% loss (degradation of PBAT portion) up to 6 °C. The electrical resistivity decreased by more than six orders of magnitude for certain CNT- or CB-added composites compared with the parent blends. The hardness of the blends slightly increased after forming the corresponding composites and then declined after the scCO₂ treatment. Full article

Degradation of ester-based polyurethane (PUR) foams results in extensive fragmentation, stickiness, and brittleness both at surfaces and in the bulk. Current methods to conserve museum objects comprising PUR foams include consolidation with solvent-based polymeric solutions. Besides the limitations of spray and brush application for deep consolidant penetration and the impracticality of immersing large-scale objects in solutions, these methods often require large amounts of toxic solvents that are harmful for both the user and environment. Carbon dioxide can be employed as a green solvent as it can be recovered, recycled, and reused without contributing to the greenhouse effect. Supercritical carbon dioxide (scCO₂)-assisted consolidation premises are that it may carry the consolidant deeper and deposit it consistently throughout the foam, whilst ensuring minimal interaction with the surface and avoiding material losses in severely degraded objects and the use of toxic solvents. The suitability of scCO₂ as a carrier is studied, and the results compared with spray application, a commonly used traditional method. Previous studies have shown that a mixture of alkoxysilanes has great potential for reinforcing the foam’s structure and hydrophobicity when applied by immersion and other impregnation techniques. In this study, scCO₂-assisted consolidation has proven to be an effective and green alternative to consolidation by spray, reducing hazardous solvent emissions. After treatment, no visual changes were detected, the samples became less sticky, and the foam flexibility improved significantly. Analytical techniques confirmed the presence of the consolidant in all tested samples, both on the top surface and in-depth layers, in contrast to foams treated by spray. Full article

Natural extracts, such as those from the residues of the Olea europaea industry, offer an opportunity for use due to their richness in antioxidant compounds. These compounds can be incorporated into porous polymeric devices with huge potential for tissue engineering such as bone, cardiovascular, osteogenesis, or neural applications using supercritical CO₂. For this purpose, polymeric scaffolds of biodegradable poly(lactic-co-glycolic acid) (PLGA) and chitosan, generated in situ by foaming, were employed for the supercritical impregnation of ethanolic olive leaf extract (OLE). The influence of the presence of chitosan on porosity and interconnectivity in the scaffolds, both with and without impregnated extract, was studied. The scaffolds have been characterized by X-ray computed microtomography, scanning electron microscope, measurements of impregnated load, and antioxidant capacity. The expansion factor decreased as the chitosan content rose, which also occurred when OLE was used. Pore diameters varied, reducing from 0.19 mm in pure PLGA to 0.11 mm in the two experiments with the highest chitosan levels. The connectivity was analyzed, showing that in most instances, adding chitosan doubled the average number of connections, increasing it by a factor of 2.5. An experiment was also conducted to investigate the influence of key factors in the impregnation of the extract, such as pressure (10–30 MPa), temperature (308–328 K), and polymer ratio (1:1–9:1 PLGA/chitosan). Increased pressure facilitated increased OLE loading. The scaffolds were evaluated for antioxidant activity and demonstrated substantial oxidation inhibition (up to 82.5% under optimal conditions) and remarkable potential to combat oxidative stress-induced pathologies. Full article