This study aimed to systematically regulate the performance of 4D printing composites by investigating the synergistic effects of dicumyl peroxide(DCP)and maleic anhydride-grafted polyethylene(MAH-g-PE)on a poly(lacti...This study aimed to systematically regulate the performance of 4D printing composites by investigating the synergistic effects of dicumyl peroxide(DCP)and maleic anhydride-grafted polyethylene(MAH-g-PE)on a poly(lactic acid)/thermoplastic polyurethane(PLA/TPU)matrix.Specifically,using a 70 wt%/30 wt%PLA/TPU matrix and an L_(9)(3^(2))orthogonal design,composites were evaluated via morphology,shape memory,mechanical tests,and multi-criteria analysis.Moderate DCP enhanced crosslinking,improving storage modulus and thermal stability,while excessive DCP caused brittleness.Furthermore,MAH-g-PE effectively improved interfacial compatibility,and its synergy with DCP was dosage-dependent.Consequently,Sample 5 achieved optimal performance,exhibiting uniform fracture morphology,a shape fixation rate of98.8%with the fastest recovery,and balanced strength-ductility.Multi-criteria analysis identified elongation at break and recovery time as the top contributing factors,with consistent rankings validated by Spearman analysis(ρ=0.833,p<0.01).In summary,adjusting DCP and MAH-g-PE contents effectively modulates the crosslinking structure and interfacial properties of PLA/TPU composites,providing a viable strategy for developing high-performance,tunable 4D printing materials.展开更多
Although amide-and hydrazide-based nucleating agents have been extensively used to enhance the crystallization performance of poly(lactic acid)(PLA),structurally similar nucleating agents exhibit significant differenc...Although amide-and hydrazide-based nucleating agents have been extensively used to enhance the crystallization performance of poly(lactic acid)(PLA),structurally similar nucleating agents exhibit significant differences in their crystallization-promoting efficiency,and the underlying mechanism remains unclear.In this study,a series of nucleating agents,including N,N-diphenylterephthalamide(DPTA),N,N,N-triphenyl-1,3,5-benzenetricarboxamide(TPTA),N,N-diphenyl terephthalohydrazide(DBTA),and N,N,N-tribenzoyl-1,3,5-benzenetricarbohydrazide(TBTA),were designed and synthesized to investigate the differences in their effects on the crystallization performance of PLA.Density functional theory(DFT)and molecular dynamics(MD)simulations showed that DBTA had a smaller electrostatic potential difference(66.2 kcal/mol).During the cooling process,DBTA could stably form more intermolecular hydrogen bonds with PLA and exhibit a higher interaction energy,thus theoretically enabling more efficient promotion of PLA crystallization.Further differential scanning calorimetry(DSC)results revealed that at a 0.5wt%loading of DBTA,the crystallization peak temperature of the PLA-DBTA composite reached 118.1℃during cooling,whereas no distinct crystallization peak was observed for pure PLA under identical conditions.The crystallinity of the composite was significantly increased to 58.4%compared to 14.6%of pure PLA.Moreover,under isothermal crystallization at 130℃,DBTA reduced the half-crystallization time of PLA to 2.9min,while the half-crystallization time for pure PLA was 27.4 min.Time-resolved Fourier transform infrared spectroscopy(FTIR)results also confirmed that DBTA promoted the formation of gt conformational isomers of PLA during the crystallization process.This study elucidates the mechanism behind the performance differences between structurally similar nucleating agents in regulating PLA crystallization from the perspective of molecular electrostatic potential and hydrogen bonding interactions,providing a theoretical basis for the molecular design of efficient nucleating agents.展开更多
The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to...The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to provide ideas for this issue.This strategy relied on using appropriate mechanical treatment and sodium lignosulfonate coating to improve the dispersion and interfacial compatibility of bamboo fibers in poly(lactic acid).By optimising the particle size and concentration of sodium lignosulphonate,high value-added and green composites were prepared using sectional pressurization with a venting procedure.The treated composite displayed an ultra-smooth surface(roughness of 0.592 nm),impressive transient properties(disintegration and degradation behaviour after 30 d),and outstanding ultraviolet(UV)shielding properties(100%).These properties hold the promise of being an excellent substrate for electronic devices,especially for high-precision processing,transient electronics,and UV damage prevention.The satisfactory interfacial compatibility of the composites was confirmed by detailed characterisation regarding the related physicochemical properties.This investigation offers a sustainable approach for producing high value-added green composites from biomass and biomass-derived materials.展开更多
This article provided a preparation protocol for poly(lactic acid)(PLA)/modified epoxidized soybean oil(ECP)/nano-magnesium oxide(n-MgO)ternary composites and studied their mechanical and antibacterial properties.By m...This article provided a preparation protocol for poly(lactic acid)(PLA)/modified epoxidized soybean oil(ECP)/nano-magnesium oxide(n-MgO)ternary composites and studied their mechanical and antibacterial properties.By means of an organic synthesis technique,epoxidized soybean oil(ESO)is chemically grafted to PLA to synthesize ESO chemically plastically modified PLA,abbreviated ECP.To fabricate PLA/ECP/n-MgO composite materials,ECP acts as a plasticizer and a compatibilizer simultaneously,and n-MgO acts as an enhancer.Then scanning electron microscopy,X-ray diffraction,differential scanning calorimetry,universal tester,and antibacterial research were exploited to characterize the morphology,thermal resistance,mechanical properties,and antibacterial performance of PLA/ECP/n-MgO composites.The experimental results show that ECP acts as a plasticizer by causing heterogeneous nucleation,which increases PLA's crystallinity.Evenly distributed n-MgO can greatly improve PLA's antibacterial qualities.Furthermore,ECP and n-MgO work together to improve the positive aspects of PLA/ECP/n-MgO composites,with PLA/ECP/n-MgO 100/1/0.5 composites having the best overall properties.While improving the mechanical performance and toughness of PLA,this work offers a prospective approach and foundational database for the creation of multifunctional biodegradable composites.展开更多
To retain its inherent biodegradability,simultaneously improving the strength and toughness of poly(lactic acid)(PLA)is a significant challenge.In this study,we propose an innovative multiple dynamic pressure(MDP)proc...To retain its inherent biodegradability,simultaneously improving the strength and toughness of poly(lactic acid)(PLA)is a significant challenge.In this study,we propose an innovative multiple dynamic pressure(MDP)process that can produce pure PLA with excellent mechanical properties.The MDP process generates a dynamic stretching effect by regulating the application and release of pressure,prompting disordered molecular chains to be arranged regularly along the direction of the dynamic force field.This promoted the formation of more ordered crystal forms(α-form)and strengthened the connection between the crystalline and amorphous regions.Results show that after MDP treatment,the tensile strength and strain at break of MDP-PLA are significantly improved,reaching 91.6 MPa and 80.1%respectively,which are 49.4%higher and 10 times higher than those of the samples before treatment.The mechanical properties of MDP-PLA can be regulated as needed by adjusting the cycle times and peak pressure.In addition,through a systematic study of the structural evolution of MDP-PLA,the performance regulation mechanism of the MDP process was thoroughly investigated,and the internal relationship among the process-structure-performance was clarified.This research not only opens a new technical path for the preparation of high-performance pure PLA but also provides important guidance for the high-performance modification of other semi-crystalline polymers,thus possessing significant scientific and engineering value.展开更多
Poly(lactic acid)(PLA),a bio-based polymer,is considered to be a sustainable alternative to conventional petroleum-based plastics.However,owing to its widespread use and relatively slow degradation rate in water,PLA s...Poly(lactic acid)(PLA),a bio-based polymer,is considered to be a sustainable alternative to conventional petroleum-based plastics.However,owing to its widespread use and relatively slow degradation rate in water,PLA still poses potential environmental pollution risks after being discarded.The efficient chemical recycling of PLA represents an attractive approach to addressing both resource reuse and environmental pollution challenges caused by its waste.Hydrolysis is the predominant method of industrial recycling.However,because PLA is insoluble in water,efficient heterogeneous hydrolysis requires high-temperature and high-pressure conditions.In this study,an efficient homogenous hydrolysis method capable of simultaneously dissolving PLA and calcium hydroxide(Ca(OH)_(2))was developed.Suitable solvents for this method were screened,and it was found that PLA hydrolysis using dioxane and 1,4,7,10,13-Pen-taoxacyclopentadecane as solvents achieved conversion rates of 93%and 90%,respectively,within 2 h at room temperature.Notably,the hydrolysis product,calcium lactate,precipitated as a solid from the solvent and therefore self-separated from the reaction solution.The solvent,acid/base conditions,water content,and depolymerization kinetics were investigated.Compared with previously reported hydrolysis methods,the enhanced efficiency observed in this study can be attributed to the concurrent solvation of PLA and Ca(OH)_(2),which maintains homogeneity throughout the reaction process.Additionally,this method facilitates closed-loop recycling of PLA and is compatible with the highly selective recovery of PLA from various types of PLA products.展开更多
AIM:To develop a 5-fluorouracil(5-FU)mesoporous poly(lactic)acid(PLA)delivery system for glaucoma filtration surgery suitable for a single subconjunctival implantation.METHODS:The 5-FU was infiltration-loaded into mes...AIM:To develop a 5-fluorouracil(5-FU)mesoporous poly(lactic)acid(PLA)delivery system for glaucoma filtration surgery suitable for a single subconjunctival implantation.METHODS:The 5-FU was infiltration-loaded into mesoporous PLA.In vitro and in vivo release experiments and ocular toxicology evaluation of the formulation were performed.The antiproliferative effect of this 5-FU-PLA tablet after glaucoma filtration surgery in rabbits was evaluated.Pathology,immunohistochemistry,and Western blot were used to further validate the inhibitory effect of this sustained release system.RESULTS:Various drug formulations were tested,and two 5-FU-PLA tablets,namely 1.5P15(5-FU 1.5 mg+PLA 15000 Da)and 2.5P15(5-FU 2.5 mg+PLA 15000 Da),had the most suitable release profiles in vitro.Further in vivo studies confirmed the safety and sustained-release profiles of both drugs.Both 5-FU-PLA tablets,relative to the free drugs,significantly inhibited tissue proliferation after glaucoma filtration and improved surgical success.Western blot showed that transforming growth factor-β(TGF-β)and connective tissue growth factor(CTGF)were inhibited by 5-FU after filtration surgery,with the effects of the 5-FU-PLA tablets being more lasting.CONCLUSION:The tested 5-FU-PLA tablets provide a sustained release of 5-FU,which may be used for a single subconjunctival implantation to inhibit proliferation after filtration surgery.展开更多
The continuous improvement in patient care and recovery is driving the development of innovative materials for medical applications.Medical sutures,essential for securing implants and closing deep wounds,have evolved ...The continuous improvement in patient care and recovery is driving the development of innovative materials for medical applications.Medical sutures,essential for securing implants and closing deep wounds,have evolved to incorporate smart materials capable of responding to various stimuli.This study explores the potential of thermoresponsive sutures,made from shape memory materials,that contract upon heating to bring loose stitches closer together,promoting optimal wound closure.We developed nanocomposites based on a blend of poly(lactic acid)(PLA)and thermoplastic polyurethane(TPU)—biopolymers that inherently exhibit shape memory—enhanced with carbon nanotubes(CNT)and graphene nanoplatelets(GN)to improve mechanical performance.PLA/TPU(50/50)nanocomposites were prepared with 1 and 2 wt%GN,as well as hybrid formulations combining 1 wt%CNT with 1 or 2 wt%GN,using a twin-screw extrusion process to form filaments.These filaments were characterized through differential scanning calorimetry(DSC),field emission gun scanning electron microscopy(FEG-SEM),tensile testing,and shape memory assessments.While the PLA/TPU blend is immiscible,TPU enhances the crystallinity(X_(c))of the PLA phase,further increased by the addition of CNT and GN.FEG-SEM images indicate CNTs primarily in the PLA phase and GN in the TPU phase.PLA/TPU with 1 or 2 wt%GN showed the highest potential for suture applications,with a high elastic modulus(~1000 MPa),significant strain at break(~10%),and effective shape recovery(~20%at 55℃ for 30 min).These findings suggest that these nanocomposites can enhance suture performance with controlled shape recovery that is suitable for medical use.展开更多
基金supported by the National Natural Science Foundation of China(No.51905543)。
文摘This study aimed to systematically regulate the performance of 4D printing composites by investigating the synergistic effects of dicumyl peroxide(DCP)and maleic anhydride-grafted polyethylene(MAH-g-PE)on a poly(lactic acid)/thermoplastic polyurethane(PLA/TPU)matrix.Specifically,using a 70 wt%/30 wt%PLA/TPU matrix and an L_(9)(3^(2))orthogonal design,composites were evaluated via morphology,shape memory,mechanical tests,and multi-criteria analysis.Moderate DCP enhanced crosslinking,improving storage modulus and thermal stability,while excessive DCP caused brittleness.Furthermore,MAH-g-PE effectively improved interfacial compatibility,and its synergy with DCP was dosage-dependent.Consequently,Sample 5 achieved optimal performance,exhibiting uniform fracture morphology,a shape fixation rate of98.8%with the fastest recovery,and balanced strength-ductility.Multi-criteria analysis identified elongation at break and recovery time as the top contributing factors,with consistent rankings validated by Spearman analysis(ρ=0.833,p<0.01).In summary,adjusting DCP and MAH-g-PE contents effectively modulates the crosslinking structure and interfacial properties of PLA/TPU composites,providing a viable strategy for developing high-performance,tunable 4D printing materials.
基金supported by the Project of the National Science Foundation of China(Nos.52173033,51773044 and 51603047)Foshan Science and Technology Innovation Project(No.FS0AA-KJ919-4402-0145)。
文摘Although amide-and hydrazide-based nucleating agents have been extensively used to enhance the crystallization performance of poly(lactic acid)(PLA),structurally similar nucleating agents exhibit significant differences in their crystallization-promoting efficiency,and the underlying mechanism remains unclear.In this study,a series of nucleating agents,including N,N-diphenylterephthalamide(DPTA),N,N,N-triphenyl-1,3,5-benzenetricarboxamide(TPTA),N,N-diphenyl terephthalohydrazide(DBTA),and N,N,N-tribenzoyl-1,3,5-benzenetricarbohydrazide(TBTA),were designed and synthesized to investigate the differences in their effects on the crystallization performance of PLA.Density functional theory(DFT)and molecular dynamics(MD)simulations showed that DBTA had a smaller electrostatic potential difference(66.2 kcal/mol).During the cooling process,DBTA could stably form more intermolecular hydrogen bonds with PLA and exhibit a higher interaction energy,thus theoretically enabling more efficient promotion of PLA crystallization.Further differential scanning calorimetry(DSC)results revealed that at a 0.5wt%loading of DBTA,the crystallization peak temperature of the PLA-DBTA composite reached 118.1℃during cooling,whereas no distinct crystallization peak was observed for pure PLA under identical conditions.The crystallinity of the composite was significantly increased to 58.4%compared to 14.6%of pure PLA.Moreover,under isothermal crystallization at 130℃,DBTA reduced the half-crystallization time of PLA to 2.9min,while the half-crystallization time for pure PLA was 27.4 min.Time-resolved Fourier transform infrared spectroscopy(FTIR)results also confirmed that DBTA promoted the formation of gt conformational isomers of PLA during the crystallization process.This study elucidates the mechanism behind the performance differences between structurally similar nucleating agents in regulating PLA crystallization from the perspective of molecular electrostatic potential and hydrogen bonding interactions,providing a theoretical basis for the molecular design of efficient nucleating agents.
基金supported by the National Natural Science Foundation of China(Nos.31971741 and 31760195)the Yunnan Fundamental Research Projects(Nos.2018FB066 and 202001AT070141)the Yunnan Agricultural Basic Research Special Projects(No.202101BD070001-086).
文摘The increasing deployment of electronics in everyday life has generated great concerns regarding the effective disposal of waste from these components.Here,we focused on a facile sustainable and economical strategy to provide ideas for this issue.This strategy relied on using appropriate mechanical treatment and sodium lignosulfonate coating to improve the dispersion and interfacial compatibility of bamboo fibers in poly(lactic acid).By optimising the particle size and concentration of sodium lignosulphonate,high value-added and green composites were prepared using sectional pressurization with a venting procedure.The treated composite displayed an ultra-smooth surface(roughness of 0.592 nm),impressive transient properties(disintegration and degradation behaviour after 30 d),and outstanding ultraviolet(UV)shielding properties(100%).These properties hold the promise of being an excellent substrate for electronic devices,especially for high-precision processing,transient electronics,and UV damage prevention.The satisfactory interfacial compatibility of the composites was confirmed by detailed characterisation regarding the related physicochemical properties.This investigation offers a sustainable approach for producing high value-added green composites from biomass and biomass-derived materials.
基金Funded by the National Natural Science Foundation of China(No.21104031)the Education Department of Hunan province in 2020(No.20C1589)。
文摘This article provided a preparation protocol for poly(lactic acid)(PLA)/modified epoxidized soybean oil(ECP)/nano-magnesium oxide(n-MgO)ternary composites and studied their mechanical and antibacterial properties.By means of an organic synthesis technique,epoxidized soybean oil(ESO)is chemically grafted to PLA to synthesize ESO chemically plastically modified PLA,abbreviated ECP.To fabricate PLA/ECP/n-MgO composite materials,ECP acts as a plasticizer and a compatibilizer simultaneously,and n-MgO acts as an enhancer.Then scanning electron microscopy,X-ray diffraction,differential scanning calorimetry,universal tester,and antibacterial research were exploited to characterize the morphology,thermal resistance,mechanical properties,and antibacterial performance of PLA/ECP/n-MgO composites.The experimental results show that ECP acts as a plasticizer by causing heterogeneous nucleation,which increases PLA's crystallinity.Evenly distributed n-MgO can greatly improve PLA's antibacterial qualities.Furthermore,ECP and n-MgO work together to improve the positive aspects of PLA/ECP/n-MgO composites,with PLA/ECP/n-MgO 100/1/0.5 composites having the best overall properties.While improving the mechanical performance and toughness of PLA,this work offers a prospective approach and foundational database for the creation of multifunctional biodegradable composites.
基金supported by the National Key Research and Development Program of China(No.2023YFC3904604)the Fundamental Research Funds for the Central Universities(No.2024ZYGXZR080)+1 种基金Science and Technology Project of Guangzhou(No.2025A04J3914)Research and Development Program of Jiangmen(No.2023780200030009506).
文摘To retain its inherent biodegradability,simultaneously improving the strength and toughness of poly(lactic acid)(PLA)is a significant challenge.In this study,we propose an innovative multiple dynamic pressure(MDP)process that can produce pure PLA with excellent mechanical properties.The MDP process generates a dynamic stretching effect by regulating the application and release of pressure,prompting disordered molecular chains to be arranged regularly along the direction of the dynamic force field.This promoted the formation of more ordered crystal forms(α-form)and strengthened the connection between the crystalline and amorphous regions.Results show that after MDP treatment,the tensile strength and strain at break of MDP-PLA are significantly improved,reaching 91.6 MPa and 80.1%respectively,which are 49.4%higher and 10 times higher than those of the samples before treatment.The mechanical properties of MDP-PLA can be regulated as needed by adjusting the cycle times and peak pressure.In addition,through a systematic study of the structural evolution of MDP-PLA,the performance regulation mechanism of the MDP process was thoroughly investigated,and the internal relationship among the process-structure-performance was clarified.This research not only opens a new technical path for the preparation of high-performance pure PLA but also provides important guidance for the high-performance modification of other semi-crystalline polymers,thus possessing significant scientific and engineering value.
基金financially supported by the National Key R&D Program of China(No.2021YFB3801901)the National Natural Science Foundation of China(No.22075188 and U19A2095)supported by State Key Laboratory of Materials Processing and Die&Mould Technology,Huazhong University of Science and Technology。
文摘Poly(lactic acid)(PLA),a bio-based polymer,is considered to be a sustainable alternative to conventional petroleum-based plastics.However,owing to its widespread use and relatively slow degradation rate in water,PLA still poses potential environmental pollution risks after being discarded.The efficient chemical recycling of PLA represents an attractive approach to addressing both resource reuse and environmental pollution challenges caused by its waste.Hydrolysis is the predominant method of industrial recycling.However,because PLA is insoluble in water,efficient heterogeneous hydrolysis requires high-temperature and high-pressure conditions.In this study,an efficient homogenous hydrolysis method capable of simultaneously dissolving PLA and calcium hydroxide(Ca(OH)_(2))was developed.Suitable solvents for this method were screened,and it was found that PLA hydrolysis using dioxane and 1,4,7,10,13-Pen-taoxacyclopentadecane as solvents achieved conversion rates of 93%and 90%,respectively,within 2 h at room temperature.Notably,the hydrolysis product,calcium lactate,precipitated as a solid from the solvent and therefore self-separated from the reaction solution.The solvent,acid/base conditions,water content,and depolymerization kinetics were investigated.Compared with previously reported hydrolysis methods,the enhanced efficiency observed in this study can be attributed to the concurrent solvation of PLA and Ca(OH)_(2),which maintains homogeneity throughout the reaction process.Additionally,this method facilitates closed-loop recycling of PLA and is compatible with the highly selective recovery of PLA from various types of PLA products.
基金Supported by the National Natural Science Foundation of China(No.82301211)Beijing Natural Science Foundation(No.J230028).
文摘AIM:To develop a 5-fluorouracil(5-FU)mesoporous poly(lactic)acid(PLA)delivery system for glaucoma filtration surgery suitable for a single subconjunctival implantation.METHODS:The 5-FU was infiltration-loaded into mesoporous PLA.In vitro and in vivo release experiments and ocular toxicology evaluation of the formulation were performed.The antiproliferative effect of this 5-FU-PLA tablet after glaucoma filtration surgery in rabbits was evaluated.Pathology,immunohistochemistry,and Western blot were used to further validate the inhibitory effect of this sustained release system.RESULTS:Various drug formulations were tested,and two 5-FU-PLA tablets,namely 1.5P15(5-FU 1.5 mg+PLA 15000 Da)and 2.5P15(5-FU 2.5 mg+PLA 15000 Da),had the most suitable release profiles in vitro.Further in vivo studies confirmed the safety and sustained-release profiles of both drugs.Both 5-FU-PLA tablets,relative to the free drugs,significantly inhibited tissue proliferation after glaucoma filtration and improved surgical success.Western blot showed that transforming growth factor-β(TGF-β)and connective tissue growth factor(CTGF)were inhibited by 5-FU after filtration surgery,with the effects of the 5-FU-PLA tablets being more lasting.CONCLUSION:The tested 5-FU-PLA tablets provide a sustained release of 5-FU,which may be used for a single subconjunctival implantation to inhibit proliferation after filtration surgery.
基金This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoalde Nível Superior-Brasil(CAPES)-Finance Code 001.
文摘The continuous improvement in patient care and recovery is driving the development of innovative materials for medical applications.Medical sutures,essential for securing implants and closing deep wounds,have evolved to incorporate smart materials capable of responding to various stimuli.This study explores the potential of thermoresponsive sutures,made from shape memory materials,that contract upon heating to bring loose stitches closer together,promoting optimal wound closure.We developed nanocomposites based on a blend of poly(lactic acid)(PLA)and thermoplastic polyurethane(TPU)—biopolymers that inherently exhibit shape memory—enhanced with carbon nanotubes(CNT)and graphene nanoplatelets(GN)to improve mechanical performance.PLA/TPU(50/50)nanocomposites were prepared with 1 and 2 wt%GN,as well as hybrid formulations combining 1 wt%CNT with 1 or 2 wt%GN,using a twin-screw extrusion process to form filaments.These filaments were characterized through differential scanning calorimetry(DSC),field emission gun scanning electron microscopy(FEG-SEM),tensile testing,and shape memory assessments.While the PLA/TPU blend is immiscible,TPU enhances the crystallinity(X_(c))of the PLA phase,further increased by the addition of CNT and GN.FEG-SEM images indicate CNTs primarily in the PLA phase and GN in the TPU phase.PLA/TPU with 1 or 2 wt%GN showed the highest potential for suture applications,with a high elastic modulus(~1000 MPa),significant strain at break(~10%),and effective shape recovery(~20%at 55℃ for 30 min).These findings suggest that these nanocomposites can enhance suture performance with controlled shape recovery that is suitable for medical use.
