Preparation and Characterization of Polylactide/Montmorillonite Nanocomposites

The montmorillonite, a form of layered silicate, was successfully intercalated into polylactide （PLA） matrix through solvent-casting technique. In addition, PLA/MMT nanocomposite films were produced, in which homogenous distribution of the silicate lamellae plays a key role in the mechanical properties of the films. A small amount（5wt%） of OMMT intercalated into the PLA matrix resulted in their flexibility enhancement, from 3.68%（pure PLA film） to 352.65%. The results of wide-angle X-ray diffraction （WAXD） patterns confirmed that the silicate interlayer distance increased from 3.044 nm （for OMMT） to 3.56nm （for 5wt%, maximum） with increasing OMMT contents, but decreased to 3.319 nm when OMMT content was over 8wt%. FT-IR also verified the molecular-level associations between PLA chains and OMMT lamellae by vibration variances of hydrogen bonding. DSC thermograms demonstrated that thermal stabilities of the nanocomposite films enhanced, due to the silicate lamellae dispersed into PLA matrix.

Dyes with high affinity for polylactide

Attempts were made to develop dyes with high affinity for polylactide as an alternative to the existent commercial disperse dyes. The dyes synthesized according to the affinity concept of dye to polylactide exhibited excellent dyeing properties on polylactide compared with the commercial disperse dyes.

Dyeability of Polylactide Fabric with Hydrophobic Anthraquinone Dyes

The dyeability of polylactide fabric has been investigated with the substituted aminoanthraquinone hydophobic dyes. Their application to the polylactide fabric led to good exhaustion values and good wash fastness between 4 and 3. MIcroscopic assessment ot cross-sections ot the dyed polylactlde fibres confirmed that these dyes could penetrate into the fibres. The nature of the substituted amino groups showed little influence on the wash fastness, but clearly influenced.the exhauslion and light fastness.

Improving Polylactide Toughness by Plasticizing with Low Molecular Weight Polylactide-Poly(Butylene Succinate)Copolymer

A low-molecular-weight polylactide-poly(butylene succinate)(PLA-PBS)copolymer was synthesized and incorporated into polylactide(PLA)as a novel toughening agent by solvent casting.The copolymer had the same chemical structure and function as PLA and it was used as a plasticizer to PLA.The copolymer was blended with PLA at a weight ratio from 2 to 10 wt%.Phase separation between PLA and PLA-PBS was not observed from their scanning electron microscopy(SEM)images and the crystal structure of PLA almost remained unchanged based on the X-ray diffraction(XRD)measurement.The melt flow index(MFI)of the blends was higher as the amount of PLA-PBS increased,indicating that the block copolymer did improve the mobility of the PLA chains.Moreover,tensile tests revealed that PLA with greater PLA-PBS copolymer exhibited higher elongation at break and it reached the maximum at 8 wt%of PLA-PBS in PLA,which was around 6 times higher than that of pure PLA.Furthermore,the glass transition temperature,measured by differential scanning calorimetry(DSC),markedly decreased with an increasing amount of the copolymer as it decreased from 61.2℃ for pure PLA to 41.3℃when it was blended with 10 wt%PLA-PBS copolymer.Therefore,the PLA-PBS copolymer was shown to be a promising plasticizer for fully biobased and toughened PLA.

Suitability of Blends from Virgin and Reprocessed Polylactide: Performance and Energy Valorization Kinet

A blending strategy of virgin and reprocessed polylactide may be postulated as an alternative to reduce the material cost at industrial level,and as a valorization route to plastic waste management of production scraps.The performance of blends prepared from virgin polylactide and polylactide mechanically reprocessed up to two cycles(PLA-V/R)was assessed in terms of thermo-oxidative stability,morphology,viscoelasticity and thermal kinetics for energetic valorization.PLA-V/R blends showed appropriate thermo-oxidative stability.The amorphous nature of polylactide was preserved after blending.The viscoelastic properties showed an increment of the mechanical blend effectiveness,which suggested the feasibility of using PLA-V/R blends under similar mechanical conditions to those of virgin PLA goods.Finally,it was shown that the energetic valorization of PLA-V/R blends would result in a more feasible process,due to the lower required activation energy,thus highlighting the advantages of the energetic demand for the process.In conclusion,PLA-V/R blends showed similar processability,service performance and valorization routes as virgin PLA and therefore could be relevant in the sustainable circular industry of bioplastics.

Preparation of Hydroxyapatite/Polylactide Bicomposites by Absorption Process in Liquid Phase

The hydroxyapatite/polylactide biocomposites were prepared by absorption process in liquid phase. The method avoided many disadvantages, such as inaterfusion of chemical impurity substances, nonuniformity dispersal of HA in PLA, low molecular weight of PLA . HA particles were uniformly dispersed in PLA matrix, and showed well ndhesion with PLA matrix. The biocomposites have the higher mechanical properties and suitable decomposable capability.

Amorphous Polylactide Bead Foam–Effect of Talc and Chain Extension on Foaming Behavior and Compression Properties

Polylactide(PLA)bead foams show a high potential regarding their applicability in packaging or consumer products.Concerning the comparable properties of PLA to Polystyrene(PS)and the good CO_(2) footprint it represents a potential alternative to petroleum-based polymer foams.However,foaming of PLA is challenging,due to its low melt strength,therefore chemical modifiers are often used.Concerning the bead foam technology regarding PLA,the available literature is limited so far.Within this study,the bead foaming behavior of neat and modified amorphous PLA was investigated.The material was modified by talc and an epoxy-based chain extender.These compounds have been investigated regarding their sorption behavior in CO_(2) atmosphere and their foaming behavior.Foaming was conducted by using the batch foaming method based on a rapid temperature increase after saturation with CO_(2).In order to achieve welded bead foams,a one-step processing for foaming and welding has been established.Finally,the compression properties of the PLA bead foams have been investigated.Densities below 50 kg/m^(3) for single bead foams and 80 kg/m^(3) for molded foams were achieved,respectively.

Study on the Properties of Esterified Corn Starch/Polylactide Biodegradable Blends

Fully bio-based and biodegradable starch/polylactic acid blends have received increasing attentions for their biodegradability and potential to offset the use of unsustainable fossil resources,specifically,their application in packaging.Herein,corn starch was first esterified with maleic anhydride and then compounded with polylactide(PLA)to prepare esterified corn starch/polylactic acid blends with starch content up to 35 wt%.The structures,morphologies,thermal and mechanical properties of starch or blends were investigated.The results showed that corn starch was successfully grafted with maleic anhydride,which showed increased crystallinity and particle size than native starch.Esterified corn starch/polylactic acid blends showed good surficial compatibility and good thermal stability with main decomposition temperature in the range of 300℃to 400℃.Additionally,incorporation of corn starch increased the hydrophilicity and water uptake of composites.However,the tensile and flexural strengths of blends decreased with increasing esterified starch amount.

The Influence of Poly(Vinyl Alcohol)on Oil Release Behavior of Polylactide-Based Composites Filled with Linseed Cake

In order to limit the negative impact of industry on natural environment,ecological alternatives to conventional polymers are being proposed.One of the most popular“green”polymers is polylactide,which can also be successfully applied as a matrix of composites.The application of ground linseed cake as a filler for polylactide-based composites is in line with the idea of Circular Economy,and moreover it provides a modifying effect on the polymer by increasing its crystallinity and reducing its brittleness.This effect is caused by the presence of linseed oil which can be released to the polymeric matrix in a non-controlled way.In order to control the miscibility of the oil and the polymer,we modified the filler particles with poly(vinyl alcohol)before introducing it to the polylactide.We concluded that poly(vinyl alcohol),which does not mix with oil,encapsulated the active ingredients inside the filler particles.We evaluated the mechanical properties of the composites containing 5,10,20 and 30 wt%of the filler in a static tensile stress and by means of dynamic mechanical thermal analysis.Crystallinity and thermal properties were tested using differential scanning calorimetry as well as thermogravimetric analysis.Composites’microstructure was evaluated by Scanning Electron Microscopy.It was found that modifying the oil-rich filler with poly(vinyl alcohol)helps to reduce its release to the matrix and thus limits the plasticizing effect of linseed cake.This result was in accordance with our hypothesis.

Toddy Palm (Borassus Flabellifer) Fruit Fibre Bundles as Reinforcement in Polylactide (PLA) Composites: An Overview About Fibre and Composite Characteristics

Toddy palm fruit have an apparent density below 0.8 g/cm³and offer an interesting lightweight construction potential in polylactide(PLA)composites reinforced with 37 mass-%fibres.Single fibre bundles show similar mechanical properties compared with coir:tensile strength of 240 MPa,Young´s modulus of 3.8 GPa and an elongation at break of 31%.However,density and diameter(~50μm)of fruit fibre bundles are significantly lower.The compression moulded composites have a density of 0.9 g/cm³and achieved an unnotched Charpy impact strength of 12 kJ/m^(2),a tensile strength of 25 MPa,Young’s modulus of 1.9 GPa and an elongation at break of 9%.Due to the high porosity of the composites and the different stress-strain behaviour of fibre and matrix the fibre-reinforcement potential could not be fully used.Maximum stress of the composite was reached at the elongation at break of the PLA-matrix(~2%)while the fibre achieved its maximum stress at an elongation of~31%.After reaching the maximum stress of the composite,the fibres were pulled out from the matrix with low energy absorption,resulting in a decrease in stress and a limited reinforcement potential.Additionally,the study investigates whether an insect attack by the Asian fruit fly on the mesocarp has a significant influence on the mechanical fibre characteristics.The results have shown that only the rough surface of the fibre bundles is smoothed by insect infestation.The mechanical properties were not significantly affected.For this reason insect-infested fruits of the toddy palm,which are no longer suitable for food production,can be used for the production of sustainable composite materials.

Hybrid Composites of Phosphate Glass Fibre/Nano-Hydroxyapatite/Polylactide: Effects of Nano-Hydroxyapatite on Mechanical Properties and Degradation Behaviour

Hydroxyapatite/polylactide (HA/PLA) composites have been intensively investigated for their potential as biodegradable fixation devices to heal bone fractures. However, most of these composites failed to achieve a bone-mimicking level of mechanical properties, which is an essential demand of the targeted application. In this study, the nano-hydroxyapatite/polylactide composites were used as the matrix and continuous phosphate glass fibres (PGF) served as the major reinforcement to obtain the nano-HA/PGF/PLA hybrid composites. While the PGF volume fraction remained constant (25%), the nano-HA content (in weight) varied from 0% to 20%. As nano-HA loading increased, the flexural modulus of the composites increased from 8.70 ± 0.35 GPa to 14.97 ± 1.30 GPa, and the flexural strengths were enhanced from 236.31 ± 10.83 MPa to 310.55 ± 22.88 MPa. However, it is found that the degradation rates are higher with more nano-HA loaded. Enhanced water absorption ability, as well as increased voids in the composites is possible reasons for the accelerated degradation of composites with higher nano-HA loading. The hybrid composites possess mechanical properties that are superior to most of the HA/PLA composites in previous research while maintaining the biodegradability. With a proper loading of nano-HA in composites of 10 weight percent, the composites are also found with improved mechanical properties without catastrophic degradation. The composites developed in this study have great potential as biodegradable bone fixation device with enhanced load-bearing ability as confirmed and superior bioactivity as anticipated.

High Impact Polylactide Based on Organosilicon Nucleation Agent

Various sectors of the industry are searching for new materials with specific requirements,providing improved properties.The study presents novel composite materials based on polylactide that have been modified with the organosilicon compound,(3-thiopropyl)polysilsesquioxane(SSQ-SH).The SSQ-SH compound is a mixture of cage structures and not fully condensed random structures.The composite materials were obtained through injection moulding.The study includes a comprehensive characterization of the new materials that analyze their functional properties,such as rheology(MFR),mechanical strength(tensile strength,Charpy impact strength),and thermal properties.SEM microscopic photos were also taken to analyze the microstructure of the samples.The addition of a 5%by-weight organosilicon compound to polylactide resulted in a significant increase in MFR by 73.8%compared to the neat polymer.The greatest improvement in impact strength was achieved for the 5%SSQ-SH/PLA composite,increasing it by 32.0 kJ/m^(2)compared to PLA,which represents an increase of up to 187%.The conducted research confirms the possibility of modifying the properties of the polymer by employing organosilicon compounds.

Atom-economic synthesis of an oligomeric P/N-containing fire retardant towards fire-retarding and mechanically robust polylactide biocomposites

Renewable and biodegradable polylactide (PLA) has excellent mechanical strength but is highly flammable which restricts its practical applications. Many phosphorus/nitrogen (P/N)-based flame retardants are ef- fective in PLA, but their high addition loading usually decreases the mechanical strength of the PLA bulk. For polyphosphoramides, despite high fire-retardant efficiency, their chemical synthesis often generates chemical wastes as byproducts. Herein, we report an atom-economic and highly efficient oligomeric P/N fire retardant (APN) prepared using a mild Michael addition polymerization with no byproducts. Using only 3 wt% APN, the resulting PLA exhibits desired fire retardancy including a UL-94 V-0 rating and a limiting oxygen index of 37.6%. Furthermore, the toughness of the fire-retardant PLA increases by 85% compared to pure PLA, with both tensile strength and thermal stability preserved. This work offers an atom-economic strategy for synthesizing highly efficient P/N fire retardants for use in the creation of fire-resistant PLA with robust mechanical properties.

Regulating the proinflammatory response to composite biomaterials by targeting immunometabolism

Composite biomaterials comprising polylactide(PLA)and hydroxyapatite(HA)are applied in bone,cartilage and dental regenerative medicine,where HA confers osteoconductive properties.However,after surgical implantation,adverse immune responses to these composites can occur,which have been attributed to size and morphology of HA particles.Approaches to effectively modulate these adverse immune responses have not been described.PLA degradation products have been shown to alter immune cell metabolism(immunometabolism),which drives the inflammatory response.Accordingly,to modulate the inflammatory response to composite biomaterials,inhibitors were incorporated into composites comprised of amorphous PLA(aPLA)and HA(aPLA+HA)to regulate glycolytic flux.Inhibition at specific steps in glycolysis reduced proinflammatory(CD86+CD206-)and increased pro-regenerative(CD206+)immune cell populations around implanted aPLA+HA.Notably,neutrophil and dendritic cell(DC)numbers along with proinflammatory monocyte and macrophage populations were decreased,and Arginase 1 expression among DCs was increased.Targeting immunometabolism to control the proinflammatory response to biomaterial composites,thereby creating a pro-regenerative microenvironment,is a significant advance in tissue engineering where immunomodulation enhances osseointegration and angiogenesis,which could lead to improved bone regeneration.

Rheological, Thermal and Mechanical Properties of Biodegradable Poly(propylene carbonate)/Polylactide/Poly(1,2-propylene glycol adipate) Blown Films

Poly（propylene carbonate） （PPC） was blended with polylactide （PLA） and poly（1,2-propylene glycol adipate） （PPA） using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.

Sustainable Blends of Poly(propylene carbonate)and Stereocomplex Polylactide with Enhanced Rheological Properties and Heat Resistance

Sustainable blends of poly(propylene carbonate)(PPC)and stereocomplex polylactide(sc-PLA)were prepared by melt blending equimolar poly(L-lactic acid)(PLLA)and poly(D-lactide acid)(PDLA)with PPC to form sc-PLA crystals in situ in the melt blending process.Differential seanning calorimetry analysis revealed that only sc-PLA,no homo-crystallization of PLLA or PDLA,formed in the PPC matrix as the sc-PLA con tent was more than 10 wt%.Very in triguingly,scan ning electronic microscopy observati on showed that sc-PLA was evenly dispersed in the PPC phase as spherical particles and the sizes of sc-PLA particles did not obviously increase with in creasing sc-PLA con tent.As a con seque nee,the rheological properties of PPC were greatly improved by incorporation of sc-PLA.When the sc-PLA con tent was 20 wt%,a percolati on n etwork structure was formed,and the blends showed solid-like behavior.The sc-PLA particles could reinforce the PPC matrix,especially at a temperature above the glass transition temperature of PPC.Moreover,the Vicat softening temperature of PPC/sc-PLA blends could be increased compared with that of neat PPC.

Improvement in Toughness of Polylactide by Melt Blending with Bio-based Poly(ester)urethane

Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The miscibility, mechanical properties, phase morphology and toughening mechanism of the blend were investigated. Both DSC and DMTA results manifested that the addition of TPU elastomer not only accelerated the crystallization rate, but also increased the final degree of crystallinity, which proved that TPU has limited miscibility with PLA and has functioned as a plasticizer. All the blend samples showed distinct phase separation phenomenon with sea-island structure under SEM observation and the rubber particle size in the PLA matrix increased with the increased contents of TPU. The mechanical property variation of PLA/TPU blends could be quantitatively explained by Wu＇s model. With the variation of TPU, a brittle-ductile transition has been observed for the TPU/PLA blends. When these blends were under tensile stress conditions, the TPU particles could be debonded from the PLA matrix and the blends showed a high ability to induce large area plastic deformation before break, which was important for the dissipation of the breaking energy. Such mechanism was demonstrated by tensile tests and scanning electron microcopy （SEM） observations.

Preparation and Characteristics of Poly(butylene adipate-coterephthalate)/Polylactide Blend Films via Synergistic Efficiency of Plasticization and Compatibilization

Polylactide(PLA)films blended with poly(butylene adipate-co-terephthalate)(PBAT)were hot melted using a twin screw extruder with the addition of triethyl citrate(TEC)as a plasticizer and toluene diisocyanate(TDI)as a compatibilizer.The synergistic effects of the two additives on the mechanical,thermal,and morphological properties of the PLA/PBAT blend films were investigated.The influence of TEC content on the plasticized PLA films and the effect of TDI’s presence on the PLA/PBAT blend films were also studied by comparing them with neat PLA.The results showed a pronounced increase in elongation at break of the plasticized PLA films with increasing TEC levels,but a slight reduction in thermal stability.Also,the addition of TEC and TDI to the blend system not only synergistically enhanced the tensile properties and tensile-impact strength of the PLA/PBAT blends,but also affected their crystallinity and cold crystallization rate,a result of the improvement of interfacial interaction between PLA and PBAT,including the enhancement of their chain mobility.The synergy of the plasticization and compatibilization processes led to the improvement of tensile properties,tensile-impact strength,and compatibility of the blends,accelerating cold crystallization without affecting crystallization.

Sustained release of isoniazid from polylactide microspheres prepared using solid/oil drug loading method for tuberculosis treatment

Polylactide(PLA) microspheres were prepared using the solid-in-oil(S/O) spray-drying method to achieve the sustained release of a hydrophilic drug for the treatment of tuberculosis, via intratracheal instillation. Isoniazid(IN), a low-molecular-weight hydrophilic drug, was used as a model drug. The effects of various sizes of micronized IN powder, different drug/polymer ratios, spray-drying process parameters, and drug-release characteristics were studied to optimize the manufacturing parameters. A high entrapment efficiency(87.3%) was obtained using this method; furthermore, the microspheres were spherical and smooth. They were individually and homogenously distributed, with a mean diameter of 5.6 μm; furthermore, they showed a satisfactory extended sustained-release phase. After administration of the microspheres to rats, pulmonary drug concentrations were maintained at a relatively stable level for up to 4 weeks.