Ageing of polylactide and polylactide nanocomposite filaments

An experimental study was carried out in order to check the influence of various parameters on the ageing of PLA filaments performed in a climatic room. Initially, two grades of PLA with different d-isomer contents were analysed. Even after several weeks of ageing, properties of PLA filaments with less than 0.5% d-isomer content did not vary extensively. On the other hand, the mechanical and thermal properties of PLA filaments with 4% d-isomer content underwent strong modifications. Subsequently, a selected organomodified bentonite (Bentone^®104 - noted as B104) was blended with PLA and then melt-spun to study the influence of a nanofiller on the ageing of PLA filaments. Faster degradation of PLA nanocomposite filaments was then observed.     

The effect of halloysite nanotubes and N,N'- ethylenebis (stearamide) on the properties of polylactide nanocomposites with amorphous matrix

Amorphous polylactide/halloysite nanotube (PLA/HNT) nanocomposites were prepared and examined. Neat HNT and HNT treated with N,N'- ethylenebis(stearamide) (EBS) were used as nanofillers. The role of HNT and/or EBS content on the cold crystallization of amorphous PLA matrix, HNT dispersion, as well as on the dynamic mechanical and optical properties of the materials was determined.The PLA/HNT-based nanocomposites contained well-distributed nanotubes and occasionally micron-sized aggregates, especially at high loading. HNT, EBS treated HNT and EBS influenced the cold crystallization of PLA, therefore the formation of the disorder α′ and the order α crystallographic forms of PLA.The nanocomposites exhibited increased stiffness and decreased transparency compared to the neat PLA. Due to the reinforcing effect and additional specific features of HNT, the addition of the nanofiller allows tuning of the properties of the nanocomposites with amorphous PLA matrix.     

Combustion properties and thermal degradation behavior of polylactide with an effective intumescent flame retardant

An intumescent flame retardant spirocyclic pentaerythritol bisphosphorate disphosphoryl melamine (SPDPM) has been synthesized and its structure was characterized by Fourier transformed infrared spectrometry (FTIR), ¹H and ³¹P nuclear magnetic resonances (NMR). A series of polylactide (PLA)-based flame retardant composites containing SPDPM were prepared by melt blending method. The combustion properties of PLA/SPDPM composites were evaluated through UL-94, limiting oxygen index (LOI) tests and microscale combustion calorimetry (MCC) experiments. It is found that SPDPM integrating acid, char and gas sources significantly improved the flame retardancy and anti-dripping performance of PLA. When 25 wt% flame retardant was added, the composites achieved UL-94 V0, and the LOI value was increased to 38. Thermogravimetric analysis (TGA) showed that the weight loss rate of PLA was decreased by introduction of SPDPM. In addition, the thermal degradation process and possible flame retardant mechanism of PLA composites with SPDPM were analyzed by in situ FTIR.     

Rheology and thermal stability of polylactide/clay nanocomposites

Polylactide/clay nanocomposites (PLACNs) were prepared by melt intercalation. The intercalated structure of PLACNs was investigated using XRD and TEM. Both the linear and nonlinear rheological properties of PLACNs were measured by parallel plate rheometer. The results reveal that percolation threshold of the PLACNs is about 4 wt%, and the network structure is very sensitive to both the quiescent and the large amplitude oscillatory shear (LAOS) deformation. The stress overshoots in the reverse flow experiments were strongly dependent on the rest time and shear rate but shows a strain-scaling response to the startup of steady shear flow, indicating that the formation of the long-range structure in PLACNs may be the major driving force for the reorganization of the clay network. The thermal behavior of PLACNs was also characterized. However, the results show that with the addition of clay, the thermal stability of PLACNs decreases in contrast to that of pure PLA.     

Effect of natural weather on the structure and properties of polylactide/Cloisite 30B nanocomposites

The degradation of polylactide (PLA)/Cloisite 30B nanocomposites under natural weathering was investigated as a function of clay loadings (1, 3 and 5 wt.%) for up to 130 days using Fourier transform infrared (FT-IR) spectroscopy, size exclusion chromatography (SEC), nanoindentation measurements, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). For comparative purposes, the neat PLA was also considered. The FT-IR results showed that the photo-oxidation mechanism of PLA was not modified in the presence of Cloisite 30B, but only the degradation rates were accelerated. Moreover, the photo-oxidative degradation of PLA nanocomposite samples led to the formation of vinyl unsaturation, carbonyls, anhydrides and hydroperoxides groups as a result of the occurrence of several chemical mechanisms simultaneously. The decrease of the weight-average molecular weight, and the number-average molecular weight associated with an enhanced polydispersity of the nanocomposite samples indicated that chain scission was the most prominent phenomenon in natural weathering. The thermal degradation of the PLA was faster in the presence of clay. Modulus and hardness measured by nanoindentation increased slightly with exposure time for both neat PLA and PLA nanocomposite samples; the increase is also a function of the clay content. Finally, the weathering effect on the morphology of exposed samples observed by SEM revealed that the fractured surfaces exhibited many voids and cracks. These defects were much more pronounced for the PLA nanocomposites.     

Synergistic effect between a novel hyperbranched charring agent and ammonium polyphosphate on the flame retardant and anti-dripping properties of polylactide

A novel hyperbranched polyamine charring agent (HPCA), a derivative of triazines, was synthesized and well characterized by ¹H NMR and FTIR. HPCA and ammonium polyphosphate (APP) were added into polylactide (PLA) resin as an intumescent flame retardant (IFR) system to impart flame retardancy and dripping resistance to PLA. The flammability and thermal stability of IFR-PLA composites were investigated by limiting oxygen index (LOI), UL-94 vertical burning, cone calorimetry and thermogravometric analysis (TGA) tests. The results showed that the IFR system had both excellent flame retardant and anti-dripping abilities for PLA. The TGA curves suggested that HPCA has good ability of char formation and when combined with APP, would induce synergistic effect which could be clearly observed. This effect greatly promoted the char formation of IFR-PLA composites, hence improved the flame retardant property. Additionally, the structure and morphology of char residues were studied by XPS, FTIR and SEM.     

The influence of matrix crystallinity,filler grain size and modification on properties of PLA/calcium carbonate composites

Thermal and mechanical properties of polylactide (PLA) composites with different grades of calcium carbonate, 40 nm and 90 nm nanoparticles, and also with submicron particles, unmodified and modified with calcium stearate or stearic acid, obtained by melt mixing, were compared. Films with amorphous and crystalline matrices were prepared and examined.T_g of PLA in the composites remained unaffected whereas its cold crystallization was enhanced by the fillers and predominantly depended on filler content. Filling decreased thermal stability of the materials but their 5% weight loss temperatures well exceeded 250 °C, evidencing stability in the temperature range of PLA processing. The amorphous nanocomposites with modified nanoparticles exhibited improved drawability and toughness without a significant decrease of tensile strength; nearly two-fold increase of the elongation at break and tensile toughness was achieved at 5 wt% content of the modified nanofiller. Lack of surface modification of the filler, larger grain size with an average of 0.9 μm, and matrix crystallinity had a detrimental effect on the drawability. However, the presence of nanofillers and crystallinity improved tensile modulus of the materials by up to 15% compared to neat amorphous PLA.     

Poly(cetyl trimethylammonium 4-styrenesulfonate)-wrapped carbon nanotubes filled in polylactide nanocomposites: Fabrication and properties

Poly(cetyl trimethylammonium 4-styrenesulfonate) (PSS-CTA) was synthesized by the ionic exchange reaction of poly(sodium 4-styrenesulfonate) (PSS-Na) with cetyl trimethylammonium bromide (CTAB). It was then used as a surface modifier for carbon nanotubes (CNTs) to improve dispersion in and interfacial adhesion with a polylactide (PLA) matrix to fabricate high performance PLA/CNT nanocomposites via a solution precipitation method. The morphology, electrical conductivity, crystallization and mechanical properties of the PLA nanocomposites were investigated in detail. The results indicate that CNTs wrapped (coated) with a suitable amount of PSS-CTA dispersed in the PLA matrix homogeneously. The electrical conductivity of PLA was enhanced by up to 10 orders of magnitude with the incorporation of 1.0 wt% PSS-CTA-modified CNTs (mCNTs). The crystallization rate of PLA was improved due to the nucleation effect of mCNTs towards the crystallization of PLA, but the crystallization mechanisms and crystal structure of PLA remained unchanged with the incorporation of mCNTs. Both the tensile strength and toughness of PLA were improved by the incorporation of mCNTs, and the fracture behaviour of PLA changed from brittle e to ductile during tensile testing.     

Viscoelasticity and thermal stability of polylactide composites with various functionalized carbon nanotubes

Polylactide (PLA) nanocomposites containing various functionalized multi-walled carbon nanotubes (MWCNTs) were prepared directly by melt compounding. The linear rheology and thermal stability of the PLA nanocomposites were, respectively, investigated by the parallel plate rheometer and TGA, aiming at examining the effect of surface functionalization on the dispersion of MWCNTs by using viscoelastic and thermal properties. Among three MWCNTs used in this work, the carboxylic MWCNTs present better dispersion in PLA matrix than the hydroxy and purified MWCNTs because the corresponding composite shows the lowest rheological percolation threshold, which is further confirmed by the TEM and solution experiments. The presence of all these three MWCNTs, however, nearly cannot improve the thermal stability effectively at the initial stage of degradation and the temperature corresponding to a weight loss of 5 wt% (T_5 wt%) only shows slight increase in contrast to that of the neat PLA while with increase of decomposition level, the presence of carboxylic and purified MWCNTs retards the depolymerization of PLA evidently, showing remarkable increase in the temperature corresponding to maximum rate of decomposition (T_max). Both the dispersion state and the surface functionalization of MWCNTs are very important to the thermal stability of PLA matrix.     

Tough and transparent blends of polylactide with block copolymers of ethylene glycol and propylene glycol

In order to modify its physical properties, particularly the drawability and toughness, polylactide (PLA) was melt blended with a set of PEG-b-PPG-b-PEG block copolymers with varying ratio of the hydrophilic (PEG) and hydrophobic (PPG) blocks. Miscibility of the copolymers with PLA depended on their molar mass and PEG content. Interestingly, the best drawability was achieved in the case of partially miscible blends, in which fine liquid inclusions of the modifier were dispersed in PLA rich matrix with glass transition temperature only moderately decreased, to about 50 °C. About 37 fold increase of the elongation at break and about 1.5 fold increase of the tensile impact strength with respect to neat PLA were reached at small content (10 wt.%) of the modifier. Despite the phase separation, the blends remained transparent. In addition, the barrier properties for oxygen were improved.     

Polylactide/montmorillonite nanocomposites: Structure, dielectric, viscoelastic and thermal properties

Polylactide-based systems composed of an organoclay (Cloisite^® 30B) and/or a compatibilizer (Exxelor VA1803) prepared by melt blending were investigated. Two types of not compatibilized nanocomposites containing 3 wt% or 10 wt% of the organoclay were studied to reveal the effect of the filler concentration on the nanostructure and physical properties of such systems. The 3 wt%-nanocomposite was also additionally compatibilized in order to improve the nanoclay dispersion. Neat polylactide and polylactide with the compatibilizer processed in similar conditions were used as reference samples. The X-ray investigations showed the presence of exfoliated nanostructure in 3 wt%-nanocomposite. Compatibilization of such system noticeably enhanced the degree of exfoliation of the organoclay. Viscoelastic spectra (DMTA) showed an increase of the storage and loss moduli with the increase of the organoclay content and dispersion. Dielectric properties of the nanocomposites show a weak influence of the nanoclay on segmental (α_S) and local (β)-relaxations in PLA, except for the highest nanoclay content. Above T_g a strong increase of dc conductivity related to ionic species in the clay is observed. It gives rise also to the Maxwell-Wagner-Sillars interfacial polarization and both real and imaginary parts of ε strongly increase. In the temperature dependence of low frequency dielectric constant and mechanical moduli (at 1 Hz) an additional maximum around 80-90 °C is observed due to cold crystallization of PLA.     

Tough crystalline blends of polylactide with block copolymers of ethylene glycol and propylene glycol

The effect of crystallinity of polylactide (PLA) on the structure and properties of tough PLA blends with PEG-b-PPG-b-PEG block copolymers was studied. PLA was melt blended with a set of the copolymers with varying ratio of the hydrophilic (PEG) and hydrophobic (PPG) blocks. Although the blend phase structure depended on the copolymer molar mass and PEG content, as well as on the copolymer concentration in the blend, crystallinity also played an important role, increasing the copolymer content in the amorphous phase and enhancing phase separation. The influence of crystallinity on the thermal and mechanical properties of the blends depended on the copolymer used and its content. The blends, with PLA crystallinity of 25 ÷ 34 wt%, exhibited relatively high glass transition temperature ranging from 45 to 52 °C, and melting beginning above 120 °C. Although with a few exceptions crystallinity worsened the drawability and toughness, these properties were improved with respect to neat crystalline PLA in the case of partially miscible blends, in which fine liquid inclusions of the modifier were dispersed in PLA rich matrix. About 20-fold increase of the elongation at break and about 4-fold increase of the tensile impact strength were reached at a small content (10 wt%) of the modifier. Moreover, crystallinity decreased oxygen and water vapor transmission rates through neat PLA and the blend, and the barrier property for oxygen of the latter was better than that of neat polymer.     

The production and properties of polylactide composites filled with expanded graphite

Composites have been produced by melt-blending biodegradable polylactide (PLA) with commercially available expanded graphite (EG). Using different techniques of addition, the manifold effects of EG on PLA molecular, thermo-mechanical and fire-retardant properties were evaluated. The EG nanofiller provides PLA composites with competitive functional properties. They have a high rigidity, with Young's modulus and storage modulus increasing with EG content. They also have excellent thermal stability while preserving the glass transition and melting temperature of the original PLA matrix. Purification and pre-dispersion of EG nanofiller proved beneficial for preserving PLA molecular weights and led to improved mechanical performance. The presence of dispersed graphene nanolayers in PLA significantly accelerated the polyester crystallization process. The flame retardant properties also displayed improvements with a large decrease in the maximum rate of heat release as recorded by cone calorimetry, whereas the horizontal burning test (UL94 HB) was successfully passed revealing non-dripping and char formation.     

Structural-phase state and surface properties of composite materials based on polylactide and hydroxyapatite

The phase composition and unit cell parameters were determined for composites based on polylactide and hydroxyapatite with the polylactide/hydroxyapatite weight ratios of 90/10, 80/20, 70/30, and 60/40. As the polylactide content of the composites is increased, they become less hydrophilic, and the surface energy σ_S-G increases from 29.13 to 74.35 mJ m^–2. The sample with the component weight ratio of 70/30 is characterized by the maximal roughness, and the Ca²⁺ and Mg²⁺ ions from simulated body fluid are actively adsorbed onto its surface, as proved by SEM examination of the composites.     

Thermal analysis applied to the characterization of degradation in soil of polylactide: II. On the thermal stability and thermal decomposition kinetics

The disposal stage of polylactide (PLA) was assessed by burying it in active soil following an international standard. Degradation in soil promotes physical and chemical changes in the polylactide properties. The characterization of the extent of degradation underwent by PLA was carried out by using Thermal Analysis techniques. In this paper, studies on the thermal stability and the thermal decomposition kinetics were performed in order to assess the degradation process of a commercial PLA submitted to an accelerated soil burial test by means of multi-linear-non-isothermal thermogravimetric analyses. Results have been correlated to changes in molecular weight, showing the same evolution as that described by the parameters of thermal stability temperatures and apparent activation energies. The decomposition reactions can be described by two competitive different mechanisms: Nucleation model (A2) and Reaction Contracting Volume model (R3). The changes in the kinetic parameters and kinetic models are in agreement with the calorimetric and dynamic-mechanical-thermal results, presented in the Part I of the study [1].     

New titanium and zirconium initiators for the production of polylactide

Two new group 4 initiators based on N,N′-Bis(2-hydroxybenzyl)ethylenediamine have been prepared and fully characterised via multi-nuclear NMR spectroscopy and single crystal X-ray diffraction studies. The complexes have been tested for the production of polylactide. The phenolate ligand complexes to Ti(IV) to generate the β-cis isomer in the solid-state. Whereas for Zr(IV) the isolated species (regardless of stoichiometery) is a diligated complex.     

Mechanical,aging, optical and rheological properties of toughening polylactide by melt blending with poly(ethylene glycol) based copolymers

Two novel biodegradable copolymers, including poly(ethylene glycol)-succinate copolymer (PES) and poly(ethylene glycol)-succinate-l-lactide copolymer (PESL), have been successfully synthesized via melt polycondensation using SnCl₂ as a catalyst. The copolymers were used to toughen PLA by melt blending. The DSC and SEM results indicated that the two copolymers were compatible well with PLA, and the compatibility of PESL was superior to that of PES. The results of tensile testing showed that the extensibility of PLA was largely improved by blending with PES or PESL. At same blending ratios, the elongation at break of PLA/PESL blends was far higher than that of PLA/PES ones. The elongation maintained stable through aging for 3 months. The moisture absorption of the blends enhanced due to the strong moisture absorption of PEG segments in PES or PESL molecules, which did not directly lead to enhance the hydrolytic degradation rate of the PLA. The PLA blends containing 20–30 wt% PES or PESL were high transparent materials with high light scattering. The toughening PLA materials could potentially be used as a soft biodegradable packaging material or a special optical material.     

Design of toughened PLA based material for application in structures subjected to severe loading conditions. Part 2. Quasi-static tensile tests and dynamic mechanical analysis at ambient and moderately high temperature

The suitability of a ternary composition 58 wt% polylactide (PLA) - 25 wt% poly (methyl methacrylate) (PMMA) - 17 wt% Impact modifier (Biomax^®Strong - BS) for use in technical parts subjected to severe loading conditions continues to be investigated. Previous work has demonstrated that PLA-PMMA-BS composition presents very appealing tensile properties at ambient temperature over a wide range of strain-rate, and can compete with petro-sourced blends for use in highly-loaded technical parts. Attention is paid now to its mechanical behavior at moderately high temperature (up to 60 °C), through tensile tests and dynamic mechanical analyses. Results highlight the improvement of mechanical properties in the considered range of temperature, thanks to the presence of PMMA in the blend, and prove that PLA-PMMA-BS composition can be suitable for use in technical parts subjected to high strain-rate and/or moderately high temperature.     

Fluorescent and thermal properties of siloxane-polyurethanes based on 1,8-naphthalimide

A series of fluorescent siloxane-polyurethanes(HPMS-PUs) containing an amino-functionalized,1 8-naphthalimide,fluorescent monomer(AABD) as a chain extender were synthesized.The properties of the HPMS-PUs were investigated by UV–vis and fluorescence spectroscopies,thermogravimetric analysis and thermal migration behavior.The maximum absorption and emission wavelengths of HPMS-PUs showed a red shift of about 4 nm and a blue shift of about 9 nm,respectively,compared to those of AABD.The Stokes shifts of AABD and HPMS-PU2 were 3514 and 2931 cm 1,respectively.The quantum yield of HPMS-PU2 was 0.79,which was six times higher than that of AABD.Concentration self-quenching was observed in both AABD and HPMS-PUs.The fluorescence of HPMS-PUs was quite stable with respect to both temperature and fluorescence quencher effects.The thermal stability of HPMS-PUs increased with AABD content.The fluorophore units in the HPMS-PUs did not readily migrate.