Influence of cellulose nanowhiskers on the hydrolytic degradation behavior of poly(d,l-lactide)

This paper reports the preparation of bionanocomposites based on poly(d,l-lactide) and cellulose nanowhiskers (PDLLA/CNWs) and studies the influence of the CNWs on the hydrolytic degradation behavior of the polylactide. The hydrolytic degradation process was studied in a phosphate buffer medium through the sample weight loss and also by FTIR, DSC and TGA measurements. The presence of CNWs induced a strong delay in the hydrolytic degradation of the PDLLA, even when the concentration of the nanofillers was only 1%. This effect was related to the physical barrier created by the highly crystalline CNWs that inhibited water absorption and hence retarded the hydrolytic degradation of the bionanocomposites. In addition, the incorporation of cellulose nanocrystals in the PDLLA also made the biopolymer more thermally stable, increasing the initial temperature of mass loss even after the degradation in phosphate medium. The results presented here show the possibility of controlling the biodegradability and prolonging the service life of a polylactide through the incorporation of a small quantity of nanofillers obtained from renewable materials.     

Characterization of polylactic acid green composites and its biodegradation in a bacterial environment

The growing interest in the preservation of our environment is pushing for solutions to develop less impacting materials. Thus, the development of biocomposites and is recyclable and compostable end-of-life resources seem an interesting alternative. In this study, the characterization of Polylactic acid (PLA) reinforced with treated and untreated Olive husk flour (OHF) were investigated. More then, their biodegradation with a Bacillus sp. has been evaluated. The main results show that the bacteria degraded both the PLA and the composite. This degradation was confirmed by the release of reducing sugars as well as increasing weight loss of PLA matrix and composites.     

Effects of Rice Straw Powder (RSP) Size and Pretreatment on Properties of FDM 3D-Printed RSP/Poly(lactic acid) Biocomposites

To develop a new kind of environment-friendly composite filament for fused deposition modeling (FDM) 3D printing, rice straw powder (RSP)/poly(lactic acid) (PLA) biocomposites were FDM-3D-printed, and the effects of the particle size and pretreatment of RSP on the properties of RSP/PLA biocomposites were investigated. The results indicated that the 120-mesh RSP/PLA biocomposites (named 120#RSP/PLA) showed better performance than RSP/PLA biocomposites prepared with other RSP sizes. Infrared results showed that pretreatment of RSP by different methods was successful, and scanning electron microscopy indicated that composites prepared after pretreatment exhibited good interfacial compatibility due to a preferable binding force between fiber and matrix. When RSP was synergistically pretreated by alkaline and ultrasound, the composite exhibited a high tensile strength, tensile modulus, flexural strength, and flexural modulus of 58.59, 568.68, 90.32, and 3218.12 MPa, respectively, reflecting an increase of 31.19%, 16.48%, 18.75%, and 25.27%, respectively, compared with unmodified 120#RSP/PLA. Pretreatment of RSP also improved the thermal stability and hydrophobic properties, while reducing the water absorption of 120#RSP/PLA. This work is believed to provide highlights of the development of cost-effective biocomposite filaments and improvement of the properties of FDM parts.     

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.     

Thermal characterization and electrical properties of Fe-modified cellulose long fibers and micro crystalline cellulose

Thermal properties of polylactic acid (PLA) filled with Fe-modified cellulose long fibers (CLF) and microcrystalline cellulose (MCC) were studied using thermo gravimetric analysis (TG), differential scanning calorimetry, and dynamic mechanical analysis (DMA). The Fe-modified CLFs and MCCs were compared with unmodified samples to study the effect of modification with Fe on electrical conductivity. Results from TG showed that the degradation temperature was higher for all composites when compared to the pure PLA and that the PLA composites filled with unmodified celluloses resulted in the best thermal stability. No comparable difference was found in glass transition temperature (T _g) and melting temperature (T _m) between pure PLA and Fe-modified and unmodified CLF- and MCC-based PLA biocomposites. DMA results showed that the storage modulus in glassy state was increased for the biocomposites when compared to pure PLA. The results obtained from a femtostat showed that electrical conductivity of Fe-modified CLF and MCC samples were higher than that of unmodified samples, thus indicating that the prepared biocomposites have potential uses where conductive biopolymers are needed. These modified fibers can also be tailored for fiber orientation in a matrix when subjected to a magnetic field.     

The effect of heat treatment on water sorption in polylactide and polylactide composites via changes in glass‐transition temperature and crystallization kinetics

Water sorption into polylactide (PLA) and polylactide‐montmorillonite (PLLA‐MONT) composites containing 5 wt % of montmorillonite (MONT) under different heat treatment conditions was studied using the quartz crystal microbalance/heat conduction calorimetry (QCM/HCC) technique. Results showed that water sorption in neat polymer films and composite films increased with heat treatment temperature up to 120 °C. Differential scanning calorimetry was used to measure the glass‐transition temperature and isothermal crystallization kinetics of all samples. The mobility of the amorphous domain in all samples increased with heat treatment temperature, indicated by the decrease in glass‐transition temperature. PLA composites crystallized at a much faster rate than neat PLA did because MONT acted as a nucleating agent. Under the same heat treatment condition, water sorption in PLLA‐MONT composites was always higher than that in neat PLA due to the presence of the hydrophilic hydroxyl groups on the surface of MONT particles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Cationic polymerization of L,L‐lactide

Cationic bulk polymerization of L ,L‐ lactide (LA) initiated by trifluromethanesulfonic acid [triflic acid (TfA)] has been studied. At temperatures 120–160 °C, polymerization proceeded to high conversion (>90% within ～8 h) giving polymers with M_n ～ 2 × 10⁴ and relatively high dispersity. Thermogravimetric analysis of resulting polylactide (PLA) indicated that its thermal stability was considerably higher than the thermal stability of linear PLA of comparable molecular weight obtained with ROH/Sn(Oct)₂ initiating system. Also hydrolytic stability of cationically prepared PLA was significantly higher than hydrolytic stability of linear PLA. Because thermal or hydrolytic degradation of PLA starting from end‐groups is considerably faster than random chain scission, both thermal and hydrolytic stability depend on molecular weight of the polymer. High thermal and hydrolytic stability, in spite of moderate molecular weight of cationically prepared PLA, indicate that the fraction of end‐groups is considerably lower than in linear PLA of comparable molecular weight. According to proposed mechanism of cationic LA polymerization growing macromolecules are fitted with terminal ? OH and ? C(O)OSO₂CF₃ end‐groups. The presence of those groups allows efficient end‐to‐end cyclization. Cyclic nature of resulting PLA explains its higher thermal and hydrolytic stability as compared with linear PLA. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2650–2658, 2010     

Molecular dynamics and crystallization precursors in polylactide and poly(lactide)/CNT biocomposites in the insulating state

The early stages of the cold crystallization process and the formation of a rigid amorphous phase as seen by the dielectric response of polylactide, PLA, and composites polylactide/carbon nanotubes, PLA/CNT, are studied here by broadband dielectric spectroscopy for CNT concentrations below percolation. The presence of precursors during the nucleation and crystallization process is demonstrated by the existence of a time shift between the decline in the number of mobile segments and the growth of a 3D ordered phase as seen by variable temperature wide angle X-ray scattering measurements. Also, the loss of the mobile amorphous phase is not justified by the slow lamellar growth in identical conditions. The variation of the molecular dynamics, either for short range reorientations or cooperative motions, is followed in both amorphous and semicrystalline states. The changes observed in the composites PLA/CNT show a moderate heterogeneous nucleating effect of the nanofiller and a sensitivity of the three subglass transitions to the chain ordering. The relaxation parameters of the segmental relaxation are not very sensitive to the presence either of lamellae or of the nanofiller.     

The effect of environmental factors on biodegradable polylactide-based materials

This study focuses on the effect of environmental factors on composites of polylactide and lowdensity polyethylene with oxidized polyethylene added as an analogue of recyclable materials. Moisture and ultraviolet light were found to significantly affect the polylactide–polyethylene composites at the first stage. The presence of oxidized polyethylene in the composite containing 30 wt % polylactide has a minor effect on water uptake by the composites. The average weight loss in the samples incubated in soil for 360 days is 5–10%.     

Thermal degradation of ethanolamine treated poly(vinyl chloride)/wood flour composites

The influence of ethanolamine treatment of wood flour on the thermal degradation behaviour of PVC/wood flour composites was investigated. The decomposition of untreated and treated wood flour and PVC/wood flour composites was measured using thermogravimetric analysis (TGA). The TGA indicated an accelerated degradation of the composite after treatment in a temperature range between 240 and 350 °C. This was caused by a synergistic decomposition of treated wood flour and polymer. Additionally, the colour of the material was measured in order to analyse the effect of the treatment. The lightness of the composite was reduced with increasing ethanolamine concentration.     

Synergistic effect between expandable graphite and ammonium polyphosphate on flame retarded polylactide

Synergistic effect was observed between expandable graphite (EG) and ammonium polyphosphate (APP) on flame retarded polylactide (PLA) in this paper using limiting oxygen index (LOI), thermal gravimetric analysis (TGA), scanning electron microscopy (SEM) and X-ray spectroscopy (XPS) and cone calorimeter tests etc. In the experiments, PLA composites with 15 wt% of APP/EG(1:3) combinations showed a LOI value of 36.5 and V-0 rating in UL-94 tests, greatly improved flame retardant properties from composites with APP or EG alone. Results from TGA and cone calorimeter demonstrated that APP/EG combination could retard the degradation of polymeric materials above the temperature of 520 °C by promoting the formation of a compact char layer. This char layer protects the matrix effectively from heat penetrating inside and prevents its further degradation, resulting in lower weight loss rate and better flame retarded performance.     

乙酰柠檬酸丁酯增韧竹粉/聚乳酸生物质复合材料的制备与性能

以竹粉(bamboo flour,BF)为生物质填料,乙酰柠檬酸丁酯(acetyl tributyl citrate,ATBC)为增韧剂,通过与聚乳酸(polylactic acid,PLA)熔融共混制备了BF/PLA增韧复合材料,并采用红外光谱、热重分析、转矩流变仪、扫描电镜及力学性能测试等考察了ATBC添加对BF/PLA复合材料结构与性能的影响。结果表明,ATBC可改善BF/PLA复合材料的加工流变性,降低复合材料玻璃化转变温度、冷结晶温度及熔融温度,但对复合材料的热稳定性没有影响。FTIR分析显示,ATBC的加入可使BF/PLA复合材料C—O红外吸收峰位增大,表明ATBC与PLA之间存在一定相互作用。当ATBC用量为15%时,BF/PLA复合材料断裂伸长率由增韧前的8.1%增加到35.6%,提高了339.5%。SEM图片显示,此时复合材料断面粗糙,表现出韧性断裂形貌。该研究结果可为进一步探索增韧竹纤维/聚乳酸复合材料制备及应用,提供试验数据和理论参考。     

Carbodiimide additive to control hydrolytic stability and biodegradability of PLA

Enhanced durability of bio-based polylactic acid (PLA) is one of the prerequisites to be a considered as alternative to petroleum-based polymers in long time application. The effect of bis(2,6-diisopropylphenyl)carbodiimide (BDICDI) additive in various concentration on the extent of hydrolytic stabilization and subsequent degradation kinetics of PLA was studied in the process of abiotic hydrolysis and microbial decomposition under composting conditions. The study showed that BDICDI acts as an efficient stabilizer suppressing the hydrolytic scission of ester bonds of PLA in both degradation processes tested, especially at concentrations above 1.5% w/w. Within the stabilization period which strongly depends on concentrations of BDICDI, suppression of hydrolytic degradation also triggered preservation of thermal and mechanical properties. After the period of stabilization as the dose of stabilizer is depleted, probably via reaction with water molecules and carboxylic groups, the material was hydrolyzed at a comparable or even slightly higher rate than pure PLA. By applying the appropriate amount of BDICDI, the approximate duration of stabilization could be set to suit the desired requirements of the final product.     

Effects of Water and Chemical Solutions Ageing on the Physical,Mechanical, Thermal and Flammability Properties of Natural Fibre-Reinforced Thermoplastic Composites

Biocomposites comprising a combination of natural fibres and bio-based polymers are good alternatives to those produced from synthetic components in terms of sustainability and environmental issues. However, it is well known that water or aqueous chemical solutions affect natural polymers/fibres more than the respective synthetic components. In this study the effects of water, salt water, acidic and alkali solutions ageing on water uptake, mechanical properties and flammability of natural fibre-reinforced polypropylene (PP) and poly(lactic acid) (PLA) composites were compared. Jute, sisal and wool fibre- reinforced PP and PLA composites were prepared using a novel, patented nonwoven technology followed by the hot press method. The prepared composites were aged in water and chemical solutions for up to 3 week periods. Water absorption, flexural properties and the thermal and flammability performances of the composites were investigated before and after ageing each process. The effect of post-ageing drying on the retention of mechanical and flammability properties has also been studied. A linear relationship between irreversible flexural modulus reduction and water adsorption/desorption was observed. The aqueous chemical solutions caused further but minor effects in terms of moisture sorption and flexural modulus changes. PLA composites were affected more than the respective PP composites, because of their hydrolytic sensitivity. From thermal analytical results, these changes in PP composites could be attributed to ageing effects on fibres, whereas in PLA composite changes related to both those of fibres present and of the polymer. Ageing however, had no adverse effect on the flammability of the composites.     

Moisture sorption, transport, and hydrolytic degradation in polylactide

Management of moisture penetration and hydrolytic degradation of polylactide (PLA) is extremely important during the manufacturing, shipping, storage, and end-use of PLA products. Moisture transport, crystallization, and degradation, in PLA have been measured through a variety of experimental techniques including size-exclusion chromatography, differential scanning calorimetry, and X-ray diffraction. Quartz crystal microbalance and dynamic vapor sorption experiments have also been used to measure moisture sorption isotherms in PLA films with varying crystallinity. A surprising result is that, within the accuracy of the experiments, crystalline and amorphous PLA films exhibit identical sorption isotherms.     

Effect of wood flour content on surface properties of 3D printed materials produced from wood flour/PLA filament

Amount of wood flour was gradually increased from 0 to 50?wt% in the production of polylactic acid (PLA) based filaments with 1.75?mm diameter using twin screw extruder. Surface roughness and wettability were measured of the specimens. Surface roughness of the specimens significantly increased with incorporation of wood flour into PLA filament. Wettability of the specimens significantly decreased with increasing wood flour content. This was mainly attributed to the higher surface free energy of PLA than the beech wood. Contact angle values of the 3D printed wood/PLA specimens having wood flour content up to 30?wt% were less than 90°.     

Thermogravimetric analysis of rice husk flour filled thermoplastic polymer composites

The thermal degradation and thermal stability of rice husk flour (RHF) filled polypropylene (PP) and high-density polyethylene (HDPE) composites in a nitrogen atmosphere were studied using thermogravimetric analysis. The thermal stability of pure PP and HDPE was found to be higher than that of wood flour (WF) and RHF. As the content of RHF increased, the thermal stability of the composites decreased and the ash content increased. The activation energy of the RHF filled PP composites increased slowly in the initial stage until α=0.3 (30% of thermal degradation region) and thereafter remained almost constant, whereas that of the RHF filled HDPE composites decreased at between 30 and 40 mass% of RHF content. The activation energy of the composites was found to depend on the dispersion and interfacial adhesion of RHF in the PP and HDPE matrix polymers. This revised version was published online in July 2006 with corrections to the Cover Date.     

Moisture sorption, transport, and hydrolytic degradation in polylactide

Management of moisture penetration and hydrolytic degradation of polylactide (PLA) is extremely important during the manufacturing, shipping, storage, and end-use of PLA products. Moisture transport, crystallization, and degradation, in PLA have been measured through a variety of experimental techniques including size-exclusion chromatography, differential scanning calorimetry, and X-ray diffraction. Quartz crystal microbalance and dynamic vapor sorption experiments have also been used to measure moisture sorption isotherms in PLA films with varying crystallinity. A surprising result is that, within the accuracy of the experiments, crystalline and amorphous PLA films exhibit identical sorption isotherms.     

Effect of temperature and nanoparticle type on hydrolytic degradation of poly(lactic acid) nanocomposites

PLA and its nanocomposite films based on modified montmorillonite (CLO30B) or fluorohectorite (SOM MEE) and unmodified sepiolite (SEPS9) were processed at a clay loading of 5 wt% and hydrolytically degraded at 37 and 58 °C in a pH 7.0 phosphate-buffered solution. An effective hydrolytic degradation for neat PLA and nanocomposites was obtained at both temperatures of degradation, with higher extent at 58 °C due to more extensive micro-structural changes and molecular rearrangements, allowing a higher water absorption into the polymer matrix.The addition of CLO30B and SEPS9 delayed the degradation of PLA at 37 °C due to their inducing PLA crystallization effect and/or to their high water uptake reducing the amount of water available for polymer matrix hydrolysis. The presence of SOM MEE also induced polymer crystallization, but it was also found to catalyze hydrolysis of PLA. Concerning hydrolysis at 58 °C, the presence of any nanoparticle did not significantly affect the degradation trend of PLA, achieving similar molecular weight decreases for all the studied materials. This was related to the easy access of water molecules to the bulk material at this temperature, minimizing the effect of polymer crystallinity clay nature and aspect ratio on the polymer degradation.     

Thermal and burning properties of wood flour-poly(vinyl chloride) composite

The present study deals with the effects of wood flour on thermal and burning properties of wood flour-poly(vinyl chloride) composites (WF-PVC) using thermogravimetric (TG), cone calorimetry (CONE), and pyrolysis?Cgas chromatography/mass spectrometry (Py?CGC/MS). TG tests show that an interaction occurred between wood flour and PVC during the thermal degradation of WF-PVC. Wood flour decreased the temperature of onset of decomposition of PVC. However, the char formation could be increased by adding wood flour to PVC. CONE test indicates that wood flour had positive effects on heat release and smoke emission of PVC. Comparing with PVC, WF-PVC reduced average heat release rate and the peak HRR by about 14 and 28%, respectively; smoke production rate was also decreased. The degradation mechanism was studied by Py?CGC/MS. The results show that the volatile pyrolysis products of WF-PVC are very different from PVC. The yields of HCl and aromatic compounds decreased dramatically, and the aliphatic compounds increased by the incorporation of WF.