Thermal and Biodegradable Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide)/Poly(ε-Caprolactone) Compounded with Functionalized Organoclay

Poly(l-lactide) (PLLA)/Poly(ε-caprolactone) (PCL) blends were compounded with commercially available organoclay Cloisite 25A (C25A) and C25A functionalized with epoxy groups, respectively. Epoxy groups on the surface of C25A were introduced by treating C25A with (glycidoxypropyl)trimethoxy silane (GPS) to produce so called Functionalized Organoclay (F-C25A). The silicate layers of PLLA/PCL/F-C25A were exfoliated to a larger extent than PLLA/PCL/C25A. Incorporation of the epoxy groups on C25A improved significantly mechanical properties of PLLA/PCL/C25A. The larger amount of exfoliation of the silicate layers in PLLA/PCL/F-C25A as compared with that in PLLA/PCL/C25A was attributed to the increased interfacial interaction between the polyesters and the clay due to chemical reaction. Thermo gravimetric analysis revealed that the nanocomposites with exfoliated silicate layers were more thermally stable than those with intercalated silicate layers. The biodegradability of the neat PLLA/PCL and corresponding nanocomposite was studied under compost, and the rate of biodegradation of PLLA/PCL increased after nanocomposite preparation.     

Crystal and Thermal Properties of PLLA/PDLA Blends Synthesized by Direct Melt Polycondensation

We herein report the effects of the component ratio and method of blending on the synthesis of stereocomplex poly(lactic acid) (SC-PLA) based on poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) prepolymers. PLLA and PDLA were prepared by direct melt polycondensation of lactic acid (DMP). Combined with the dual catalyst system, PLA prepolymers with M_w more than 20,000 were prepared by DMP. PLLA was mixed by powder blending or melt blended with PDLA. It is revealed that melt-point and spherulite growth rate of SC-PLA is strongly dependent on the perfection of SC structure. The melt point of PLA can be increased by nearly 50 °C because of the particular strong intermolecular interaction between PLLA and PDLA chains. Solid-state polycondensation (SSP) is an efficient method to increase the molecular weight of SC-PLA, but it can have a negative effect on the regularity of linear chains of SC-PLA. Thermogravimetry analyzer (TGA) results show that SC structure cannot cause the delay reaction on the thermal degradation of PLA.     

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), ¹H and ¹³C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, ¹³C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.     

The Effect of Nanoclays on the Properties of PLLA-modified Polymers Part 1: Mechanical and Thermal Properties

Organically modified montmorillonite clays were incorporated at a 5% loading level into film grade of poly-L-lactic acid (PLLA) using a variety of masterbatches based on either semi-crystalline or amorphous poly-(lactic acid), as well as biodegradable aromatic aliphatic polyester. The PLLA masterbatches and compounded formulations were prepared using a twin screw compounding extruder, while the films were prepared using a single screw cast film extruder. The thermal and mechanical properties of the films were examined in order to determine the effect of the clay and different carriers on the polymer–clay interactions. In the optimal case, when a PLLA-based masterbatch was used, the tensile modulus increased by 30%, elongation increased by 40%, and the cold crystallization temperature decreased by 15 °C, compared to neat PLLA. The properties improvement of PLLA films containing nano clays demonstrated the possibility to extend the range of biodegradable film applications, especially in the field of packaging.     

Enzymatic Degradation of Poly(l-Lactic Acid): Effects of UV Irradiation

Amorphous and crystallized poly(l-lactic acid) (PLLA-A and PLLA-C, respectively) films were prepared, and the proteinase K-catalyzed enzymatic degradation of UV-irradiated and non-irradiated PLLA-A and PLLA-C films was investigated for periods up to 10 h (PLLA-A) and 60 h (PLLA-C). The molecular weights of both the PLLA-A and PLLA-C films can be manipulated by altering the UV irradiation time. The enzymatic weight loss values of the UV-irradiated PLLA films were higher than or similar to those of the non-irradiated PLLA film, when compared with the specimens of same crystallinities. UV irradiation is expected to cause the PLLA films to undergo chain cleavage (a decrease in molecular weight) and the formation of C=C double bonds. It seems that the acceleration effects from decreased molecular weight on enzymatic degradation were higher than or balanced with the disturbance effects caused by the formation of C=C double bonds. After enzymatic degradation, a fibrous structure appeared on the spherulites of the UV-irradiated PLLA-C film. This structure may have arisen from chains containing or neighboring on the C=C double bonds, which were enzymatically undegraded and assembled on the film surface during enzymatic degradation. The results of this study strongly suggest that UV irradiation will significantly affect the biodegradation behavior of PLLA materials in the environment.     

Recycling Ability of Biodegradable Matrices and Their Cellulose-Reinforced Composites in a Plastic Recycling Stream

The effect of multiple injection-moulding reprocessing of three biodegradable matrices on their mechanical properties, melt flow rate, molecular weight, phase transition temperatures and degradation temperature is presented. It has been found that, with successive reprocessing, tensile, flexural and impact strength decreased. Drop in mechanical properties has been assigned to degradation of the matrices, as corroborated by melt flow and molecular weight analysis. Although reprocessing did not significantly affect the glass transition, it diminished the melting point and degradation temperature of polymers. Results indicate that neat PLLA can be recycled for up to five times without suffering a drastic loss in mechanical and thermal properties. The aliphatic polyester Mater-Bi TF01U/095R can be recycled for up to 10 times, whilst starch-based Mater-Bi YI014U/C wastes should be destined to composting, since its recyclability is very poor. The effect of reprocessing on composites reinforced with chemithermomechanical pulp (CTMP) followed the tendencies observed for the neat matrices. Whilst CTMP-fibres behave mainly as filler in PLLA composites, reinforced thermoplastic starch-based composites presented enhanced mechanical properties and recyclability.     

Synthesis,Characterization, and Evaluation of Degussa P25/Chitosan Composites for the Photocatalytic Removal of Sertraline and Acid Red 18 from Water

Journal of Polymers and the Environment - Degussa P25 titanium dioxide/chitosan composites (P25/CS) were prepared using three different methods and two different chitosan materials. The obtained...     

Biomass Carbon Ratio of Polymer Composites Measured by Accelerator Mass Spectrometry

The evaluation method of biomass carbon ratio of polymer composite samples including organic and inorganic carbons individually was investigated. Biodegradable plastics and biobased plastics can have their mechanical properties improved by combining with inorganic fillers. Polymer composites consisting of biodegradable plastics and carbonate were prepared by two different methods. Poly(lactic acid) (PLA) composite was prepared by synthesis from l-lactide with catalyst and calcium carbonate (CaCO₃) powders from lime. Poly(butylene succinate) (PBS) composite was prepared by hot-pressing the mixture of PBS powder and CaCO₃ powders from oyster shells. The mechanical properties of composite samples were investigated by a tensile test and a compression test using an Instron type mechanical tester. Tensile test with a dumbbell shape specimen was performed for PBS composite samples and compression test with a column shape specimen for PLA composite samples. Strength, elastic modulus and fracture strain were obtained from the above tests. Biomass carbon ratio is regulated in the American Standards for Testing and Materials (ASTM). In ASTM standards on biomass carbon ratio, it is required that carbon atoms from carbonates, such as CaCO₃, are omitted. Biomass carbon ratio was evaluated by ratio of ¹⁴C to ¹²C in the samples using Accelerator Mass Spectrometry (AMS). The effect of pretreatment, such as oxidation temperature and reaction by acid, on results of biomass carbon ratio was investigated. Mechanical properties decrease with increasing CaCO₃ content. The possibility of an evaluation method of biomass carbon ratio of materials including organic and inorganic carbons was shown.     

The Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactide) Prepared by Different Synthesis Procedure

Different synthesis methods were applied to determine optimal conditions for polymerization of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (l-lactide), in order to obtain poly(l-lactide) (PLLA). Bulk polymerizations (in vacuum sealed vessel, high pressure reactor and in microwave field) were performed with tin(II) 2-ethylhexanoate as the initiator. Synthesis in the vacuum sealed vessel was carried out at the temperature of 150 °C. To reduce the reaction time second polymerization process was carried out in the high pressure reactor at 100 °C and at the pressure of 138 kPa. The third type of rapid synthesis was done in the microwave reactor at 100 °C, using frequency of 2.45 GHz and power of 150 W at the temperature of 100 °C. The temperature in this method was controlled via infrared system for in-bulk measuring. The solution polymerization (with trifluoromethanesulfonic acid as initiator) was possible even at the temperature of 40 °C, yielding PLLA with narrow molecular weight distribution in a very short period of time (less than 6 h). The obtained polymers had the number-average molecular weights ranging from 43,000 to 178,000 g mol⁻¹ (polydispersity index ranging from 1 to 3) according to the gel permeation chromatography measurements. The polymer structure was characterized by Fourier transform infrared and NMR spectroscopy. Thermal properties of the obtained polymers were investigated using thermogravimetry and differential scanning calorimetry.     

Photodegradation of Poly(lactic acid) Stereocomplex by UV-Irradiation

Neat poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) films and PLLA/PDLA blend films were prepared by solution casting, and their photodegradation by UV-irradiation was investigated using wide-angle X-ray scattering (WAXS), gel permeation chromatography, differential scanning calorimetry, tensile testing, and polarized optical microscopy. The PLLA/PDLA blend film was more photodegradation-resistant than the neat PLLA and PDLA films when photodegradation was monitored by molecular weight, melting temperature, and WAXS crystalline peak positions. This indicates that the chains in both amorphous and crystalline regions of the PLLA/PDLA blend film were photo-cleavage-resistant compared to those of the neat PLLA and PDLA films. The changes in melting temperature and WAXS crystalline peak positions before and after photodegradation respectively indicated the increased crystalline lattice disorder and the decreased crystalline lattice sizes of the neat PLLA and PDLA films, whereas these changes were insignificant for the blend films. Photodegradation caused no significant change in tensile properties, with the exception of significant decreases in the tensile strength and elongation at break of PLLA/PDLA blend film. However, the tensile strength and elongation at break of the PLLA/PDLA blend film retained higher values compared to those of the neat PLLA and PDLA films during photodegradation. In spite of the slower photodegradation of the PLLA/PDLA blend film traced by M _n, T _m, and WAXS crystalline peak positions than that of neat PLLA and PDLA films, the rapid decrease in tensile strength and elongation at break of the former than that of the latter should be due to the highly-ordered structural difference between them, i.e., the three dimensional dry gel of the former and the spherulites of the latter.     

Mechanical and Thermal Properties of PLLA/PCL Modified Clay Nanocomposites

Poly(l-lactic acid) (PLLA)/poly(caprolactone) (PCL) and two types of organoclay (OMMT) including a fatty amide and ocatdecylamine montmorillonite (FA-MMT and ODA-MMT) were employed to produce polymer nanocomposites by melt blending. Materials were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), elemental analysis, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Mechanical properties were also investigated for these nanocomposites. The nanocomposites showed increasing mechanical properties and thermal stability. XRD results indicated that the materials formed nanocomposites. SEM morphology showed that increasing content of OMMT reduced the domain size of phase separated particles. TEM outcomes have confirmed the intercalated type of nanocomposite. Additionally, a solution casting process has been used to prepare these nanocomposites and characterized to compare these results with the above process.     

交联壳聚糖/沸石复合吸附剂的制备及性能

用沸石负载由缩水甘油基三乙基氯化铵交联的壳聚糖，制得了性能良好的交联壳聚糖/沸石复合吸附剂。研究了该吸附剂应用性能的影响因素，探讨了该吸附剂的吸附性、沉降性和重复使用性，利用FTIR仪和高倍透射电子显微镜对该吸附剂的结构进行了表征。实验结果表明:壳聚糖的交联度为0.93、交联壳聚糖与沸石的质量比为0.045时，制得的交联壳聚糖/沸石复合吸附剂对腐殖酸的去除率可达81.4%，吸附量为4.07mg/g;交联壳聚糖/沸石复合吸附剂对腐殖酸的吸附性能较沸石有显著提高，沉降时间较交联壳聚糖明显缩短;经二次洗脱后腐殖酸去除率仍可达80.2%，腐殖酸吸附量为4.01mg/g。     

Effect of Cotton Fiber Contents and Lengths on Properties of Thermoplastic Starch Composites Prepared from Rice and Waxy Rice Starches

Biodegradable polymer was prepared as thermoplastic starch (TPS) using rice and waxy rice starches. In order to increase mechanical properties and reduce water absorption of the TPS, cotton fiber was incorporated as the fiber reinforcement into the TPS matrix. The effect of cotton fiber contents and lengths on properties of the TPS was examined. Internal mixer and compression molding machine were used to mix and shape the samples. It was found that the thermoplastic rice starch (TPRS) showed higher stress at maximum load and Young’s modulus but lower strain at maximum load than the thermoplastic waxy rice starch (TPWRS). In addition, stress at maximum load and Young’s modulus of both TPRS and TPWRS increased significantly with the addition of the cotton fiber. Cotton fiber contents and lengths also affected mechanical properties of the TPRS and TPWRS composites. Moreover, water absorption of the TPRS and TPWRS composites decreased by the use of the cotton fibers. FT-IR and XRD techniques were used to study a change in functional group and crystallinity of the thermoplastic starch composites. Morphological, thermal and biodegradable properties of different thermoplastic starch composites were also investigated.     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.     

Influence of the Concentrations of Chitosan and Glycerol on Edible Film Properties Showed by Response Surface Methodology

The individual and interactive effects of glycerol and chitosan concentrations on edible film properties were investigated using response surface methodology. The results of ANOVA indicated that all the independent variables exhibited significant effect on the film properties. Chitosan concentration had a positive effect on CO₂ permeability and negative effect on O₂ while the glycerol concentration had a positive effect on permeability to both gases. Regarding water vapor permeability, the chitosan concentration had a negative effect, whereas the glycerol had no influence. Moreover, both chitosan and glycerol concentration influenced the elongation at break point (%A), and only glycerol concentration had a significant effect on tensile strength. Optimization by desirability approach was carried out on the independent variables to get the optimum levels within the experimental conditions. It was found that 1.5 % of chitosan and 25 % of glycerol (wt/wt of chitosan) retarded respiration and showed a strong permeability to water vapor.     

Preparation and Thermo-Mechanical Characterization of Chitosan Loaded Methylcellulose-Based Biodegradable Films: Effects of Gamma Radiation

Chitosan (0.1–1%, w/w), dissolved in 2% acetic acid solution, was added into 1% methylcellulose (MC)-based formulation containing 0.5% vegetable oil, 0.25% glycerol and 0.025% Tween^?80. Films were prepared by casting. Puncture strength (PS), puncture deformation (PD), viscoelasticity coefficient and water vapour permeability (WVP) of the films were measured. The PS value of 312 N/mm was observed for MC-based films containing 0.25% chitosan. Values of PD, viscoelasticity coefficient and WVP of these films were 5.0 mm, 44.1%, and 6.0 g mm/m² day kPa, respectively. The MC-based films containing 0.25% chitosan were also exposed to gamma radiation (0.5–50 kGy). The PS of the treated films decreased significantly from 312 at 0 kGy to 201 N/mm when treated at a dose of 50 kGy. However, WVP values were not affected by increasing irradiation the dose used. The Fourier Transform Infrared spectroscopy supported the molecular interactions due to addition of chitosan in MC-based films. Thermo gravimetric analysis and differential scanning calorimetric experiments showed that thermal properties of the films were significantly improved by chitosan loading. Surface topography of the films was studied by scanning electron microscopy and found rougher due to chitosan addition.     

Crystallization Behavior and Dynamic Mechanical Properties of Poly(l-Lactic Acid) with Poly(Ethylene Glycol) Terminated by Benzoate

Effect of the addition of poly(ethylene glycol) terminated by benzoate (PEG-BA) on the crystallization behavior and dynamic mechanical properties of poly(l-lactic acid) PLLA is studied as compared with poly(ethylene glycol) (PEG-OH). It is found that PEG-BA is miscible with PLLA and shows good plasticizing effect. Because PEG-OH having the same degree of polymerization is immiscible with PLLA, the end group in PEG-BA, i.e., benzoate, plays an important role in the miscibility. Furthermore, PEG-BA does not induce the PLLA degradation at melt-processing, whereas PEG-OH leads to the hydrolysis degradation. Finally, the addition of PEG-BA pronounces the crystallization rate of PLLA at low crystallization temperatures and thus enhances the degree of crystallinity at conventional processing. Consequently, the temperature dependence of dynamic mechanical properties are similar to that for isotactic polypropylene.     

Fatigue Life Behaviour of Glass/Kenaf Woven-Ply Polymer Hybrid Biocomposites

Investigation on the fatigue life of hybrid composites is critical to extend their applications and acceptance among industries; however, there is a lack of research focus on fatigue performance of the hybrid composite. In this study, the fatigue life of glass/kenaf woven-ply hybrid composite with thermoplastic and thermoset polymer matrix was investigated. Hybrid composites consist of two different fibre configurations: kenaf/glass/kenaf and glass/kenaf/glass. Thermoplastic hybrid composites were manufactured through the hot press moulding compression method, while thermoset hybrid composites were fabricated through the vacuum-assisted resin infusion method. The tensile strength and fatigue strengths of the kenaf/glass/kenaf composite have been identified to be significantly lower than those of the glass/kenaf/glass composite regardless of the types of matrix used. However, thermoplastic-based kenaf/glass/kenaf composites are less fatigue sensitive compared to glass/kenaf/glass composites; however, this phenomenon is vice versa for thermoset composites due to the epoxy matrix, which limits the stiffening effect in natural fibres.     

Vegetable fibres from agricultural residues as thermo-mechanical reinforcement in recycled polypropylene-based green foams

Novel lightweight composite foams based on recycled polypropylene reinforced with cellulosic fibres obtained from agricultural residues were prepared and characterized. These composites, initially prepared by melt-mixing recycled polypropylene with variable fibre concentrations (10-25 wt.%), were foamed by high-pressure CO₂ dissolution, a clean process which avoids the use of chemical blowing agents. With the aim of studying the influence of the fibre characteristics on the resultant foams, two chemical treatments were applied to the barley straw in order to increase the α-cellulose content of the fibres. The chemical composition, morphology and thermal stability of the fibres and composites were analyzed. Results indicate that fibre chemical treatment and later foaming of the composites resulted in foams with characteristic closed-cell microcellular structures, their specific storage modulus significantly increasing due to the higher stiffness of the fibres. The addition of the fibres also resulted in an increase in the glass transition temperature of PP in both the solid composites and more significantly in the foams.     

Novative Biomaterials Based on Chitosan and Poly(ε-Caprolactone): Elaboration of Porous Structures

The swelling capability of chitosan was explored in order to use water both, as volatile plasticizer and as pore-forming agent. Chitosan powder was swelled in acidic aqueous solution and melt blended with poly(ε-caprolactone) (PCL). After stabilization at 57% RH and 25 °C, samples suffered a water mass loss of around 30 wt% without dimensions variation. Despite the low miscibility of these biopolymers, quite homogeneous dispersion of chitosan within the polyester matrix was obtained. Some interactions between both biopolymers could be observed. To obtain chitosan phase with a thermoplastic-like behaviour, the plasticization effect was also studied by the addition of 25 wt% glycerol as non volatile plasticizer. The equilibrium moisture content of samples increased with the incorporation of glycerol due to its hydrophilic nature. Morphology, thermal and mechanical properties of the blends were determined after stabilization. The preparation of rich PCL blends allowed the formation of macroporous structures since samples were not contracted after water loss and stabilization. These biomaterials with such a porous structure could be used for biomedical applications.