Cellulose nanowhisker-incorporated poly(lactic acid) composites for high thermal stability

In this study, biodegradable composites were prepared using cellulose nanowhiskers and poly(lactic acid). For processing at high temperature over 200 °C, cellulose nanowhiskers were prepared by ultra-sound treatment, with the high thermal stability of natural cellulose. The nanowhiskers were confirmed using transmission electron microscopy, X-ray diffraction, and thermo-gravimetric analysis. Surface modification of the cellulose nanowhiskers was performed to increase the adhesion between hydrophilic nanofillers and hydrophobic polymer matrix. The dynamic mechanical thermal analysis of the composites showed better reinforcing effect of the modified cellulose nanocrystals. The effects of cellulose nanowhiskers on the biodegradability of poly(lactic acid) were studied using a microbial oxidative degradation analyzer.     

Polylactic acid/carbon fiber composites: Effects of functionalized elastomers on mechanical properties,thermal behavior,surface compatibility,and electrical characteristics

In this study, the maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer (SEBS-g-MA) is used as the compatilizer for polylactic acid (PLA)/carbon fiber (CF) composites. The effects of SEBS-g-MA on the mechanical properties, thermal behavior, interfacial compatibility, and electrical characteristics of composites are then evaluated. The mechanical property tests indicate that when the amount of compatilizer increases, the tensile properties and flexural property of the composites decrease while their impact strength increases. The SEM results show that the compatilizer can decrease the interstices between PLA and CF, and thereby augments their interfacial compatibility. The differential scanning calorimetry (DSC) results confirm that the compatilizer results in a greater crystallization temperature and a greater crystallinity of the composites. The electrical characteristic results indicate that neither PLA nor SEBS-g-MA is not interfered with the conductive network that is constructed by CF, which is exemplified by an average electromagnetic shielding effect of above ?30 dB. This study confirms that SEBS-g-MA can improve interfacial compatibility and toughness, as well as attain good electrical characteristics of PLA/CF composites.     

Preparation and UV-protective property of PVAc/ZnO and PVAc/TiO<Subscript>2</Subscript> microcapsules/poly(lactic acid) nanocomposites

The poly(vinyl acetate) (PVAc)/zinc oxide (ZnO) microcapsule and PVAc/titanium dioxide (TiO₂) microcapsule were synthesized via in-situ emulsion polymerization method. The PVAc/ZnO microcapsule and PVAc/TiO₂ microcapsule were characterized by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis(TG), transmission electron microscopy (TEM), and UV-visible spectroscopy (UV-vis). Effect of PVAc/ZnO microcapsule and PVAc/TiO₂ microcapsule on properties of poly(lactic acid) (PLA) was evaluated by UV-vis, SEM and mechanical properties test. The results showed that the addition of PVAc/ZnO and PVAc/TiO₂ microcapsules as a UV-blocking additive could significantly enhance UV-blocking property of PLA/PVAc/ZnO microcapsule composites and PLA/PVAc/TiO₂ microcapsule composites compared with pure PLA, PLA/ZnO composites and PLA/TiO₂ composites. The mechanical properties of PLA/PVAc/ZnO microcapsule composites were better than those of PLA/ZnO composites due to good dispersability and compatibility of PVAc/ZnO microcapsule in PLA matrix. Also, the mechanical properties of PLA/PVAc/TiO₂ microcapsule composites were better than those of pure PLA and PLA/TiO₂ composites. This study demonstrates the great potentials of the intrinsically UV shield additive PVAc/ZnO and PVAc/TiO₂ microcapsules in the application of high performance matrix resin and composite material.     

Synthesis and hydrophilicity of poly(trimethylene 2,6-naphthalate)/poly(ethylene glycol) copolymers

Poly(trimethylene 2,6-naphthalate) (PTN)/poly(ethylene glycol) (PEG) copolymers were synthesized by the two-step melt copolymerization process of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) with 1,3-propanediol (PD) and PEG. The copolymers produced had different PEG molecular weights and contents. The structure, thermal property, and hydrophilicity of these copolymers were studied by proton nuclear magnetic resonance (¹H-NMR) analysis, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and by contact angle, moisture content, and instantaneous elastic recovery measurements. The intrinsic viscosity and the instantaneous elastic recovery of the PTN/PEG copolymers increased with increasing PEG molecular weight and content, whereas the glass transition, melting, and cold crystallization temperatures, and the heat of fusion of the PTN/PEG copolymers all decreased with increasing PEG molecular weight or content. The thermal stability of the copolymers was not affected by PEG molecular weight or content. The hydrophilicity, as determined by contact angle and moisture content measurements of the copolymer films, was significantly improved with increasing PEG molecular weight and content.     

Mechanical properties of denim fabric reinforced poly(lactic acid)

Denim, a twilled cotton fabric, was used to enhance the mechanical and thermal properties of poly(lactic acid) (PLA). The denim fabric reinforced composites with different numbers of denim layers were fabricated by using a hand layup method. The impact, tensile, and dynamic mechanical properties of the composites were observed with increasing denim layers to examine the reinforcing effect of denim fabrics. Numerical analysis was carried out to model the elastic modulus of the composite by using a commercial software. Three-dimensional geometry of the denim fabric reinforced PLA composite was generated through a CAD program, and the elastic modulus was calculated by applying uniform deformation on one surface. The impact strength, tensile strength, and thermal properties of the composites were improved by piling denim fabrics. The denim fabric reinforced composites exhibited outstanding impact strength due to the retarded crack propagation as well as large energy dissipation. The 3 layer denim reinforced composite showed best results among all specimens, and its impact strength, tensile strength, and tensile modulus were measured to be 82 J/m, 75.76 MPa, and 4.65 GPa, respectively. The PLA/denim composites have good mechanical properties and can substitute traditional composites such as glass fiber or carbon fiber reinforced composites.     

Unique crystallization behavior of multi-walled carbon nanotube filled poly(lactic acid)

Although poly(lactic acid) (PLA) possesses many desirable properties such as miscible, reproducible, nontoxic, and biodegradable properties, extremely slow crystallization rate is a weak point in comparison with other commercial thermoplastics. Addition of nucleating agents can be a good method to increase the overall crystallization rate and multi-walled carbon nanotube (MWCNT) is generally known as a good nucleating agent as well as reinforcement. MWCNT reinforced PLA nanocomposites were prepared by melt blending and the unique nucleation and crystallization behaviors of pure PLA and MWCNT/PLA nanocomposites were investigated. Slow homogeneous nucleation and crystallization behavior of the pure PLA and fast heterogeneous crystallization behavior of MWCNT/PLA nanocomposites were observed. Crystallization behavior of MWCNT/PLA nanocomposites was irrespective of cooling rate and the peculiar behavior was due to fast heterogeneous crystallization caused by the nucleating effect of MWCNT and fast PLA chain mobility.     

Effects ofIn Vitro degradation on the weight loss and tensile properties of PLA/LPCL/HPCL blend fibers

PLA/LPCL/HPCL blend fibers composed of poly (lactic acid) (PLA), low molecular weight poly (ɛ-caprolactone) (LPCL), and high molecular weight poly (ɛ-caprolactone) (HPCL) were prepared by melt blending and spinning for bioabsorbable filament sutures. The effects of blending time and blend composition on the X-ray diffraction patterns and tensile properties of PLA/LPCL/HPCL blend fibers were characterized by WAXD and UTM. In addition, the effect ofin vitro degradation on the weight loss and tensile properties of the blend fibers hydrolyzed during immersion in a phosphate buffer solution at pH 7.4 and 37°C for 1–8 weeks was investigated. The peak intensities of PLA/LPCL/HPCL blend fibers in X-ray diffraction patterns decreased with an increase of blending time and LPCL contents in the blend fibers. The weight loss of PLA/LPCL/HPCL blend fibers increased with an increase of blending time, LPCL contents, and hydrolysis time while the tensile strength and modulus of the blend fibers decreased. The tensile strength and modulus of the blend fibers were also found to be increased with an increase of HPCL contents in the blend fibers. The optimum conditions to prepare PLA/LPCL/HPCL blend fibers for bioabsorbable sutures are LPCL contents of 5 wt%, HPCL contents of 35 wt%, and blending time of 30 min. The strength retention of the PLA/LPCL/HPCL blend fiber prepared under optimum conditions was about 93.5% even at hydrolysis time of 2 weeks.     

Effect of CaCO3 contents on the properties of polyethylene nanocomposites sheets

Nanocomposites of high-density polyethylene/linear low-density polyethylene (HDPE/LLDPE) filled with untreated and surface treated nano-calcium carbonate (nCC) were prepared. The influence of isopropyl tri-(dioctylpyrophosphato) titanate (JN114) treatment of nCC on the morphology, mechanical, crystallization and flow properties of the nanocomposites were studied. The results of scanning electron microscopy (SEM) showed that JN114 treated nCC was better dispersion in the matrix than the untreated one. A fine dispersion of the treated nanoparticles in the nanocomposites was observed by transmission electron microscopy (TEM). The FTIR spectrum analysis revealed that the JN114 could change the surface properties of nCC, resulting in greater hydrophobicity of the surface and enhanced compatibility with nonpolar matrices. The tensile elastic modulus (E _c ) and Izod impact strength (SIC) of nanocomposites increased with the increasing of nCC content while tensile fracture strength (σ _b ) decreased. The JN114 treated nanocomposites had superior mechanical properties to those of the untreated ones. The compatibility of these nanocomposites was examined by DSC to estimate melting point (T _m ) and crystallization temperature (T _c ). Furthermore, the melt flow index (MFI) of the nanocomposite materials were measured. It was found that the MFI decreased with the addition of weight fraction of the nCC particles.     

New biopolymer nanocomposites based on epoxidized soybean oil plasticized poly(lactic acid)/fatty nitrogen compounds modified clay: Preparation and characterization

Biodegradable polymers, such as poly(lactic acid) (PLA) have attracted a lot of attention in the scientific community recently due to a rapid growth of intensive interest in the global environment for alternatives to petroleum-based polymeric materials. Fatty nitrogen compounds (FNCs), fatty amides (FA), fatty hydroxamic acids (FHA), and carbonyl difatty amides (CDFA), which were synthesized from vegetable oils, were used as one of organic compounds to modify natural clay (sodium montmorillonite). The clay modification was carried out by stirring the clay particles in an aqueous solution of FA, FHA, and CDFA, by which the clay layer thickness increased from 1.23 to 2.61, 2.84 and 3.19 nm, respectively. The modified clay was then used in the preparation of the PLA/epoxidized soybean oil (ESO) blend nanocomposites. They were prepared by incorporating 2% of CDFA-MMT and 3% of both FA-MMT and FHA-MMT. The interaction of the modifier in the clay layer was characterized by X-ray diffraction (XRD), and Fourier transform infrared (FTIR). Elemental analysis was used to estimate the presence of FNCs in the clay. The nanocomposites were synthesized by solution casting of the modified clay and a PLA/ESO blend at the weight ratio of 80/20, which has the highest elongation at break. The XRD and transmission electron microscopy (TEM) results confirmed the production of nanocomposites. PLA/ESO modified clay nanocomposites show higher thermal stability and significant improvement of mechanical properties in comparison with those of the PLA/ESO blend. The novelty of this study is use of FNCs which reduces the dependence on petroleum-based surfactants.     

Effects of surface treatment of ramie fibers in a ramie/poly(lactic acid) composite

The chemical and morphological properties of ramie fibers treated by chemical surface modification were examined with Fourier transform infrared (FT-IR) spectroscopy. The mechanical and thermal decomposition properties were evaluated with respect to tensile strength, tensile modulus and thermogravimetric analysis (TGA). Surface morphological changes were investigated with scanning electron microscopy (SEM). Finally, the capabilities of composites reinforced with various chemically treated fibers were analyzed by investigating tensile and impact strengths. Additionally, the thermal mechanical properties of the composites were investigated with thermal mechanical analysis (TMA). Based on the results of these analyses, we concluded that pectin, lignin and hemicellulose were removed and thermal stability was increased with chemical treatments. The composites reinforced with ramie fiber showed better properties compared with pure PLA matrix with respect to tensile and impact strengths. The peroxide-treated fiber composite had the smallest thermal expansion.     

Preparation and characterization of intumescent flame retardant biodegradable poly(lactic acid) nanocomposites based on sulfamic acid intercalated layered double hydroxides

A novel sulfamic acid intercalated MgAl-LDH (SA-LDH) was prepared by intercalating NH₃SO₃^? into MgAl-layered double hydroxides (LDH), and it was then introduced into poly(lactic acid) (PLA) resin in association with intumescent flame retardant (IFR) by melt blending to prepare a flame-retardant biodegradable PLA composite. The effects of SA-LDH on the flame retardancy of PLA composites were characterized by limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimeter test (CONE). The results showed that the composite sample containing 19.0 wt% IFR and 1.0 wt% SA-LDH achieved the maximal LOI value of 48.7 %, passed the UL-94 V-0 rating, and significantly decreased the peak heat release rate from 306.3 kW/m² of neat PLA to 58.1 kW/m². Thermogravimetric analysis showed that both the thermal stability and the char formation were enhanced. The char morphology observation revealed that SA-LDH was beneficial to form dense and compact char layers. It was demonstrated that there existed a synergistic effect between IFR and SA-LDH in promoting the char formation and enhancing the fire resistance. The mechanical and crystallization properties were also tested and discussed.     

Preparation of new polymer nanocomposites based on poly(lactic acid)/fatty nitrogen compounds modified clay by a solution casting process

In this study, different organoclays (OMMTs) were prepared using various fatty nitrogen compounds (FNCs) and natural clay, sodium montmorillonite (MMT). The clay modification was carried out by stirring the clay particles in an aqueous solution of fatty amides (FA), fatty hydroxamic acids (FHA), and carbonyl difatty amides (CDFA). These OMMTs were then used for nanocomposites production to improve the property balance of poly(lactic acid) (PLA) by solution casting process. All sets of OMMTs and nanocomposites were characterized using various apparatuses. In the nanocomposites, where the clay surface is pretreated with FA, FHA and CDFA, the basal spacing of the clay increased to 2.94, 3.26 and 3.80 nm, respectively The X-ray diffraction (XRD) and transmission electron microscopy (TEM) results confirmed the production of nanocomposites. PLA modified clay nanocomposites show higher thermal stability and significant improvement of mechanical properties in comparison with pure PLA.     

Preparation and crystallization behavior of polylactide nanocomposites reinforced with POSS-modified montmorillonite

We herein report the preparation and crystallization behavior of polylactide (PLA) nanocomposites reinforced with polyhedral oligomeric silsesquioxane-modified montmorillonite (POSS-MMT), which is prepared by exchanging sodium cations of pristine sodium montmorillonite (Na-MMT) with protonated aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS-NH₃ ⁺). PLA nanocomposites with 1–10 wt% POSS-MMT contents are manufactured via melt-compounding, and their structures and melt-crystallization behavior are investigated. It is characterized that POSS-MMT nanoparticles in the nanocomposites have an exfoliated structure of MMT silicates with POSS-NH₃ ⁺ and partial POSS-NH₂ crystals. DSC cooling thermograms suggest that the overall melt-crystallization rates of the nanocomposite with only 3 wt% POSS-MMT are remarkably enhanced in comparison with the neat PLA. From the isothermal crystallization analysis based on the Avrami model, the overall melt-crystallization of PLA/POSS-MMT nanocomposites is found to be dominated by the heterogeneous nucleation and three-dimensional spherulite growth. Isothermal melt-crystallization experiments using a polarized optical microscope show that the spherulite nucleation density of PLA/POSS-MMT nanocomposites is much higher than that of the neat PLA, whereas the spherulite growth rates of all the nanocomposites are almost identical with the rate of the neat PLA. It is concluded that the highly enhanced melt-crystallization rates of PLA/POSS-MMT nanocomposites stem from the dominant nucleation effect of POSS-MMT nanoparticles for PLA crystals.     

Properties of thermoplastic starch from cassava bagasse and cassava starch and their blends with poly (lactic acid)

Cassava bagasse is an inexpensive and broadly available waste byproduct from cassava starch production. It contains roughly 50% cassava starch along with mostly fiber and could be a valuable feedstock for various bioproducts. Cassava bagasse and cassava starch were used in this study to make fiber-reinforced thermoplastic starch (TPS_B and TPS_I, respectively). In addition, blends of poly (lactic acid) and TPS_I (20%) and TPS_B (5, 10, 15, 20%) were prepared as a means of producing low cost composite materials with good performance. The TPS and PLA blends were prepared by extrusion and their morphological, mechanical, spectral, and thermal properties were evaluated. The results showed the feasibility of obtaining thermoplastic starches from cassava bagasse. The presence of fiber in the bagasse acted as reinforcement in the TPS matrix and increased the maximum tensile strength (0.60 MPa) and the tensile modulus (41.6 MPa) compared to cassava starch TPS (0.40 and 2.04 MPa, respectively). As expected, blending TPS with PLA reduced the tensile strength (55.4 MPa) and modulus (2.4 GPa) of neat PLA. At higher TPS_B content (20%) the maximum strength (19.9 MPa) and tensile modulus (1.7 GPa) were reduced about 64% and 32%, respectively, compared to the PLA matrix. In comparison, the tensile strength (16.7) and modulus (1.2 GPa) of PLA blends made with TPS_I were reduced 70% and 51% respectively. The fiber from the cassava bagasse was considered a filler since no increase in tensile strength of PLA/TPS blends was observed. The TPS_I (33.1%) had higher elongation to break compared to both TPS_B (4.9%) and PLA (2.6%). The elongation to break increased from 2.6% to 14.5% by blending TPS_I with PLA. In contrast, elongation to break decreased slightly by blending TPS_B with PLA. Thermal analysis indicated there was some low level of interaction between PLA and TPS. In PLA/TPS_B blends, the TPS_B increased the crystallinity of the PLA component compared to neat PLA. The fiber component of TPS_B appeared to have a nucleating effect favoring PLA crystallization.     

Effect of various parameters on the chemical grafting of amide monomers to poly(lactic acid)

Radical melt graft copolymerizations of poly (lactic acid) (PLA) with amide monomers using benzoyl peroxide as an initiator during reactive extrusion is studied. The effects of two monomer types at various concentrations, reaction temperatures and initiator concentrations on the grafting yield are investigated. The results showed that percentage of grafting was significantly enhanced by increasing benzoyl peroxide concentrations up to 12 mpm and then decreased by an increase in the initiator concentration. Furthermore, increasing each monomer concentration up to 450 mpm, improved the grafting yield significantly. Further increase brings about a marked fall in the grafting yield. Fourier Transform Infrared Spectroscopy (FTIR), back titration and nitrogen analyses confirmed that monomers of acrylamide and methacrylamide were successfully grafted onto PLA. The Gel Permeation Chromatography (GPC) data showed that the molecular weight of the grafted PLA samples under optimum conditions does not show any dramatic drop of PLA molecular weight by thermal degradation or hydrolysis of polyester chains, while the polydispersity index is poorly affected by the chemical modification of PLA. Also, the monomer structures affected the grafting yield as well as polymer chain combination. In addition under the same conditions, the grafting yield of acrylamide was more than that of methacrylamide. Thermal properties, molecular weight, density, moisture regain and tensile properties of the samples were also measured.     

Synthesis and hydrophilicities of Poly(ethylene 2,6-naphthalate)/Poly(ethylene glycol) copolymers

Poly(ethylene 2,6-naphthalate) (PEN)/Poly(ethylene glycol) (PEG) copolymers were synthesized by two step reaction during the melt copolymerization process. The first step was the esterification reaction of dimethyl-2,6-naphthalenedicarboxylate (2,6-NDC) and ethylene glycol (EG). The second step was the condensation polymerization of bishydroxyethylnaphthalate (BHEN) and PEG. The copolymers contained 10 mol% of PEG units with different molecular weights. Structures and thermal properties of the copolymers were studied by using¹H-NMR, DSC, TGA, etc. Especially, while the intrinsic viscosities of PEN/PEG copolymers increased with increasing molecular weights of PEG, but the glass transition temperature, the cold crystallization temperature, and the weight loss temperature of the copolymers decreased with increasing molecular weights of PEG. Consequently, the hydrophilicities by means of contact angle measurement and moisture content of the copolymer films were found to be significantly improved with increasing molecular weights of PEG.     

The effects of blend composition and blending time on the ester interchange reaction and tensile properties of PLA/LPCL/HPCL blends

PLA/LPCL/HPCL blends composed of poly(lactic acid) (PLA), low molecular weight poly(ε-caprolactone) (LPCL), and high molecular weight poly(ε-caprolactone) (HPCL) were prepared by melt blending for bioabsorbable filament sutures. The effects of blend composition and blending time on the ester interchange reaction by alcoholysis in the PLA/LPCL/HPCL blends were studied. Their thermal properties and the miscibility due to the ester interchange reaction were investigated by¹H-NMR, DSC, X-ray, and UTM analyses. The hydroxyl group contents of LPCL in the blends decreased by the ester interchange reaction due to alcoholysis. Thus, the copolymer was formed by the ester interchange reaction at 220 °C for 30–60 minutes. The thermal properties of PLA/LPCL/HPCL blends such as melting temperature and heat of fusion decreased with increasing ester interchange reaction levels. However, the miscibility among the three polymers was improved greatly by ester interchange reaction. Tensile strength and modulus of PLA/LPCL/HPCL blend fibers increased with increasing HPCL content, while the elongation at break of the blend fibers increased with increasing LPCL content.     

Mechanical and thermal properties of recycled poly(ethylene terephthalate) reinforced newspaper fiber composites

This study presents the mechanical and thermal properties of environment-friendly composites made from recycled newspaper fibers reinforced recycled poly(ethylene terephthalate) (rPET) resin with the addition of styrene-ethylene-butylene-styrene grafted maleic anhydride (SEBS-g-MA) as compatibilizer. The effect of SEBS-g-MA addition (i.e., 10 phr) by using a twin-screw extruder to the rPET resin, followed by different fiber content (5, 10 and 15 wt.%) on the tensile, flexural and impact properties of the composites were determined. Stiffness of composites increased significantly compared to those of rPET/SEBS-g-MA blend. Fiber addition resulted in moderate increases in both tensile and flexural strength of the composites. Scanning electron microscope (SEM) photomicrographs of the impact fracture surfaces demonstrate good adhesion at 5 and 10 % fiber content. Differential scanning calorimetry (DSC) showed that the presence of newspaper fibers enhanced the nonisothermal crystallization kinetics and crystallinity. Thermal stability of the composites was improved as indicated by thermogravimetric analysis (TGA).     

Thermo-mechanical and morphological properties of short natural fiber reinforced poly (lactic acid) biocomposite: Effect of fiber treatment

Untreated oil palm empty fruit bunch (REFB), alkali treated EFB (AEFB), ultrasound treated EFB (UEFB) and simultaneous ultrasound-alkali treated EFB (UAEFB) short fibers were incorporated in poly(lactic acid) (PLA) for fabricating bio-composites. The REFB fiber-PLA (REPC) and treated EFB (TEFB) fiber-PLA (TEPC) composites were prepared and characterized. Glass transition temperature, crystal melting temperature, decomposition temperature, melt flow index, density and mechanical properties (tensile strength, tensile modulus and impact strength) of TEPC are found to be higher than those of REPC. The observed crystallization temperature of TEPC is lower than that of REPC. Among all samples, TEPC prepared from UAEFB fiber shows better performances than other samples fabricated by REFB and AEFB fibers. Scanning electron microscopy, Fourier transform infrared spectroscopy and XRD analyses well support all the observed results.     

Compatibilization of immiscible poly(<Emphasis Type="Italic">l</Emphasis>-lactide) and low density polyethylene blends

Blends of poly(l-lactide) (PLA) and low density polyethylene (LDPE) were prepared by melt mixing in order to improve the brittleness of PLA. A reactive compatibilizer with glycidyl methacrylate (GMA), PE-GMA, was required as a compatibilizer due to the immiscibility between PLA and LDPE. It contributes to reduce the domain size of dispersed phase and enhance the tensile properties of PLA/LDPE blends, especially for PLA matrix blends. A reaction product between PLA and PE-GMA, which was formed during melt-mixing and considered to act as a reactive compatibilizer, was characterized using¹H-NMR spectroscopy.