Influence of montmorillonite layered silicate on plasticized poly(l-lactide) blown films

Plasticized poly(l-lactide) (PLA) montmorillonite layered silicate (MLS) nanocomposites were compounded and blown-film processed using a co-rotating twin screw extruder. PLA was mixed with 10 wt% acetyltriethyl citrate ester plasticizer and 5 wt% of an organically modified montmorillonite at various screw speeds. Wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) determined that the compounded pellets and the blown film PLA/MLS nanocomposites were intercalated. The effect of processing screw speeds on the barrier, thermal, mechanical, and biodegradation properties of the nanocomposites were analyzed and compared to the neat polymer. Nanocomposite films show a 48% improvement in oxygen barrier and a 50% improvement in water vapor barrier in comparison to the neat PLA. The thermogravimetric analysis (TGA) showed an overall 9 °C increase in the decomposition temperature for all of the nanocomposites. Differential scanning calorimetry (DSC) has determined that the glass transition, cold crystallization and melting point temperatures were not significantly influenced by the presence of MLS. Mechanical properties of the nanocomposites showed that the Young's modulus increased by 20% and the ultimate elongation of the nanocomposites were not sacrificed in comparison to the neat samples. Biodegradation rates in soil were slightly greater for the PLA/MLS nanocomposite than the pure PLA. However, none of the PLA pure and nanocomposites achieved significant biodegradation levels after 180 days.     

Rheology,mechanical properties,and biodegradation of poly(ε‐caprolactone)/silica nanocomposites

Biodegradable poly(ε‐caprolactone) (PCL)/silica nanocomposites containing 1–9 wt% silica nanoparticles were prepared by melt compounding in this work. The rheology, mechanical properties, and biodegradation were investigated. PCL/silica nanocomposite shows a high percolation threshold, which is between 7 and 9 wt%. Once percolation network structure forms, the long‐range motion of PCL chains is highly restrained. From the results of mechanical tests, the tensile strength, modulus, and yield strength of the nanocomposites are enhanced by the incorporation of silica nanoparticles. Moreover, it is interesting to find that the biodegradation rates have been enhanced obviously in the PCL/silica nanocomposites than in neat PCL, which may be of great use for the practical application of PCL. POLYM. COMPOS., 34:1620–1628, 2013. © 2013 Society of Plastics Engineers     

纤维素纳米纤维对聚乳酸结晶、流变和拉伸性能的影响

采用熔融共混⁃注射成型制备了聚乳酸（PLA）/纤维素纳米纤维（CNFs）可生物降解纳米复合材料,利用差示扫描量热仪、流变测试、拉伸性能测试等手段,考察了CNFs含量对PLA/CNFs复合材料结晶行为、流变特性和力学性能的影响规律。结果表明,少量的CNFs能均匀分散在PLA基体中,CNFs可作为PLA的异相成核剂,提高结晶速率常数,缩短半结晶时间,CNFs的含量为5 %（质量分数,下同）时,半结晶时间由纯PLA的10.4 min缩短至2.9 min;CNFs体现出润滑作用,使PLA/CNFs复合材料的储能模量和损耗模量均低于纯PLA;CNFs的含量为3 %时,复合材料的断裂伸长率较纯PLA提高了41.2 %。     

New polylactide-layered silicate nanocomposites. 2. Concurrent improvements of material properties, biodegradability and melt rheology

Our continuing research on the preparation, characterization, materials properties, and biodegradability of polylactide (PLA)-layered silicate nanocomposites has yielded results for PLA-montmorillonite nanocomposites. Montmorillonite modified with trimethyl octadecylammonium cation was used as an organically modified layered silicate for the nanocomposites preparation. The internal structure of the nanocomposites in the nanometer range has been established by using wide-angle X-ray diffraction and transmission electron microscope analyses. All the nanocomposites exhibited superior improvement of practical materials properties such as storage modulus, flexural modulus, flexural strength, heat distortion temperature, and gas barrier property as compared to that of neat PLA. The biodegradability of neat PLA and a representative nanocomposite was also studied under compost, and the rate of biodegradation of neat PLA significantly increased after nanocomposites preparation. The melt rheology of neat PLA and various PLACNs was also studied.     

Crystallization and morphology studies of biodegradable poly(ε‐caprolactone)/silica nanocomposites

Biodegradable poly(ε‐caprolactone) (PCL)/silica nanocomposites at various silica loadings were prepared via direct melt compounding method in this work. Scanning electron microscopy observation indicated that when the silica content was < 3 wt%, the nanoparticles dispersed evenly in the PCL matrix and exhibited only aggregates with particle size of less than 100 nm. The results of nonisothermal melt crystallization showed that the crystallization peak temperature was higher in the nanocomposites than in neat PCL; moreover, the overall crystallization rate was faster in the nanocomposites than in neat PCL during isothermal melt crystallization. Both nonisothermal and isothermal melt crystallization studies suggested that the crystallization of PCL was enhanced by the presence of silica and influenced by the silica loading. The effect of silica on the crystallization behavior was twofold: the presence of silica may provide heterogeneous nucleation sites for the PCL crystallization while the aggregates of silica may restrict crystal growth of PCL. However, the crystal structure of PCL remained almost unchanged despite the presence of silica in the nanocomposites. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Rheology and morphology study of immiscible linear low‐density polyethylene/poly(lactic acid) blends filled with nanosilica particles

The objectives of this study are to investigate the effect of silica nanoparticles on the morphology and rheological behavior of immiscible linear low‐density polyethylene/poly(lactic acid) (LLDPE/PLA) blends. Melt blending method is applied to prepare the blends and their nanocomposites. Scanning electron microscope and parallel plate rheometer were used to investigate morphology and rheological behavior of the blend nanocomposites. Scanning electron microscope results demonstrated a significant change in morphology behavior by incorporation of silica nanoparticles. A significant reduction in the PLA droplet for LLDPE/PLA (75/25) with 8 wt % silica was observed. The rheological studies illustrated that for all samples storage modulus and complex viscosity of blend nanocomposites are higher than neat blends. Finally, melt rigidity of blend nanocomposites was estimated by measurement of rheological properties using a rotational rheometer through small amplitude oscillatory shear experiments. As a result, through the shear data, a high value quantity as a criteria for melt rigidity is obtained for the LLDPE/PLA (75/25) with 8 wt % silica in comparing to the other samples. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45526.     

Effects of thermoplastic polyurethane on the properties of poly(lactic acid)/organo‐montmorillonite nanocomposites based on novel vane extruder

Polylactic acid (PLA)/organo‐montmorillonite (OMMT) nanocomposites toughened with thermoplastic polyurethane (TPU) were prepared by melt‐compounding on a novel vane extruder (VE), which generates global dynamic elongational flow. In this work, the mechanical properties of the PLA/TPU/OMMT nanocomposites were evaluated by tensile, flexural, and tensile tests. The wide‐angle X‐ray diffraction and transmission electron microscopy results show that PLA/TPU/OMMT nanocomposites had clear intercalation and/or exfoliation structures. Moreover, the particles morphology of nanocomposites with the addition of TPU was investigated using high‐resolution scanning electronic microscopy. The results indicate that the spherical TPU particles dispersed in the PLA matrix, and the uniformity decreased with increasing TPU content (≤30%). Interestingly, there existed abundant filaments among amount of TPU droplets in composites with 30 and 40 wt% TPU. Furthermore, the thermal properties of the nanocomposites were examined with differential scanning calorimeter and dynamic mechanical analysis. The elongation at break and impact strength of the PLA/OMMT nanocomposites were increased significantly after addition of TPU. Specially, Elongation at break increased by 30 times, and notched impact strength improved 15 times when TPU loading was 40 wt%, compared with the neat PLA. Overall, the modified PLA nanocomposites can have greater application as a biodegradable material with enhanced mechanical properties. POLYM. ENG. SCI., 54:2292–2300, 2014. © 2013 Society of Plastics Engineers     

Influence of Mesoporous Silica and Butyral Content on the Mechanical,Water Absorption,and Permeability Properties of in situ Synthesized Silica/PVB Nanocomposite Films

Poly(vinyl butyral)–silica nanocomposites were synthesized in situ with three different degrees of butyral and with varying silica content for each vinyl butyral polymer ratio. The glass transition temperatures of the polymer nanocomposites were found to be ～40–46 and ～52°C for the neat polymer, respectively. The 4 wt% silica loaded film showed higher strength and lower strain to failure compared with the neat polymer. The matrix with 0.5 and 0.75 butyral:alcohol for 2.5–4 wt% silica exhibited good water vapor transmission and the efficiencies of these films were 50% higher than their encapsulated pristine polymer films.     

Solvent-Free One-Pot Synthesis of high performance silica/epoxy nanocomposites

High performance silanized silica/epoxy nanocomposites were prepared through mixing epoxy, tetraethyl orthosilicate (TEOS), (3-aminopropyl)trimethoxysilane (APTMS) and ammonia solution at 50 °C. This all-in-one “Solvent-Free One-Pot Synthesis” results in nanocomposites with uniform dispersion of oval shaped silica nanoparticles and strong adhesion between silica and epoxy matrix. The influence of the synthesis conditions, such as molar ratio of NH₃:TEOS, aging time, curing process and silica content on the thermal mechanical properties of nanocomposites were studied. The silanized silica/epoxy nanocomposite prepared in this study exhibits better thermal mechanical property in comparison with neat epoxy, non-functionalized silica/epoxy and commercialized silica/epoxy systems. The prepared nanocomposite with 3 wt% silanized silica exhibits 20%, 17% and 6% improvements on flexural, tensile and storage modulus over those of neat epoxy, respectively.     

Measurement of the mechanical and dynamic properties of 3D printed polylactic acid reinforced with graphene

In this paper, three-dimensional (3D) printing system based on fused deposition modeling (FDM) is used for the fabrication of polylactic acid (PLA) specimens with and without graphene and to measure their dynamic mechanical properties. In particular, 3D printed PLA/graphene nanocomposites containing 10wt% graphene in PLA matrix were characterized by compression tests, cyclic compression tests, nanoindentation and modal tests. The results of the mechanical tests reveal that the incorporation of multifunctional graphene has improved the modulus, the strength and the hardness of the 3D printed nanocomposites. The damping as calculated by cyclic compression and modal tests was substantially increased compared to neat PLA samples.     

Degradability Enhancement of Poly(Lactic Acid) by Stearate-Zn(3)Al LDH Nanolayers

Recent environmental problems and societal concerns associated with the disposal of petroleum based plastics throughout the world have triggered renewed efforts to develop new biodegradable products compatible with our environment. This article describes the preparation, characterization and biodegradation study of poly(lactic acid)/layered double hydroxide (PLA/LDH) nanocomposites from PLA and stearate-Zn₃Al LDH. A solution casting method was used to prepare PLA/stearate-Zn₃Al LDH nanocomposites. The anionic clay Zn₃Al LDH was firstly prepared by co-precipitation method from a nitrate salt solution at pH 7.0 and then modified by stearate anions through an ion exchange reaction. This modification increased the basal spacing of the synthetic clay from 8.83 Å to 40.10 Å. The morphology and properties of the prepared PLA/stearate-Zn₃Al LDH nanocomposites were studied by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), thermogravimetric analysis (TGA), tensile tests as well as biodegradation studies. From the XRD analysis and TEM observation, the stearate-Zn₃Al LDH lost its ordered stacking-structure and was greatly exfoliated in the PLA matrix. Tensile test results of PLA/stearate-Zn₃Al LDH nanocomposites showed that the presence of around 1.0–3.0 wt % of the stearate-Zn₃Al LDH in the PLA drastically improved its elongation at break. The biodegradation studies demonstrated a significant biodegradation rate improvement of PLA in the presence of stearate-Zn₃Al LDH nanolayers. This effect can be caused by the catalytic role of the stearate groups in the biodegradation mechanism leading to much faster disintegration of nanocomposites than pure PLA.     

Effects of thermoplastic poly(ether-ester) elastomer and bentonite nanoclay on properties of poly(lactic acid)

This work presented the influence of thermoplastic poly(ether-ester) elastomer (TPEE) and bentonite (BTN) on improving the mechanical and thermal properties of poly(lactic acid) (PLA). PLA was initially melt mixed with TPEE at six different loadings (5–30 wt%) on a twin screw extruder and then injection molded. The mechanical tests revealed an increasing impact strength and elongation at break with increasing TPEE loading, but a diminishing Young's modulus and tensile strength with respect to pure PLA. The blend at 30 wt% TPEE provided the optimum improvement in toughness, exhibiting an increase in the impact strength and elongation at break by 3.21- and 10.62-fold over those of the pure PLA, respectively. Scanning electron microscopy analysis illustrated a ductile fractured surface of the blends with the small dispersed TPEE domains in PLA matrix, indicating their immiscibility. The 70/30 (wt/wt) PLA/TPEE blend was subsequently filled with three loadings of BTN (1, 3, and 5 parts by weight per hundred of blend resin [phr]), where the impact strength, Young's modulus, tensile strength and thermal stability of all the blends were improved, while the elongation at break was deteriorated. Among the three nanocomposites, that with 1 phr BTN formed exfoliated structure and so exhibited the highest impact strength, elongation at break, and tensile strength compared to the other intercalated nanocomposites. Moreover, the addition of BTN was found to increase the thermal stability of the neat PLA/TPEE blend due to the barrier properties and high thermal stability of BTN.     

Morphology,biodegradability, mechanical,and thermal properties of nanocomposite films based on PLA and plasticized PLA

In this study, melt intercalation method is applied to prepare poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG)‐plasticized PLA nanocomposite films including 0, 3, and 5% organoclay (Cloisite 30B) using a laboratory scale compounder, which is connected to a microcast film device. To evaluate the nanomorphology and the dispersion state of the clays, X‐ray diffraction (XRD) and transmission electron microscopy (TEM) are conducted. Tensile tests are performed to characterize the mechanical behavior of the films. Biodegradation rate is determined by degradation tests in composting medium. Differential scanning calorimeter (DSC) is applied to observe the thermal behavior of the films. XRD and TEM show that the exfoliation predominantly occurrs in plasticized PLA nanocomposites, whereas unexfoliated agglomerates together with exfoliated clays are observed in the nonplasticized PLA. Tensile tests indicate that the addition of 3% clay to the neat‐PLA does not affect the strength; however, it enhances the modulus of the nanocomposites in comparison to neat‐PLA. Incorporation of 3% clay to the plasticized PLA improves the modulus with respect to PLA/PEG; on the other hand, the strain at break value is lowered ～ 40%. The increase in the rate of biodegradation in composting medium is found as in the order of PLA > PLA/PEG > 3% Clay/PLA/PEG > 5% Clay/PLA/PEG > 3% Clay/PLA. DSC analysis shows that the addition of 3% clay to the neat PLA results in an increase in T_g. The addition of 20% PEG as a plasticizer to the neat‐PLA decreases T_g about 30°C, however incorporation of clays increases T_g by 4°C for the plasticized PLA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polylactide/transition metal ion modified montmorillonite nanocomposite—a critical evaluation of mechanical performance and thermal stability

Polylactide (PLA) nanocomposite was prepared by melt blending of PLA and transition metal ion (TMI) adsorbed montmorillonite (MMT). PLA nanocomposite was characterized for mechanical performance, and the results revealed that the tensile modulus, flexural modulus, and impact strength were increased marginally. The nanocomposite was optimized at 5 wt% of TMI‐modified MMT (TMI‐MMT) loading. Thermogravimetric analysis displayed increase in onset of degradation temperature, and differential scanning calorimetry showed marginal increase in glass transition temperature (T_g) and melting temperature (T_m) in case of PLA nanocomposites, when compared with virgin PLA. The flammability testing of nanocomposites indicated good fire retardance characters. X‐ray diffraction patterns of TMI‐MMT and the corresponding nanocomposites indicated an intercalation of the metal ions into the clay interlayer. Fourier transform infrared spectroscopy analysis indicate formation of [Zn(EDA)₂]²⁺ and [Cu(EDA)₂]²⁺ complexes in the MMT interlayer. Dynamic mechanical analysis shows increase in glass transition temperature (T_g) and storage modulus (E′) in case of PLA nanocomposites reinforced with 5 wt% modified MMT. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Fabrication and characterization of biodegradable poly(lactic acid)/layered silicate nanocomposites

In this study biocompatible/biodegradable poly(lactic acid) (PLA)/layered silicate nanocomposites (PLSNs) were successfully prepared by the intercalation of PLA polymer into organically modified layered silicate through the solution mixing process. Both X‐ray diffraction data and transmission electron microscopy images of PLSNs indicate most of the swellable silicate layers were disorderedly intercalated into the PLA matrix. Mechanical properties of the 0.1 wt% silicate‐containing fabricated nanocomposites performed by dynamic mechanical analysis have significant improvements in the storage modulus when compared to that of neat PLA matrix. Adding more layered silicates into PLA matrix induced a decrease in the mechanical properties of PLSNs, probably due to the presence of a large dimension of porosity in the fabricated nanocomposites. POLYM. ENG. SCI., 45:1615–1621, 2005. © 2005 Society of Plastics Engineers     

Graphene Nanoplatelets as Novel Reinforcement Filler in Poly(lactic acid)/Epoxidized Palm Oil Green Nanocomposites: Mechanical Properties

Graphene nanoplatelet (xGnP) was investigated as a novel reinforcement filler in mechanical properties for poly(lactic acid) (PLA)/epoxidized palm oil (EPO) blend. PLA/EPO/xGnP green nanocomposites were successfully prepared by melt blending method. PLA/EPO reinforced with xGnP resulted in an increase of up to 26.5% and 60.6% in the tensile strength and elongation at break of the nanocomposites respectively, compared to PLA/EPO blend. XRD pattern showed the presence of peak around 26.5° in PLA/EPO nanocomposites which corresponds to characteristic peak of graphene nanoplatelets. However, incorporation of xGnP has no effect on the flexural strength and modulus. Impact strength of PLA/5 wt% EPO improved by 73.6% with the presence of 0.5 wt% xGnP loading. Mechanical properties of PLA were greatly improved by the addition of a small amount of graphene nanoplatelets (<1 wt%).     

Preparation,characterization, and biodegradation of PS:PLA and PS:PLA:OMMT nanocomposites using Aspergillus niger

Poly(lactic acid) (PLA) was synthesized using l ‐lactic acid by condensation polymerization. Polystyrene (PS) and surface modified montmorillonite (OMMT) was used for the preparation of PS:PLA composites and PS:PLA:OMMT nanocomposites. The composite materials prepared had varying amount of PLA (10–30%) and OMMT (0.5–5 phr). These composites were subjected to degradation in minimal medium using the fungi Aspergillus niger (A. niger) under controlled conditions. Scanning electron microscopy (SEM) showed the growth of microorganism on the polymer surface and fracture within the polymer matrix as a result of degradation. Fourier transform infra red spectroscopy (FTIR) was further used to determine the mechanism leading to biodegradation. It was found that the biodegradation of both PS:PLA and PS:PLA:OMMT took place mainly via break down and utilization of ester group, as can be seen from disappearance of absorption peak of ester group and simultaneous appearance of a typical IR absorption of microbial mass at 1450 cm⁻¹. The thermal stability of PS:PLA:OMMT nanocomposites was found to increase with increasing concentration of OMMT, as observed from thermo gravimetric analysis (TGA), while mechanical property was found to be decreased after degradation at 30% of PLA and 5 wt% of OMMT content. Change in extracellular protein content, biomass production and % degradation with respect to time (up to 28 days) were studied and correlated to evaluate the effectiveness of A. niger in biodegradation of the composites. POLYM. COMPOS., 35:263–272, 2014. © 2013 Society of Plastics Engineers     

Synergetic association of grafted PLA and functionalized graphene on the properties of the designed nanocomposites

The synergetic association of poly(lactic acid) grafted with maleic anhydride (MA-g-PLA) containing 0.44 wt% of maleic anhydride and epoxy-functionalized graphene (GFe) on the properties of the designed nanocomposites was studied. Rheological, mechanical and barrier properties of PLA nanocomposites were studied using different content of epoxy-functionalized graphene and MA-g-PLA compatibilizer. The PLA/MA-g-PLA/GFe nanocomposites prepared by melt blending, containing 5 wt% of MA-g-PLA, yield a maximum in storage modulus G′ and a rheological plateau at low frequencies, with a content of epoxy-functionalized graphene comprised between 4 and 7 wt%. This phenomenon was ascribed to a pseudo-solid behavior resulting from the high degree of epoxy-functionalized graphene exfoliation due to strong interfacial interactions with PLA and epoxy-functionalized graphene. The better mechanical and barrier performances were obtained with PLA/GFe containing 10 wt% of epoxy-functionalized graphene and 5 wt% of MA-g-PLA compatibilizer. The variation of the percentage of compatibilizer showed that 5 wt% of maleated PLA was sufficient to improve the thermal, rheological, mechanical and barrier properties of the PLA nanocomposite containing 7 wt% of epoxy-functionalized graphene.     

Preparation and characterization of nanocomposites based on polylactides tethered with polyhedral oligomeric silsesquioxane

A series of polylactides tethered with polyhedral oligomeric silsesquioxane (POSS–PLAs) were synthesized via the ring‐opening polymerization of L ‐lactide with 3‐hydroxypropylheptaisobutyl polyhedral oligomeric silsesquioxane (3‐hydroxypropylheptaisobutyl POSS) at a concentration of 0.02–2.00 mol % in the presence of a stannous(II) octoate catalyst. 1 H‐NMR spectra and a composition analysis of the POSS–PLA hybrids confirmed that 3‐hydroxypropylheptaisobutyl POSS served as an initiator for L ‐lactide in the ring‐opening polymerization. X‐ray diffraction patterns evidenced that polyhedral oligomeric silsesquioxane (POSS) molecules of POSS–PLA hybrids were well dispersed without the formation of their crystalline aggregates. The POSS–PLA hybrid with 0.50 mol % POSS content was solution‐blended with a neat polylactide (PLA) homopolymer to obtain PLA/POSS–PLA nanocomposites with various POSS–PLA contents of 1–30 wt %. The X‐ray diffraction results of the PLA/POSS–PLA nanocomposites demonstrated that the POSS–PLA was well dispersed in the neat PLA matrix. The thermal and thermooxidative degradation properties of the nanocomposites were found to be improved at POSS–PLA contents of 1–20 wt %, compared to the neat PLA. The crystallization rates and crystallinities of the PLA/POSS–PLA nanocomposites were faster and higher, respectively, with increasing POSS–PLA content because of the nucleation effect of the POSS molecules in the neat PLA matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Enzymatic degradation of polylactide/layered silicate nanocomposites: Effect of organic modifiers

Biodegradable polylactide (PLA)/layered silicate nanocomposites have been prepared via solution route using two different kinds of organically modified nanoclays. The nanostructure as observed from wide‐angle X‐ray diffraction indicates intercalated hybrids and the extent of intercalation depends on the type of organic modifiers used. Melt‐quenched PLA and its nanocomposites are predominantly amorphous but, after annealing, they are fairly crystalline. The nanohybrids show significant improvement in thermal properties as compared to neat polymer. The nature of interaction between nanoclays and matrix polymer depends on the organic modifiers used, as evident from varying heat of fusion and shifting of Fourier transform infrared peaks. The nanoclays act as nucleating agent, and thereby, control the spherulite dimension of the matrix. The comparison of biodegradation of PLA and its nanocomposites has been studied in enzyme, compost, and buffer solution. Biodegradability of PLA has significantly been enhanced in the presence of nanoclays and the rate varies on organic modifications. The surface morphology, before and after enzymatic degradation, confirms the relative rate of degradation through laser scanning confocal images, scanning electron microscope, and atomic force microscope. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013