Preparation,characterization, structure‐property relationships,and thermal degradation kinetics of poly (lactic acid)/amidated potassium hydrogen phthalate intercalated layered double hydroxides nanocomposites

A novel nucleating agent, amidated potassium hydrogen phthalate intercalated layered double hydroxides (AP‐LDHs) were prepared using an amidation reaction. Through the structural characterization, it was found that AP‐LDHs had been successfully prepared. Meanwhile, the antibacterial activity of AP‐LDHs was studied. In order to improve the performance of poly (lactic acid) (PLA), PLA/AP‐LDHs nanocomposites were prepared by melt blending. Morphological analysis showed that PLA nanocomposites had an exfoliated structure. Mechanical properties test showed that the mechanical properties of PLA nanocomposites were enhanced. And the fracture scanning electron microscope analysis indicated that the PLA/AP‐LDHs nanocomposites exhibited ductile fracture characteristics. Moreover, differential scanning calorimetry and polarized optical microscopy analysis results demonstrated that the crystallization rate, nucleation density, and crystallinity of PLA/AP‐LDHs were improved. Thermogravimetric analysis and thermal degradation kinetics showed that the thermal stability of the PLA nanocomposites was significantly improved.     

Synthesis,characterization of layered double hydroxide‐poly(methylmethacrylate) graft copolymers via activators regenerated by electron transfer for atom transfer radical polymerization and its effect on the performance of poly(lactic acid)

Layered double hydroxide‐poly(methylmethacrylate) (LDH‐PMMA) graft copolymers were prepared via activators regenerated by electron transfer for atom transfer radical polymerization. The results showed that the hydrophobicity of LDH‐PMMA was improved by the incorporation of hydrophilic groups. Moreover, poly(lactic acid) (PLA)/LDH‐PMMA nanocomposites were prepared by melt blending to enhance the performances of PLA. The crystallization and mechanical properties of the PLA/LDH‐PMMA nanocomposites were studied by differential scanning calorimetry, tensile testing, and polarized optical microscopy, respectively. Results of mechanical testing showed that the tensile strength, elongation at break, and impact strength of PLA/LDH‐PMMA nanocomposites were increased by 5.64%, 37.95%, and 49.70%, respectively, compared with PLA. The differential scanning calorimetry results indicated that LDH‐PMMA eliminated the cold crystallization of PLA matrix and improved the crystallinity of PLA by 37.26%. The polarized optical microscopy of PLA/LDH‐PMMA nanocomposites demonstrated that LDH‐PMMA increased the crystallization rate of PLA. It was also found that the rheological behaviors of the PLA nanocomposites were significantly enhanced. Based on these results, a new choice for modified LDHs was provided and used as a nucleating agent to improve the properties of PLA.     

Biodegradable poly(lactic acid)/chitosan-modified montmorillonite nanocomposites: Preparation and characterization

In this study, the biodegradable poly(lactic acid) (PLA)/montmorillonite (MMT) nanocomposites were successfully prepared by the solution mixing process of PLA polymer with organically-modified montmorillonite (m-MMT), which was first treated by n-hexadecyl trimethyl-ammonium bromide (CTAB) cations and then modified by biocompatible/biodegradable chitosan to improve the chemical similarity between the PLA and m-MMT. Both X-ray diffraction data and transmission electron microscopy images of PLA/m-MMT nanocomposites indicate that most of the swellable silicate layers were disorderedly intercalated into the PLA matrix. Mechanical properties and thermal stability of the PLA/m-MMT nanocomposites performed by dynamic mechanical analysis and thermogravimetric analysis have significant improvements in the storage modulus and 50% loss in temperature when compared to that of neat PLA matrix. The degradation rates of PLA/m-MMT nanocomposites are also discussed in this study.     

The effects of intralayer metal composition of layered double hydroxides on glass transition, dispersion, thermal and fire properties of their PMMA nanocomposites

A series of aluminum-containing layered double hydroxides (LDHs), containing Mg, Ca, Co, Ni, Cu and Zn as the divalent metals, have been prepared by the co-precipitation method and used to prepare nanocomposites of PMMA by in situ bulk polymerization. The additives were characterized by Fourier transform infrared spectroscopy, X-ray diffraction spectroscopy (XRD) and thermogravimetric analysis while the polymer composites were characterized by XRD, transmission electron microscopy, differential scanning calorimetry and cone calorimetry. Polymerization of methyl methacrylate in the presence of these undecenoate LDHs results in composites with enhanced thermal stability. The glass transition temperatures of the composites and the pristine polymers are found to be around 110 °C; this suggests that the presence of these additives has little effect on the polymer. It is found that the additive composition and the dispersion state of LDHs agglomerates in the polymer matrix influence the fire properties of composites as measured by cone calorimetry.     

Nanosize and microsize clay effects on the kinetics of the thermal degradation of polylactides

Polylactide (PLA)-montmorillonite (MMT) micro- and nanocomposites based on semicrystalline and amorphous polymers and unmodified or organomodified clays at 5 wt% content were produced by melt mixing. Based on the three different test methods that were used to follow thermal degradation, different conclusions were obtained. During melt processing, thermomechanical degradation was more pronounced in the presence of all fillers, which apparently acted catalytically, but to different degrees. During isothermal degradation in air from 180 °C to 200 °C, degradation rate constants were calculated from novel equations incorporating changes in intrinsic viscosity (IV). Results show that the thermal degradation rate constants of the amorphous PLA and its composites are lower than those of the semicrystalline PLA and its composites. Due to better filler dispersion in the polymer matrix, the thermal degradation rate constants of the nanocomposites are significantly lower than those of the unfilled polymers and their microcomposites under air. As per dynamic TGA data and thermal kinetic analysis from weight losses and activation energy calculations, organomodified nanofillers have a complex effect on the polymer thermal stability; the unmodified fillers, however, reduce polymer thermal stability. These TGA data and kinetic analysis results also support the findings that the thermal stability of the amorphous PLA and its composites is higher than that of the semicrystalline polymer and its composites and the thermal stability of the nanocomposites is higher than that of the microcomposites. In general, mathematical modeling based on random thermal scission equations was satisfactory for fitting the TGA experimental data.     

乳液聚合法制备聚苯乙烯/Mg-Al层状双氢氧化物纳米复合材料

采用乳液聚合法制备阻燃性聚苯乙烯MgAl层状双氢氧化物(LDHs)纳米复合材料.通过对不同合成条件下复合材料的XRD谱,讨论了纳米复合材料的形成过程;经SEM图证实了LDHs是以剥离的纳米级层片分散在基体中的;TG和DSC谱图揭示了LDHs纳米层板可有效提高PS的热稳定性,并可使PS的玻璃化转化温度明显提高;当层状双氢氧化物在插层复合材料中含量为14.92%时,纳米复合材料的氧指数可达23.5%,其用量比在PS中直接添加纳米LDHs时要少约一倍.文中还分析了纳米复合材料的形成过程.     

Elastomer/LDH nanocomposites: Synthesis and studies on nanoparticle dispersion, mechanical properties and interfacial adhesion

Layered double hydroxides (LDHs) based elastomer nanocomposites have been synthesized and characterized in terms of nanoparticle dispersion, mechanical properties and interfacial adhesion. Since LDH has basic hydroxyl groups on its surface, its potential as reinforcing filler in elastomers and in additionally a crosslinking agent in carboxylated elastomers has been investigated in details. For this purpose, two different elastomers having widely different polarities and functional groups (e.g., ethylene propylene diene terpolymer, i.e. EPDM and carboxylated nitrile rubber, i.e. XNBR) have been used as the matrix. The pristine LDH based on Mg and Al was modified with decane sulfonate by the regeneration method. The morphological analysis of the nanocomposites (done by X-ray diffraction analysis and electron microscopy) shows that in both matrices LDH particles are dispersed in three different forms, i.e. as primary particles, as exfoliated layers and as soft clusters formed by both of them. However, their relative proportion differs drastically in the two matrices. We have shown in this study that the LDH can significantly improve the mechanical properties in both the system. In XNBR/LDH nanocomposites containing no conventional metal oxide curative, this improvement is very prominent due to secondary interaction between LDH and XNBR matrix indicating that LDH can crosslink carboxalated elastomers. It is also observed that LDH particle promotes strain-induced crystallization in XNBR/LDH. The fracture surface analysis shows that in XNBR/LDH nanocomposite very stable polymer-filler interface is formed and tensile failure takes place through the matrix rather than through the interface. In case of EPDM/LDH nanocomposites the opposite is observed and the polymer matrix hardly wets the surface of the LDH particle.     

Synthesis and physical properties of new surfactants based on ionic liquids: Improvement of thermal stability and mechanical behaviour of high density polyethylene nanocomposites

Ionic liquids based on alkyltriphenyl phosphonium and dialkyl imidazolium cations with long alkyl chains have been synthesized and used as new surfactants for cationic exchange of layered silicates. The influence of the alkyl chain length and the chemical nature of the conteranion or of the cation on the thermal stability of these new intercalating agents and on imidazolium- (MMT-I) or phosphonium- (MMT-P) modified montmorillonites have been analyzed by thermogravimetric analysis (TGA). Thermoplastic nanocomposites based on these modified montmorillonites with a very low amount of nanofillers (1wt.%) have been processed by melt mixing using a twin screw extruder. The distribution of the clay layers in a high density polyethylene (HDPE) matrix was characterized and finally the mechanical and thermal properties of the corresponding nanocomposites were determined.     

Replication and surface properties of micro injection molded PLA/MWCNT nanocomposites

Multi-walled carbon nanotube (MWCNT) reinforced polylactide (PLA) nanocomposites were injected molded into a mold with micro needle patterns. In order to alleviate the hesitation effect caused by an increased melt viscositgy of PLA/CNT nanocomposites, the effects of the injection speed and holding pressure on the replication property were investigated. The effects of MWCNTs on the crystallization, thermal behavior, replication properties, replication and surface properties of micro injection molded PLA/CNT nanocomposites were investigated. An analysis of crystallinity and thermal behavior indicated that the MWCNTs promoted the unique α’ to α crystal transition of PLA, leading to an enhancement of surface modulus and hardness, as measured using a nanoindentation technique. The specific interaction between PLA and MWCNTs was characterized using an equilibrium melting point depression technique. Furthermore, the MWCNTs increased the activation energy for thermal degradation of PLA due to the physical barrier effect. The improved replication quality of the microfeatures in the PLA/MWCNT nanocomposites has been achieved by elevating injection speed and holding pressure, which enhances the polymer filling ability within the micro cavity. A replication ratio greater than 96% for the micro injection molded PLA/CNT nanocomposites were achieved at holding pressure of 100 MPa and injection speed of 120 mm/s. This study shows that processing conditions significantly influence the replication and surface properties of micro injection molded PLA/CNT nanocomposites.     

Preparation of PLA-based nanocomposites modified by nano-attapulgite with good toughness-strength balance

Polylactic acid (PLA) was modified by poly (butylene adipate-co-terephthalate) (PBAT) and nano-attapulgite (AT) using the melt blending technique. Ethylene-butyl acrylate-glycidyl methacrylate (E-BA-GMA) was used as a compatibilizer which can bond the AT nanoparticles with PLA/PBAT matrix by interaction between the epoxy and hydroxyl groups. The effects of the AT content on the mechanical properties, thermal properties, crystallinity and morphology of PLA/PBAT/ATT nanocomposites were investigated. The results showed that the tensile strength, elongation at break and impact strength of PLA/PBAT could be simultaneously increased by incorporating AT nanoparticles. PLA/PBAT/AT nanocomposites possessed higher thermal stability than pure PLA/PBAT. In the ternary composite system of PLA/PBAT/AT, AT acted as a heterogeneous nucleating agent and was able to increase the crystallization temperature. When the AT content was low (≤2.5 wt%), AT nanoparticles could uniformly disperse in the PLA/PBAT matrix. In general, AT was an effective filler to reinforce and toughen PLA/PBAT blend simultaneously, and the PLA/PBAT/AT nanocomposite with 2.5 wt% AT exhibited a good combination of strength and toughness.     

Highly efficient flame retardant poly(lactic acid) using imidazole phosphate poly(ionic liquid)

Because of good thermal stability, nonflammability and rich structural designability, ionic liquids (ILs) have been used as flame retardants for poly(lactic acid) (PLA). However, as a small molecule, IL has the disadvantages of poor thermal stability and water resistance, and so on. In this paper, an imidazole‐type poly(ionic liquid) (PIL) containing a phosphate anion was synthesized using 1‐vinylimidazole, triethyl phosphate, and 1,2‐divinylbenzene and marked as PDVE[DEP]. The PDVE[DEP] was used to improve the flame retardancy of PLA. The flame retardancy and thermal degradation behaviors of PLA/PDVE[DEP] composites were investigated by the limited oxygen index (LOI), UL‐94 vertical burning, cone calorimetry, and thermal gravity analysis, and so on. The results showed that only 1.0 wt% PDVE[DEP] allows PLA to achieve the UL‐94 V0 rating and obtain LOI value 25.6 vol%. The PDVE[DEP] improve the flame retardancy of PLA by melting‐away mode. In addition, it catalyzes the transesterification of PLA and changes the degradation products.     

Preparation of polylactic acid/epoxidized palm oil/fatty nitrogen compounds modified clay nanocomposites by melt blending

In this study, new biopolymer nanocomposites have been prepared. Fatty nitrogen compounds (FNCs); fatty amide (FA), fatty hydroxamic acid (FHA), and carbonyl difatty amide (CDFA), which were synthesized from palm oil, have been 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 distance increases from 1.23 to 2.71, 2.91 and 3.23 nm, respectively. The modified clay was then used in the preparation of the polylactic acid/epoxidized palm oil (PLA/EPO) blend nanocomposites. 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 melt blending of the modified clay and PLA/EPO blend at the weight ratio of 80/20. The nanocomposites were then characterized using XRD, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and tensile properties measurements. The XRD and TEM results confirmed the production of nanocomposites. PLA/EPO modified clay nanocomposites show higher thermal stability and significant improvement of mechanical properties in comparison with those of the PLA/EPO blend.     

Effect of processing method on the structure and properties of HDPE/EAA/LDHs nanocomposites

High-density polyethylene/ethylene–acrylic acid copolymer/layered double hydroxides (LDHs) nanocomposites were prepared by the methods of one-step extrusion and twice extrusion in this paper. The structure and properties of the nanocomposites were also studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermogravimetry (TG), and the cone calorimeter. The results of XRD, SEM, and TEM analyses demonstrated that the method of twice extrusion gave the LDHs a higher level of exfoliation within the matrix compared with the method of one-step extrusion. The DSC and TG analysis revealed that the crystalline property and the thermal stability of the nanocomposites could be improved by the method of secondary extrusion. The cone calorimeter test showed that the method of secondary extrusion could improve the flame retardant property of the nanocomposites to some degree.     

Melt compounding of polylactide/organoclay: Structure and properties of nanocomposites

A Brabender mixer was used to deagglomerate and disperse organomodified montmorillonite Cloisite® 30B (3 wt %) in polylactide (PLA) matrix to obtain nanocomposite systems. The influence of compounding conditions such as blending time (6.5, 10, 20, and 30 min) and compression molding on the nanostructure of nanocomposites was investigated. Molecular weight changes of the PLA matrices induced by melt compounding were determined. Good rheological behavior of the PLA during melt blending with Cloisite® 30B was observed. Prolongation of the blending process improved homogenization of the nanocomposites with the formation of more intercalated and exfoliated structures as revealed by transmission electron microscopy (TEM) and X‐ray analysis. Some orientation of the silicate nanoplatelets induced by compression molding of the nanocomposites was revealed by TEM. It was found that an increase of dispersion degree of the silicate layers modified pronouncedly the physical properties of nanocomposites through an increase of thermal stability as revealed by the thermogravimetric analysis, a decrease of crystallizability of the PLA matrix during melt‐crystallization and upon heating from the glassy, amorphous state. Rheological properties of the nanocomposites determined during dynamic frequency sweep appeared to be very sensitive to the nanostructure evolution. Moreover, the scanning electron microscopy and light microscopy investigations showed the presence of the micron‐size inorganic contaminations in the nanocomposites originating from organoclay Cloisite® 30B. These inclusions were resistive to deagglomeration during melt processing. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3392–3405, 2006     

Multifunctional properties of 3D printed poly(lactic acid)/graphene nanocomposites by fused deposition modeling

In this work, three-dimensional (3D) printing system based on fused deposition modeling (FDM) is used for the fabrication of conductive polymer nanocomposites. This technology consists in the additive multilayer deposition of polymeric nanocomposite based on poly(lactic acid) (PLA) and graphene by means of a in house made low-cost commercial bench-top 3D printer. Further, 3D printed PLA/graphene nanocomposites containing 10 wt% graphene in PLA matrix were characterized for their mechanical, electrical and electromagnetic induction shielding properties of the nanocomposite. Furthermore X-ray computed micro-tomography analyses showed that printed samples have good dimensional accuracy and are significantly closer to the predefined design and the results of scanning electron microscopy (SEM) printed samples showed a uniform dispersion of graphene in PLA matrix The proposed material has uniquely advantageous when implemented in 3D printed structures, because incorporation of multifunctional graphene has been shown to substantially improve the properties of the resulting nanocomposite.     

Polylactide/exfoliated graphite nanocomposites with enhanced thermal stability,mechanical modulus,and electrical conductivity

We have prepared a series of polylactide/exfoliated graphite (PLA/EG) nanocomposites by melt‐compounding and investigated their morphology, structures, thermal stability, mechanical, and electrical properties. For PLA/EG nanocomposites, EG was prepared by the acid treatment and following rapid thermal expansion of micron‐sized crystalline natural graphite (NG), and it was characterized to be composed of disordered graphite nanoplatelets. It was revealed that graphite nanoplatelets of PLA/EG nanocomposites were dispersed homogeneously in the PLA matrix without forming the crystalline aggregates, unlike PLA/NG composites. Thermal degradation temperatures of PLA/EG nanocomposites increased substantially with the increment of EG content up to ～3 wt %, whereas those of PLA/NG composites remained constant regardless of the NG content. For instance, thermal degradation temperature of PLA/EG nanocomposite with only 0.5 wt % EG was improved by ～10 K over PLA homopolymer. Young's moduli of PLA/EG nanocomposites increased noticeably with the increment of EG content up to ～3 wt %, compared with PLA/NG composites. The percolation threshold for electrical conduction of PLA/EG nanocomposites was found to be at 3–5 wt % EG, which is far lower graphite content than that (10–15 wt % NG) of PLA/NG composites. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 850–858, 2010     

Effect of expanded graphite/layered-silicate clay on thermal, mechanical and fire retardant properties of poly(lactic acid)

Preparation of PLA based nanocomposites was carried out by using two different nanofillers: expanded graphite and organically modified montmorillonite. The addition and co-addition of these nanofillers to PLA using the melt-blending technique provides nanocomposites that showed significant enhancements in rigidity, thermal stability and fire retardancy of the polymer matrix. The presence of dispersed graphite nanolayers in PLA significantly accelerated the polyester crystallization, whereas the essential increase of thermal resistance is mainly connected to the addition of organoclay. The structure of the nanocomposites was examined by Wide Angle X-ray Scattering Analysis and Transmission Electron Microscopy. The improvement of thermal and mechanical properties obtained by the presence of both nanoparticles in PLA were associated to the good (co)dispersion and to the co-reinforcement effect, whilst the fire retardant properties were found to be related to the combined additive action of both nanofillers.     

Effect of graphene nanoplatelets as nanofiller in plasticized poly(lactic acid) nanocomposites

Plasticized PLA-based nanocomposites were prepared by melt blending of the matrix with 5 mass% of epoxidized palm oils (EPO) and different amount of graphene nanoplatelets (xGnP). Plasticized PLA (p-PLA) reinforced with 0.3 mass% 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. Thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) were performed to study the thermal behavior of the prepared nanocomposites. p-PLA reinforced with xGnP shows that increasing the xGnP content triggers a substantial increase in thermal stability. Crystallinity of the nanocomposites as well as cold crystallization and melting temperature did not show any significant changes upon addition of xGnP. However, there is a significant decrease of glass transition temperature up to 0.3 mass% of xGnP incorporation.     

Melt‐blending of unmodified and modified cellulose nanocrystals with reduced graphene oxide into PLA matrix for biomedical application

In this article, we successfully fabricated the bionanocomposites using cellulose nanocrystals (CNCs) and reduced graphene oxide (rGO) reinforced into biodegradable polylactic acid (PLA) matrix through melt‐mixing method. Due to the affinity difference between hydrophilic CNC and hydrophobic PLA, the surface modification of CNC was employed using quaternary ammonium salts (CTAB) as a surfactant. The nanocomposites were developed using different blend ratios of CNC/modified CNC (1, 2, and 3) wt% and (0.5 wt%) rGO into the polymer matrix. The morphology of CNC, q‐CNC (modified CNC), and nanocomposites were inspected by atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM). It is demonstrated from tensile tests that, the nanocomposite with 1 wt% CNC and rGO showed maximum tensile strength compared with PLA and its nanocomposites. Moreover, the nanocomposite with 1 wt% CNC and rGO was also having maximum thermal stability. From cytotoxicity evaluation, it is observed that all the nanocomposites are nontoxic and cytocompatible to HEK293 cells. In addition to this, the nanocomposite with q‐CNC showed enhanced barrier properties compared with PLA and PLA/CNC/rGO nanocomposite. The results obtained from different characterizations showed that the incorporation of surfactant onto CNC improved the dispersion in PLA but at the same time deteriorated the PLA matrix.     

Thermal properties of poly(lactic acid)/organo-montmorillonite nanocomposites

Poly(lactic acid)/organo-montmorillonite nanocomposites were prepared by melt intercalation technique. Maleic anhydride-grafted ethylene propylene rubber (EPMgMA) was added into the PLA/OMMT in order to improve the compatibility and toughness of the nanocomposites. The samples were prepared by single screw extrusion followed by compression molding. The effect of OMMT and EPMgMA on the thermal properties of PLA was studied. The thermal properties of the PLA/OMMT nanocomposites have been investigated by using differential scanning calorimeter (DSC) and thermo-gravimetry analyzer (TG). The melting temperature (T _m), glass transition temperature (T _g), crystallization temperature (T _c), degree of crystallinity (χ_c), and thermal stability of the PLA/OMMT nanocomposites have been studied. It was found that the thermal properties of PLA were greatly influenced by the addition of OMMT and EPMgMA.