Kinetic patterns for thermal oxidation of binary and ternary blends based on polylactide and polyethylene

Russian Chemical Bulletin - The effect of introduced aged low density polyethylene (LDPE-A) on structure and properties of mixed blends based on polylactide (PLA) and low density polyethylene...     

Structural-phase state and surface properties of composite materials based on polylactide and hydroxyapatite

The phase composition and unit cell parameters were determined for composites based on polylactide and hydroxyapatite with the polylactide/hydroxyapatite weight ratios of 90/10, 80/20, 70/30, and 60/40. As the polylactide content of the composites is increased, they become less hydrophilic, and the surface energy σ_S-G increases from 29.13 to 74.35 mJ m^–2. The sample with the component weight ratio of 70/30 is characterized by the maximal roughness, and the Ca²⁺ and Mg²⁺ ions from simulated body fluid are actively adsorbed onto its surface, as proved by SEM examination of the composites.     

Novel pentablock copolymer (PLA–PCL–PEG–PCL–PLA)-based nanoparticles for controlled drug delivery: effect of copolymer compositions on the crystallinity of copolymers and in vitro drug release profile from nanoparticles

The purpose of this investigation was to design novel pentablock copolymers (polylactide–polycaprolactone–polyethylene glycol–polycaprolactone–polylactide) (PLA–PCL–PEG–PCL–PLA) to prepare nanoparticle formulations which provide continuous delivery of steroids over a longer duration with minimal burst effect. Another purpose was to evaluate the effect of poly(l-lactide) (PLLA) and poly(d,l-lactide) (PDLLA) incorporation on crystallinity of pentablock copolymers and in vitro release profile of triamcinolone acetonide (selected as model drug) from nanoparticles. PLA–PCL–PEG–PCL–PLA copolymers with different block ratio of PCL/PLA segment were synthesized. Release of triamcinolone acetonide from nanoparticles was significantly affected by crystallinity of the copolymers. Burst release of triamcinolone acetonide from nanoparticles was significantly minimized with incorporation of proper ratio of PDLLA in the existing triblock (PCL–PEG–PCL) copolymer. Moreover, pentablock copolymer-based nanoparticles exhibited continuous release of triamcinolone acetonide. Pentablock copolymer-based nanoparticles can be utilized to achieve continuous near–zero-order delivery of corticosteroids from nanoparticles without any burst effect.     

Composite Materials Based on Polylactide and Poly-3-hydroxybutyrate “Green” Polymers

Blends of polylactide with low-density polyethylene and of poly-3-hydroxybutyrate with synthetic ethylene–propylene rubber with the component weight ratios of 30 : 70, 50 : 50, and 70 : 30 were prepared and studied in comparison with the pure components. The thermal characteristics of these blends were determined by differential scanning calorimetry. The melting point of polyhydroxybutyrate and polylactide in the blends changes insignificantly, by 1–2°C. The dependence of the morphology on the composition for both polymer systems was examined by scanning electron microscopy. The physicomechanical properties of the samples are determined by the major phase. The blends undergo biodegradation in soil at 20 ± 3°С. The process occurs faster for blends of polyhydroxybutyrate with ethylene–propylene rubber of all the compositions studied.     

Starch–polyethylene polymer–polymer composites obtained by polymerization filling: Structure and oxidative degradability

The polymer–polymer composites bearing polyethylene and starch are obtained by polymerization filling. The polymerization of ethylene is carried out using catalyst system [TiCl₄ + (С₂H₅)₂AlCl] under mild conditions. It is found that the catalyst activity in the presence of a biopolymer is higher than that without the filler. The polyethylene matrix has a molecular mass of 1.26–1.40 M and features a melting point of 138–140°C, a high enthalpy, and a degree of crystallinity of 60–70%. Reduction in the decomposition temperature of the polymer–polymer composites and in the rate of mass loss compared to the unfilled polyethylene and biopolymers is detected. The stress-strain characteristics of the polymer matrix are improved; in particular, the elastic modulus and relative elongation at break are increased. The photooxidative degradation of the composites under the action of sunlight and UV radiation is studied. According to the data of IR spectroscopy, the polymer–polymer composites possess resistance to photooxidative aging 2–3 times lower than the unfilled polyethylene. The polymer–polymer composites subjected to UV radiation reveal a high intensity of growth of microorganisms: the degree of biofouling is up to four points.     

Polymer‐nanofiber composites: Enhancing composite properties by nanofiber oxidation

Nanocomposites of styrene and vinyl phenol copolymers, which contain varying (10, 20, and 40 mol %) vinyl phenol content, were prepared with 1 wt % unoxidized, 1 wt % oxidized, and 5 wt % oxidized carbon nanofibers. Dynamic mechanical analysis and differential scanning calorimetry indicate that the composites prepared from oxidized nanofibers exhibit improved thermal and structural properties relative to those prepared from unoxidized nanofibers. The optimum enhancement in the mechanical and thermal properties was observed for the composite containing oxidized nanofibers and the 20% vinyl phenol copolymer. These results are in excellent agreement with our previous work on carbon nanotube–polymer composites and suggest that the presence of intermolecular interactions between the copolymer matrix and nanofibers are responsible for the observed property enhancement. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3053–3061, 2006     

Structure of composites prepared via polypyrrole synthesis in supercritical CO2 on microporous polyethylene

The synthesis of polypyrrole in supercritical carbon dioxide in the presence of the microporous polyethylene has been studied. Formation of polymer composites based on polypyrrole and polyethylene has been demonstrated. The structure of the test samples has been investigated by vibrational spectroscopy, SAXS, and atomic force and scanning electron microscopy. It has been discovered that the oxidized structure of polypyrrole forms during the synthesis under supercritical conditions.     

Pyrolysis-GC-MS reveals important differences in hydrolytic degradation process of wood flour and rice bran filled polylactide composites

Pyrolysis-GC-MS of polylactide (PLA) biocomposites before and after hydrolytic degradation revealed prominent differences in the hydrolytic degradation process of rice bran and wood flour filled biocomposites. The water uptake and mass loss for polylactide/wood flour composites were similar to that of plain PLA. Pyrolysis-GC-MS, however, showed that on prolonged ageing the hydrolysis of PLA led to increased wood flour concentration in the remaining biocomposite matrices. In contrast, the polylactide/rice bran composites exhibited larger water uptake and higher mass loss. Pyrolysis-GC-MS and FTIR analysis proved that the higher mass loss was caused by migration of rice bran from the composites. The type of natural filler could thus greatly influence the degradation process and/or the stability of the materials in aqueous or humid environments.     

Functional Composites Based on Polylactide and Graphene

New composite materials based on polylactide and graphene, suitable for creating three-dimensional objects using the 3D printing technology, were prepared. Introduction of the nanoadditive into the matrix of the biodegradable polymer enhances the tensile strength of the materials by more than 57%. In addition, the composites exhibit high electrical conductivity, reaching 0.9 S cm^–1 for the composite with 3 wt % filler, which determines the possibility of using them for the development of various electrotechnical devices and tissue engineering structures.     

Thermomechanical and crystallization behavior of polylactide-based flax fiber biocomposites

In this work, the rheological, thermal and mechanical properties of melt-compounded flax fiber-reinforced polylactide composites were investigated. The effect of compounding on fiber length and diameter, and the relationship between fiber content and the crystallization behavior of the biocomposites, at various temperatures, were also examined. After melt-compounding, fiber bundles initially present were, to a large extent, broken into individual fibers and the fiber length was decreased by 75 %, while the aspect ratio was decreased by nearly 50 %. The crystallization half-time was found to decrease with increasing flax fiber content, and showed a minimum value at 105 °C for all systems. The elastic modulus was increased by 50 % in the presence of 20 wt% flax fibers. The addition of maleic anhydride-grafted polylactide had a positive effect on the mechanical properties of the biocomposite. This system is particularly interesting in the context of sustainable development as it is entirely based on renewable resources and biodegradable.     

电纺丝法制备聚乳酸/多壁碳纳米管/羟基磷灰石杂化纳米纤维的研究

电纺丝是一种利用聚合物溶液或熔体在强电场中进行喷射纺丝的加工技术,所制得的纤维、直径一般在数十纳米至几微米之间,比传统方法制得的纤维直径小几个数量级,是获得纳米尺寸长纤维的有效方法之一．     

Effect of conductive particles on the mechanical,electrical, and thermal properties of maleated polyethylene

Inclusion of conductive particles is a convenient way for the enhancement of electrical and thermal conductivities of polymers. However, improvement of the mechanical properties of such composites has remained a challenge. In this work, maleated polyethylene is proposed as a novel matrix for the production of conductive metal–thermoplastic composites with enhanced mechanical properties. The effects of two conductive particles (iron and aluminum) on the morphological, mechanical, electrical, and thermal properties of maleated polyethylene were investigated. Morphological observations revealed that the matrix had excellent adhesion with both metal particles. Increase in particle concentration was shown to improve the tensile strength and modulus of the matrix significantly with iron being slightly more effective. Through‐plane electrical conductivity of maleated polyethylene was also substantially improved after adding iron particles, while percolation was observed at particle contents of around 20–30% vol. In the case of aluminum, no percolation was observed for particle contents of up to 50% vol., which was linked to the orientation of the particles in the in‐plane direction due to the squeezing flow. Inclusion of particles led to substantial increase (over 700%) in the thermal conductivities of both composites. The addition of high concentrations of metal particles to matrix led to the creation of two groups of materials: (i) composites with high electrical and thermal conductivities and (ii) composites with low electrical and high thermal conductivities. Such characteristics of the composites are expected to provide a unique opportunity for applications where a thermally conductive/electrically insulating material is desired. Copyright © 2015 John Wiley & Sons, Ltd.     

Volume‐exclusion effects in polyethylene blends filled with carbon black,graphite, or carbon fiber

Conductive polymer composites possessing a low percolation‐threshold concentration as a result of double percolation of a conductive filler and its host phase in an immiscible polymer blend afford a desirable alternative to conventional composites. In this work, blends of high‐density polyethylene (HDPE) and ultrahigh molecular weight polyethylene (UHMWPE) were used to produce ternary composites containing either carbon black (CB), graphite (G), or carbon fiber (CF). Blend composition had a synergistic effect on electrical conductivity, with pronounced conductivity maxima observed at about 70–80 wt % UHMWPE in the CB and G composites. A much broader maximum occurred at about 25 wt % UHMWPE in composites prepared with CF. Optical and electron microscopies were used to ascertain the extent to which the polymers, and hence filler particles, are segregated. Differential scanning calorimetry of the composites confirmed that the constituent polymers are indistinguishable in terms of their thermal signatures and virtually unaffected by the presence of any of the fillers examined here. Dynamic mechanical analysis revealed that CF imparts the greatest stiffness and thermal stability to the composites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1013–1023, 2002     

Plasticized polylactide/clay nanocomposites. II. The effect of aging on structure and properties in relation to the filler content and the nature of its organo‐modification

Plasticized polylactide (PLA) – layered silicate nanocomposites were obtained by melt blending PLA with polyethylene glycol as plasticizer (20 wt %) and with different montmorillonite fillers: Cloisite® 20A, Cloisite® 25A, and Cloisite® 30B (from 1 to 10 wt %). Comparative samples of melt‐blended polylactide (without filler) and plasticized PLA with 20 wt % PEG were considered as well. Samples have been aged for 1 and 4 years and their chemical and physical characteristics were compared with not aged reference ones. It was found that molecular weight of the PLA decreased upon melt‐processing and aging, particularly when the Cloisite content increased, without a clear relation to the nature of the organo‐modifier. On the contrary, the PEG plasticizer was practically undegraded upon melt processing and aging. Structural studies revealed that plasticized PLA and plasticized PLA‐based nanocomposites are unstable in time of aging and undergo deplasticization. They showed, after aging, the presence of a thin PEG crystalline layer at the surface of the samples and improved the order in the PLA matrix to a higher extent in plasticized polylactide than in plasticized nanocomposite (due to clay stabilization effect). The amount of PEG diffusing toward sample surface was correlated with aging time, molecular weight of PLA matrix, and Cloisite® type, in clear relation to the extent of intercalation with PLA and PEG. Some modifications of the viscoelastic properties of PLA matrix, induced by the presence of both the nanoparticlate filler and the plasticizer, as well as a deterioration of the mechanical properties upon aging were observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 312–325, 2006     

Effect of temperature on the molecular mobility in polylactide

The effects of temperature on the molecular mobility in the amorphous phase and on the structural parameters of the crystalline phase of three brands of polylactide have been studied. It was found that annealing increases the melting temperature by 2–3°C and increases the degree of crystallinity by 2–6%. X-Ray analysis showed the possibility of formation of crystal structures of the α and β modifications in polylactide. The change in correlation time of radical rotation in amorphous regions of polylactide as a function of the history of thermal pretreatment of the samples was shown via the electron paramagnetic resonance method.     

PE-CPE blends and their graphene oxide nanocomposites with reduced low temperature brittleness

The low-temperature flexibility of polyethylene (PE)–chlorinated polyethylene (CPE) blends and their composites with a small amount of graphene oxide filler was studied. Quantitative height variation in the AFM images, rheological as well as fracture analyses were employed to gain insights into the generation of flexibility in the matrix phase. The semi-crystalline CPE (CPE25) polymer did not induce viscoelastic behavior at temperatures lower than the glass transition temperature of PE, whereas the amorphous CPE (CPE35) had completely different behavior. The samples with CPE35 could not be sufficiently hardened even at ?180 °C and remained too soft for cryosectioning. Therefore, compression, which results in a 30–60 % reduction in length along the cutting direction with no change in the dimension perpendicular to it, was very prominent for both thin section and block face of the sample. The composites had even higher degree of compression due to additional effect of weak filler matrix interactions and as a consequence, the topographical variations led to filler pull out during sectioning. It was also confirmed using the rheological analysis that composites (and blends with 10 % CPE35 content) had phase immiscibility as CPE phase was suspected to concentrate near the graphene oxide phase leading to generation of chlorine-rich phases. The addition of graphene oxide did not lead to reduced flexibility and the composites also retained the modulus similar to pure polymer. The mechanical fracture of the samples also confirmed the flexibility of the CPE containing blends and composites as these samples were still flexible at ?195 °C.     

The possibility of applying a titanium-magnesium nanocatalyst in the polymerization filling of polyolefins and some properties of the obtained composites

The possibility of applying a titanium-magnesium nanocatalyst during in situ polymerization of ethylene and propylene in the presence of organomodified aluminum silicates and diatomite under mild conditions is investigated. How the substantial (2- to 3-fold) increase in the catalytic activity of the system depends on the type and amount of filler is shown. The activity of the titanium-magnesium nanocatalyst-filler system during polymerization of propylene is 3–4 times higher than that during the polymerization of ethylene. Composites based on ultrahigh-molecular-mass polyethylene (M = (1.4–1.7) × 10⁶) with 3.5–13.0 wt % filler are obtained. According to DSC and X-ray structural-analysis data, the polyethylene matrix differs by its high crystallinity and a T _m of 143–144°C. The physicochemical characteristics of the composites are 1.5–2.0 times greater than those of unfilled polyethylene; the nanocomposite containing 11 wt % mont-morillonite modified with vinyltrimethoxysilane has the best properties. It is shown that during the propylene polymerization, the effect of the type of filler affects not only the catalytic activity of the system, increasing it three times in the case of diatomite, but also the stereospecificity of the effect. Isotactic high-molecularmass (up to 390 × 10³) polypropylene is obtained in the presence of montmorillonite containing vinyltrimethoxysilane, while a low-molecular-mass ((65–75) × 10³) polymer with lower isotacticity is formed on diatomite. The deformation-strength characteristics of composites based on polypropylene testify the formation of an elastomeric material with T _m = 156–158°C.     

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

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

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     

一类新型PTC复合材料的制备及性能

一类新型ＰＴＣ复合材料的制备及性能杜伟坊,杜海清（湖南大学材料科学及应用化学研究所,长沙,４１００８２）关键词正温度系数,聚乙烯,ＹＢａ_２Ｃｕ_３Ｏ_（７－ｘ）具有正温度系数（ＰＴＣ）的材料在其转化温度附近具有电阻率大幅度上升的特点,因而在温度检测与?..