Dielectric and Mechanical Relaxational Behavior of Poly (Chlorobenzyl Methacrylate)s

Dielectric relaxational behavior of poly(monochlorobenzyl methacrylate)s (PMClBM) and poly(dichlorobenzyl methacrylate)s (PDClBM) has been analyzed. The study was carried out by determining the components of the complex dielectric permittivity *. Two relaxation processes, labelled as α and β relaxations, which were analyzed in terms of the Havriliak-Negami and Cole-Cole equations, respectively, have been experimentally observed. The relative position of the chlorine substitute in the benzyl ring determines the characteristic parameters of the relaxations. Complementary dynamic mechanical measurements on these polymers have been carried out. The relationship between the macroscopic measurements with the dipolar moment of the relaxing entities has been analyzed in terms of the Onsager-Kirkwood-Fröhlich equation.     

Correlation Between Crystallization Behavior and Mechanical Properties of Biodegradable Poly(Caprolactone-co-Cyclohexene Carbonate)

The isothermal and nonisothermal crystallization behaviors of poly(ε-caprolactone) and poly(caprolactone-co-cyclohexene carbonate) were investigated utilizing differential scanning calorimeter and polarized optical microscope. The kinetic of isothermal crystallization could be well defined by Avrami equation, while Mo model was successful to describe the nonisothermal crystallization. Based on the obtained kinetic parameters, poly(cyclohexene carbonate) segments not only act as a nucleating agent accelerating nucleating rate but also restrict the transport of poly(ε-caprolactone) segments decelerating growth rate. The mechanical properties of polymers were investigated using DMA and nanoindentation. It shows that the insertion of hard poly(cyclohexene carbonate) segments improves Young’s modulus and heat resistance but reduces hardness of copolymers.     

聚乙烯醇/膨润土杂化水凝胶的力学性能和溶胀行为

利用冷冻-解冻法制备了聚乙烯醇/膨润土杂化水凝胶. X射线衍射结果表明,膨润土以剥离形式分布在水凝胶基体中. 研究结果表明,与纯PVA5水凝胶相比,经过5个冷冻-解冻循环制备的含2%(w)膨润土的杂化水凝胶的拉伸模量、拉伸强度和断裂伸长率分别增加了44.0%, 74.2%和25.2%,而溶胀行为与5个循环的纯水凝胶相近. 含0.5%(w)膨润土的杂化水凝胶的拉伸模量和拉伸强度高于基体水凝胶,其在溶胀400 min时的溶胀度高于所有的样品.     

Poly(imide-siloxane) films with controlled thickness

Polyimides containing siloxane moieties are used in some advanced applications. For example, these polymers can be employed as separation membranes in the form of self-standing, thin films. These products are formed by components of different polarities that have the tendency, at least partly, to separate in the final materials, with an impact on their final, bulk, and/or surface properties. The aim of this work is to study the dependence of the composition of the polyimide, poly(imide-siloxane) (PIS) and copolymeric PIS self-standing films differing in thickness on their properties. The important finding is that there is a rather large difference observed in the water contact angle on the film side oriented toward the air atmosphere during film preparation and that oriented toward a hydrophobic Teflon surface. Nevertheless, the gas transport properties of carbon dioxide and methane for these membranes are more influenced by the membrane composition than by the surface properties.     

Poly(methyl methacrylate)–epoxy vitrimer composites

In this study, we synthesized poly(methyl methacrylate) (PMMA) epoxy vitrimer composites by doping methyl methacrylate (MMA) and benzoyl peroxide into a curing system of epoxy resin and citric acid. The vitrimer composites were characterized with dynamic mechanical thermal analysis, scanning electron microscopy, and stress‐relaxation and lap‐shear testing. The test results show that with increasing amount of MMA, the existence of PMMA in the epoxy vitrimer matrix in the form of intermiscible, slightly soluble, and phase separation became more evident. When the doping amount of PMMA reached 10–25 wt %, the bonding strength of the PMMA–epoxy vitrimer composites was about two times that of the epoxy vitrimer (from 2.3 to 4.3 MPa). This showed that the self‐healing strength of the vitrimer composites was better than that of the pure vitrimer. When the PMMA in the epoxy matrix was in a slightly soluble form, the linear PMMA improved the mechanical properties of the epoxy vitrimer by physical winding. At the same time, the doping of PMMA promoted the transesterification rate of the epoxy vitrimer and enhanced the bonding strength of the composites without lowering the epoxy vitrimer glass‐transition temperature. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46307.     

Preparation of Poly(ethylene terephthalate)/Poly(amino ether) Blends by means of the Addition of Poly(butylene terephthalate)

Summary: Blends based on poly(ethylene terephthalate), PET, with poly(amino ether) (PAE) contents up to 40% were obtained by the addition of 20% poly(butylene terephthalate) (PBT) to the PET matrix. PBT mixed with PET led to a decrease in the T_m of the matrix that was enough to produce homogeneous blends by mixing in the melt state. Despite the presence of a single peak observed by dynamic‐mechanical analysis, the blends were biphasic, with amorphous phases in which minor amounts of the other component, both reacted and mixed, were present. This presence of minor components gave a fine morphology and significant adhesion that, together with the higher orientation of PAE in the blends, produced blends with a clear synergism in the modulus of elasticity, notched impact strength similar to that of the neat components, and high ductility up to 30% PAE.

Young's modulus of the PET‐PBT/PAE blends.     

Properties and Phase Structure of the Poly(propylene)-Low-Density Poly(ethylene) Blends

Abstract

The phase structures of PP-LDPE blends in isotropic and oriented states were studied by the methods of DSC and polarization IR spectroscopy. The composition intervals were established that correspond to the formation of interpenetrating network structures. The presence of LDPE increases the degree of PP orientation and the mechanical strength of the blends. This indicates that LDPE acts as a structure-modifying agent, while PP plays the role of strengthening (reinforcing) filler. A relationship between the deformation and strength properties of the oriented films of the PP-LDPE blend and the phase structure of the PP component is demonstrated. The stability of the blend to oxidation in the ozone-oxygen medium is determined by the structure of a less stable system component (PP). The oxidation rate reaches maximum in samples with an isotropic PP structure and is minimum in the blends with highly oriented PP component.     

Effect of Nucleating Agents on Crystallization and Melting Behavior and Mechanical Properties of Nucleated Syndiotactic Poly(propylene)

Summary: The effects of various nucleating agents [e.g. 1,3:2,4‐dibenzylidene sorbitol (DBS), 1,3:2,4‐di‐p‐methyldibenzilidene sorbitol (MDBS), 1,3:2,4‐di‐m,p‐methylbenzylidene sorbitol (DMDBS), kaolin, talcum, marl, titanium dioxide (TiO₂) and silica (SiO₂)] on non‐isothermal melt crystallization and the subsequent melting behavior and mechanical properties of nucleated syndiotactic poly(propylene) (sPP) in comparison with those of the neat sample were investigated. Analysis of the non‐isothermal melt‐crystallization exotherms revealed that the ability of these fillers to nucleate sPP could be ranked from the best to the worst as follows: DBS > talcum > MDBS > kaolin > SiO₂ > DMDBS > marl > TiO₂. The subsequent melting endotherms for most of the sPP compounds exhibited double melting peaks, while that for the marl‐filled sPP exhibited triple melting peaks. Wide‐angle X‐ray diffraction analysis showed that addition of these fillers did not affect the crystal modification of the sPP matrix. Mechanical property measurements revealed that both the tensile strength and the percentage of elongation at yield for the sPP compounds investigated were not much different from those of the neat sPP. After natural weathering for 1 month, the tensile strength at yield for the sPP compounds investigated increased, at the expense of the percentage of elongation at yield, but, after natural weathering for 3 months, both the tensile strength and the percentage of elongation at yield were found to decrease.

Effects of various organic and inorganic nucleating agents on non‐isothermal melt‐crystallization of syndiotactic poly(propylene) (recorded at a cooling rate of 10 °C · min^?1).     

Effect of Carbon‐Based Particles on the Mechanical Behavior of Isotactic Poly(propylene)s

Different carbon‐based fillers such as carbon nanotubes (CNTs), graphite, and thermally reduced graphene oxide (TrGO) are melt mixed with an isotactic poly(propylene) (iPP) and the mechanical properties of the resulting composites in the solid and melt state are analyzed. The Young's modulus of composites is increased around 25% relative to the neat iPP at concentrations above 10 wt% of CNTs or graphite whereas composites with TrGO are increased around 40% at similar concentrations. These results are compared with theoretical models showing that the filler agglomeration and surface area are key parameters. The rheological results of the composites under oscillatory shear conditions at the melt state show that the viscous raw polymer melt experiences a solid‐like transition at a threshold concentration that strongly depends on the filler used. This transition appears at 10 wt% for CNTs, 8 wt% for TrGO, and 40 wt% for graphite. The viscosity of iPP/TrGO composites is further increased by adding CNTs particles, although the Young's modulus does not increase.

     

Poly(lactic acid)-based biocomposites reinforced with kenaf fibers

Biodegradable thermoplastic-based composites reinforced with kenaf fibers were prepared and characterized. Poly(lactic acid) (PLA) was selected as polymeric matrix. To improve PLA/fibers adhesion, low amount of a proper reactive coupling agent, obtained by grafting maleic anhydride onto PLA, was added during matrix/fibers melt mixing. Compared with uncompatibilized composites, this compatibilization strategy induces a strong interfacial adhesion and a pronounced improvement of the mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

New Miscible Poly(ether imide)/Poly(phenyl sulfone) Blends

Summary: Blends of PEI and PPSU were prepared directly during the plasticization step of an injection molding process throughout the full composition range. The molded blends were transparent and showed a single glass transition and no dispersed phase by SEM. These characteristics did not allow the presence of a single miscibilized phase to be inferred unambiguously due to the very similar T_gs and refractive indices of the two components of the blends. Miscibility was inferred after close observation of the position, height and area of the enthalpy relaxation peak of the 50/50 blend. The modulus of elasticity and yield stress changed linearly with composition, leading to polymer materials with intermediate characteristics. The linearity was attributed to the lack of decrease in free volume induced by mixing and to the similar orientation of the components before and after mixing. The PPSU presence only slightly reduced the known tendency towards brittle fracture of PEI under notched impact conditions, but the presence of a single amorphous phase led to an expected ductile behavior of the blends close to that predicted by the single rule of mixtures.

Break stress (?) and break strain (○) of PEI/PPSU blends as a function of composition.     

Structure and Mechanical Properties of Composites of Poly(6‐hexanelactam) Combining Solid Tribological Additives and Reinforcing Components

Summary: Three types of composites of polyamide 6 (PCL) with hybrid tribological additives were synthesized via anionic adiabatic “in situ” polymerization of 6‐hexanelactam (ε‐caprolactam) initiated with metallic sodium and activated with either cyclic trimer of phenyl isocyanate or diphenylmethane 4,4′‐diisocyanate. Combinations of the additives and their maximum applied concentrations (in wt.‐%) were the following: MoS₂/graphite(G)/oil(O) (5/16/9), short carbon fibers (CF)/G/O (5/20/10), and copper phthalocyanine (CPC) (7). Dynamic mechanical thermal analysis (DMTA) indicates a secondary (β) transition at about ?65 °C and the main (α) transition at temperatures close to 20 °C; the storage modulus passes through a shallow maximum as a function of the total content of additives. Tensile creep and indentation creep concurrently evidenced some increase in compliance with rising fraction of incorporated compounds. Stress‐strain tests in flexure show that flexural strength and toughness monotonically decreased with the content of MoS₂/G/O or CF/G/O, whereas the flexural modulus passed through a flat maximum. On the other hand, the strength and modulus were decreasing with CPC content, while toughness and Charpy impact tests showed some improvement.

Flexural toughness a_fU as a function of filler content C_ad in adiabatic anionic polymerization of 6‐hexanelactam.     

Poly(dimethylsiloxane)‐toughened syntactic foams

The potential of preformed elastomers as a toughening agent for epoxy–glass syntactic foam has been explored. Poly(dimethylsiloxane) microspheres were prepared by suspension polymerization. The microsphere dimensions could be varied from 58 to 255 µm by tuning the reaction parameters, particularly the stirring speed and feed concentration. Rheological studies indicated that the introduction of microballoons led to an increase in the viscosity of the resin, with the extent being proportional to the microballoon content. The zero shear viscosity increased from ～10³ mPa s at 30 °C to 10⁵ mPa s as the microballoon loading was increased to 40%. Syntactic foams containing varying amounts of microballoons (40–60% v/v) were prepared, and an analogous set of toughened foams were also prepared, where a fraction of the microballoons was replaced with poly(dimethylsiloxane) microspheres (3–7%). The effect of increasing dimensions of the elastomeric microspheres on the mechanical properties was also studied. The improvement in properties was more pronounced when the microsphere size was equivalent to that of the constituent microballoons. An improvement of 40% and 185% in flexural strength and flexural toughness was observed upon the introduction of poly(dimethylsiloxane) microspheres of optimal dimensions (diameter ～63 µm, 5% loading), without any undesirable increase in foam density. However, the compressive properties remained practically unaltered. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45882.     

对生物降解聚合物PBS共聚改性的研究

采用不同官能团如苯二甲酸(TA)、聚乙二醇(PEG,Mn=1000)对聚丁二酸丁二醇酯(PBS)主链进行共聚改性,得到了基于PBS的均聚共聚物PBST;嵌段共聚物PBES。利用1H-NMR、GPC、WXRD、热分析、拉力试验对共聚物的化学结构、相对分子质量、结晶性、热性能及力学性质的影响进行了研究。结果表明:将TA、PEG引入PBS的主链,在较短时间内得到了数均分子质量约5万的无规PBST和嵌段PBES共聚物;PEG的介入使聚合物的结晶度降低、断裂伸长率大幅度增加,最大达846.4%;TA的介入则使其结晶度增加,断裂伸长率呈逐渐减小的趋势,但仍比PBS有所增大;两种聚合物均有良好的热稳定性。     

Mechanical Behavior and Fracture Toughness of Poly(L‐lactic acid)‐Natural Fiber Composites Modified with Hyperbranched Polymers

Summary: The use of hyperbranched polymers (HBP) with hydroxy functionality as modifiers for poly(L ‐lactic acid) (PLLA)‐flax fiber composites is presented. HBP concentrations were varied from 0 to 50% v/v and the static and dynamic tensile properties were investigated along with interlaminar fracture toughness. Upon addition of HBP, the tensile modulus and dynamic storage modulus (E′) both diminished, although a greater decline was noticed in the static modulus. The elongation of the composites with HBP showed a pronounced increase as large as 314% at 50% v/v HBP. The loss factor (tan δ) indicated a lowering of the glass transition temperature (T_g) due to a change in crystal morphology from large, mixed perfection spherulites to finer, smaller spherulites. The change in T_g could have also resulted from some of the HBP being miscible in the amorphous phase, which caused a plasticizing effect of the PLLA. The interlaminar fracture toughness measured as the critical strain energy release rate (G_IC) was significantly influenced by HBP. At 10% v/v HBP, G_IC was at least double that of the unmodified composite and a rise as great as 250% was achieved with 50% v/v. The main factor contributing to high fracture toughness in this study was better wetting of the fibers by the matrix when the HBP was present. With improved ductility of the matrix, it caused ductile tearing along the fiber‐matrix interface during crack propagation.

ESEM photograph of propagation region of the interlaminar fracture toughness specimens with 30% v/v of HBP.     

Chemically Functionalized Graphene Nanosheets and Their Influence on Thermal Stability,Mechanical, Morphological,and Electrical Properties of Poly(methyl methacrylate)/Poly(ethylene Oxide) Blend

Poly(methyl methacrylate)/poly(ethylene oxide) (90/10) blend containing various contents of functionalized graphene was prepared through solution technique and characterized to investigate the effects of functionalized graphene content on mechanical, thermal, and electrical properties of the nanocomposites. Infrared results revealed the interaction between matrix and functionalized graphene. Electron microscopy images of the nanocomposites exhibited a good dispersion of functionalized graphene nanosheets in the blend. The incorporation of functionalized graphene significantly increased the thermal stability and mechanical properties of poly(methyl methacrylate)/poly(ethylene oxide) blend. At electrical percolation threshold achieved at functionalized graphene loading of 4.27?wt%, the conductivity of the nanocomposites was increased by more than eight orders of magnitude.     

Nanofibrillar Single Polymer Composites of Poly(ethylene terephthalate)

Using the experience gained from the development of polymer–polymer nanofibrillar composites (NFCs), an attempt was undertaken to manufacture PET single polymer nanofibrillar composites. For this purpose polypropylene (PP) was removed by selective extraction from a knitted textile manufactured with PP/PET (80:20 by wt) blend. The remaining PET nanofibrillar textile was then sandwiched between lower‐melting PET films and compression molded at 120 °C. The obtained PET single polymer NFCs comprised PET nanofibrils as reinforcement and showed an improvement in the tensile strength and modulus of 37–100 and 40–140%, respectively (depending on the annealing temperature after compression molding and the test direction) compared to those of the starting isotropic matrix film.

     

Poly(butylene terephthalate)/poly(ethylene glycol) blends with compatibilizers

Polymer blend systems offer a versatile approach for tailoring the properties of polymer materials for specific applications. In this study, we investigated the compatibility of polybutylene terephthalate (PBT) and poly(ethylene glycol) (PEG) blends processed using a twin-screw extruder, with the aim of enhancing their compatibility. Phthalic anhydride (PAn) and phthalic acid (PAc) were used as potential compatibilizers at different concentrations to improve interfacial interactions between PBT and PEG. Blend morphologies were characterized using scanning electron microscopy, which revealed improved interfacial compatibility and reduced phase separation with the incorporation of small amounts of PAn and PAc. Differential scanning calorimetry analysis indicated changes in the melting temperature (T_m) and glass transition temperature (T_g) of the blends owing to the compatibilizing effects of PAn and PAc. Dynamic mechanical analysis further corroborated the influence of the compatibilizers on the T_g and viscoelastic behavior. Thermogravimetric analysis demonstrated enhanced thermal stability with the addition of either PAn or PAc. Rheological measurements indicated an increase in complex viscosity with increasing compatibilizer content, indicating improved compatibility. The degradation point (T_d) of PBT/PEG blend increased from 158 to 200 and 319°C with the incorporation of 5 phr PAn and 2 phr PAc, respectively. Mechanical properties, including tensile strength, Young's modulus, and Izod impact strength, were evaluated. For instance, the tensile strength of PBT/PEG blend was enhanced from 43.5 to 48.7 and 49.7 MPa by incorporating 5 phr PAn and 2 phr PAc, respectively. However, the impact strength of PBT/PEG blend increased from 3.0 to 4.3 and 4.2 kJ/m² with the addition of 1 phr PAn and 1 phr PAc, respectively. The findings demonstrated that adding 5 phr PAn or 2 phr PAc to the PBT/PEG blends was advantageous, achieving a harmony of performance benefits and compromises. Rheological observations contributed significantly to the mechanical and thermal properties. Overall, the study highlights the significance of utilizing PAn and PAc as effective compatibilizers for enhancing the properties of PBT/PEG blends, making them potential candidates for various applications.     

Heat Resistant and Mechanical Properties of Biodegradable Poly(Lactic Acid)/Poly(Butylene Succinate) Blends Crosslinked by Polyaryl Polymethylene Isocyanate

This work focus on improving the heat resistant and mechanical properties of poly(lactic acid)/poly(butylene succinate) (PLA/PBS) blends using appropriate contents of polyaryl polymethylene isocyanate (PAPI). Some crosslinked structures were formed according to the gel fraction and rheological results, and the crosslinked structures played the role of nucleation site for the blends. And the Vicat softening temperature of the blends gradually increased with increasing PAPI content. Moreover, the addition of PAPI in the PLA/PBS blends produced a few PLA-PBS copolymers which acted as a compatibilizer and enhanced the interfacial adhesion. Thus, the mechanical properties of PLA were significantly improved.     

Improving Poly(ethylene terephthalate) Through Self‐nucleation

As‐received poly(ethylene terephthalate) (asr‐PET) may be reorganized by precipitation from trifluoroacetic acid upon gradual addition to a large excess of rapidly stirred acetone (p‐PET). Unlike asr‐PET, p‐PET repeatedly crystallizes rapidly from the melt, and can be used in small quantities (a few %) as an effective self‐nucleating agent to control and improve the bulk semi‐crystalline morphology and properties of asr‐PET. Nuc‐PET film has significantly increased hardness and Young's modulus and is much less permeable to CO₂, while its un‐drawn fibers exhibit higher tenacities and moduli. Because nuc‐PET contains no incompatible additives, it may be readily recycled.