Investigation of Dynamic Viscoelastic Asymmetric Response of PA6 Film Based on Fractional Rheological Model.

Polyamide 6 (PA6) film as a typical viscoelastic material, satisfies the time-temperature superposition (TTS), and demonstrates obvious dynamic strain amplitude and frequency correlation under dynamic load. The investigation of the dynamic mechanical behavior of PA6 film is essential to ensure the safety of these materials in practical applications. In addition, dynamic mechanical property testing under conventional experimental conditions generally focuses on the short-term mechanical performance of materials. Therefore, the dynamic viscoelasticity of PA6 film was tested using a dynamic thermo-mechanical analyzer (DMA) in this study, and the complex modulus master curve was constructed based on time-temperature superposition (TTS) to realize the accelerated characterization of long-term mechanical properties. Furthermore, according to experimentally obtained asymmetric characteristics of the Cole-Cole diagram and the loss modulus master curve of the PA6 film, the parameter distribution of the fractional Zener model and the modified fractional Zener model were compared, and the asymmetric dynamic viscoelastic response of PA6 film under different conditions was systematically investigated using these models. The results indicate that the modified fractional Zener model can truly describe the dynamic asymmetric characteristics of PA6 film, verify the feasibility and advantages of the modified fractional rheological model, and provide some theoretical guidance for exploring the tensile rheological mechanism of PA6 film.

Investigation on the creep mechanism of PA6 films based on quasi point defect theory.

Polyamide 6 (PA6) films with significant α relaxation process was selected as the model system. The creep behavior and rheological mechanism during deformation in the amorphous regions of semi-crystalline polymers are systematically investigated by carrying out creep experiments. Based on the quasi point defect (QPD) theory, the complete physical process of PA6 film creep behavior from elasticity to viscoelasticity and viscoplasticity was analyzed and modeled from the perspective of structural heterogeneity. The results demonstrate that the creep deformation of PA6 film is a typical thermo-mechanical coupling and nonlinear mechanics process, and potential creep mechanisms corresponds to stress-induced local shear deformation enhancement and thermal activation-induced particle flow diffusion. The elastic-plastic transition involved in the creep deformation process of semi-crystalline polymer originates from the activation of quasi-point defective sites in the amorphous region, the expansion of sheared micro-domains and irreversible fusion. The generalized fractional Kelvin (GFK) model is proposed, and the physical meaning of parameters is explained by combining the quasi point defect theory and creep delay spectrum(L(τ)). Finally, the effectiveness of the GFK model and the QPD theory in studying the deformation behavior of PA6 films was validated by comparing experimental data with theoretical results, which theoretically reveals the structural evolution of PA6 film during creep process.

Pseudo-Eutectic of Isodimorphism to Design Biaxially-Oriented Bio-Based PA56/512 with High Strength, Toughness and Barrier Performances.

The biaxially-oriented PA56/512 has excellent mechanical strength, extensibility and water-oxygen barrier properties and has broad application prospects in green packaging, lithium battery diaphragm and medical equipment materials. The correlation between the aggregation structure evolution and macroscopic comprehensive properties of copolymer PA56/512 under biaxial stretching has been demonstrated in this work. The structure of the random copolymerization sequence was characterized by 13C Nuclear magnetic resonance (NMR). The typical isodimorphism behavior of the co-crystallization system of PA56/512 and its BOPA-56/512 films was revealed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) tests. And the aggregation structure, including the hydrogen bond arrangement, crystal structure and crystal morphology of PA56/512 before and after biaxial stretching, was investigated by XRD, Fourier-transform infrared spectroscopy (FTIR) and polarized optical microscopy (POM) tests. Furthermore, the effect of the biaxially-oriented stretching process on the mechanical properties of PA56/512 has been demonstrated. In addition, a deep insight into the influence of the structure on the crystallization process and physical-mechanical performance has been presented. The lowest melting point at a 512 content of 60 mol% is regarded as a "eutectic" point of the isodimorphism system. Due to the high disorder of the structural units in the polymer chain, the transition degree of the folded chain (gauche conformation) is relatively lowest when it is straightened to form an extended chain (trans conformation) during biaxially-oriented stretching, and part of the folded chain can be retained. This explains why biaxially stretched PA56/512 has high strength, outstanding toughness and excellent barrier properties at the pseudo-eutectic point. In this study, using the unique multi-scale aggregation structure characteristics of a heterohomodymite polyamide at the pseudo-eutectic point, combined with the new material design scheme and the idea of biaxial-stretching processing, a new idea for customized design of high-performance multifunctional polyamide synthetic materials is provided.

Investigation on the Correlation between Biaxial Stretching Process and Macroscopic Properties of BOPA6 Film.

Biaxially oriented polyamide 6 (BOPA6) films were prepared by extrusion casting and biaxial stretching with polyamide 6. The effects of different biaxially oriented on the macroscopic properties of BOPA6 were investigated by characterizing the rheological, crystallization, optical, barrier and mechanical properties. The results show that the increase of stretching temperature leads to the diffusion and regular stacking rate of BOPA6 chain segments towards crystal nuclei increases, the relative crystallinity increases, reaching 27.87% at 180 °C, and the mechanical strength and optical performance decrease. Heat-induced crystallization promotes the transformation of ß-crystals to α-crystals in BOPA6, resulting in a more perfect crystalline structure and enhancing oxygen barrier properties. BOPA6 chains are oriented, and strain-induced crystallization (SIC) occurs during the biaxial stretching. Further increasing the stretch ratio, the relative crystallinity increased to 30.34%. The machine direction (MD) and transverse direction (TD) tensile strength of BOPA6 (B-33) are nearly two times higher than the unstretched film, reaching 134.33 MPa and 155.28 MPa, respectively. In addition, the permeation decreases to 57.61 cc·mil/(m2 day), and the oxygen barrier performance has improved by nearly 30% compared to the sample B-22. BOPA6 has a high storage modulus at a high stretching rate (300%/s). Rapid chain relaxation would promote the molecular chain disorientation, destroy the entangled network of the molecular chain, and lead to a decrease in tensile strength, reducing to about 110 MPa.

Effect of biaxial stretching on the microstructure evolution, optical, mechanical and oxygen barrier properties of biodegradable poly(lactic acid) (PLA)/poly(butylene adipate-co-terephthalate) (PBAT) films.

The poly(butylene adipate-co-terephthalate) (PBAT)/poly(lactic acid) (PLA) films have been widely used due to their biological degradability and excellent comprehensive properties. However, the reports regarding biodegradable PLA/PBAT films are rather scarce. In this work, systematical investigations of biaxially stretched PLA/PBAT films were performed. Compared with unstretched films, the PLA/PBAT 75/25 films with the stretching ratio of 5 × 1 exhibited an improvement on the crystallinity of PLA from 6 % to 58.6 %. According to 2D-WAXS results, the orientation of the α crystal in the MD increased with the increase of the stretching ratio. The stretched films showed favorable barrier properties. The oxygen permeability (OP) of 2 × 2 PLA/PBAT 75/25 films shows a decrement of 22 % compared with that of the unstretched films. Interestingly, the uniaxially stretched PLA/PBAT 75/25 films exhibits increased surface roughness (Ra) for 3 × 1 film whereas decreased Ra for the 5 × 1 film, which could be related to the phase separation under stretching. The tensile strength in the machine direction (MD) of the PLA/PBAT 75/25 films was improved up to 51.6 MPa for 5 × 1 film, which is 45 % higher than that of unstretched counterpart. The stretched films exhibit excellent mechanical and barrier properties, which could be utilized in packaging industry with high potential.

The Investigation of Copolymer Composition Sequence on Non-Isothermal Crystallization Kinetics of Bio-Based Polyamide 56/512.

A new bio-based polyamide 56/512 (PA56/512) has been synthesized with a higher bio-based composition compared to industrialized bio-based PA56, which is considered a lower carbon emission bio-based nylon. In this paper, the one-step approach of copolymerizing PA56 units with PA512 units using melt polymerization has been investigated. The structure of the copolymer PA56/512 was characterized using Fourier-transform infrared spectroscopy (FTIR) and Proton nuclear magnetic resonance (1H NMR). Other measurement methods, including relative viscosity tests, amine end group measurement, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), were used to analyze the physical and thermal properties of the PA56/512. Furthermore, the non-isothermal crystallization behaviors of PA56/512 have been investigated with the analytical model of Mo's method and the Kissinger method. The melting point of copolymer PA56/512 exhibited a eutectic point at 60 mol% of 512 corresponding to the typical isodimorphism behavior, and the crystallization ability of PA56/512 also displayed a similar tendency.

Improvement of Gas Barrier Properties for Biodegradable Poly(butylene adipate-co-terephthalate) Nanocomposites with MXene Nanosheets via Biaxial Stretching.

In order to ease the white pollution problem, biodegradable packaging materials are highly demanded. In this work, the biodegradable poly (butylene adipate-co-terephthalate)/MXene (PBAT/Ti3C2TX) composite casting films were fabricated by melt mixing. Then, the obtained PBAT/Ti3C2TX composite casting films were biaxially stretched at different stretching ratios so as to reduce the water vapor permeability rate (WVPR) and oxygen transmission rate (OTR). It was expected that the combination of Ti3C2TX nanosheets and biaxial stretching could improve the water vapor and oxygen barrier performance of PBAT films. The scanning electron microscope (SEM) observation showed that the Ti3C2TX nanosheets had good compatibility with the PBAT matrix. The presence of Ti3C2TX acted as a nucleating agent to promote the crystallinity when the content was lower than 2 wt%. The mechanical tests showed that the incorporation of 1.0 wt% Ti3C2TX improved the tensile stress, elongation at break, and Young's modulus of the PBAT/Ti3C2TX nanocomposite simultaneously, as compared with those of pure PBAT. The mechanical dynamical tests showed that the presence of Ti3C2TX significantly improved the storage modulus of the PBAT nanocomposite in a glassy state. Compared with pure PBAT, PBAT-1.0 with 1.0 wt% Ti3C2TX exhibited the lowest OTR of 782 cc/m2·day and 10.2 g/m2·day. The enhancement in gas barrier properties can be attributed to the presence of Ti3C2TX nanosheets, which can increase the effective diffusion path length for gases. With the biaxial stretching, the OTR and WVPR of PBAT-1.0 were further reduced to 732 cc/m2·day and 6.5 g/m2·day, respectively. The PBAT composite films with enhanced water vapor and water barrier performance exhibit a potential application in green packaging.

Biodegradable Poly(butylene adipate-co-terephthalate) Antibacterial Nanocomposites Reinforced with MgO Nanoparticles.

Antibacterial packaging materials can reduce the microbial contamination of food surfaces. In this study, magnesium oxide (MgO) nanoparticles were synthesized and then coated with cetrimonium bromide (CTAB). CTAB-modified MgO (MgO@CTAB) was characterized by Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and thermogravimetric analysis. Then, different loadings of MgO@CTAB were mixed with poly(butylene adipate-co-terephthalate) (PBAT) by melt compounding. The results showed that the addition of MgO@CTAB deteriorated the thermal stability of PBAT due to MgO serving as a catalyst to promote the thermal degradation of PBAT. In addition, MgO@CTAB could serve as a nucleating agent to improve the crystallinity of PBAT. With the optimal 3 wt% of MgO@CTAB, the tensile strength of PBAT/MgO@CTAB increased from 26.66 to 29.90 MPa, with a slight enhancement in elongation at break. SEM observations and dynamical rheological measurements revealed that aggregation occurred when the content of MgO@CTAB exceeded 5 wt%. The presence of MgO@CTAB endowed PBAT with antibacterial properties. The bacterial inhibition zone increased with the increasing content of MgO@CTAB. In addition, MgO@CTAB had a better antibacterial efficiency against Gram-positive bacterial S. aureus than Gram-negative bacterial E. coli.

The Effect of Stretching on the Crystal Structure and Crystal Orientation of PA510/SiO2 Films.

In order to explore the relationship between the microstructure and macroscopic properties of PA510/SiO2 films, the effect of the stretching on the crystal structure and crystal orientation of stretched PA510/SiO2 films was studied. It could be seen from the transmission electron microscopy (TEM) graphs that the layered SiO2 molecules were mainly oriented toward the machine direction (MD) and the dispersion could be improved by stretching. Through wide-angle X-ray scattering (WAXS) analysis, PA510/SiO2 stretched films only contained a γ crystal form. During uniaxial stretching, especially for 1 × 3 film, the γ1(100) crystal form was obviously oriented in the equatorial direction, and the orientation of γ2(004) and γ3(006) crystal forms could be observed in the meridian direction. According to the Herman orientation function, the orientation of the b-axis in the MD increased with the increase of the stretching ratio. It was worth noting that the orientation of the crystal region was more obvious. The addition of SiO2 and the orientation of the crystalline and amorphous regions could improve the barrier properties of the films. The changes in the optical properties of stretched films were affected by the dispersion state of SiO2 and the surface roughness.

Reactive Compatibilization of Polyamide 6/Olefin Block Copolymer Blends: Phase Morphology, Rheological Behavior, Thermal Behavior, and Mechanical Properties.

In this study, the morphology, rheological behavior, thermal behavior, and mechanical properties of a polyamide 6 (PA6) and olefin block copolymer (OBC) blend compatibilized with maleic anhydride-grafted polyethylene-octene copolymer (POE-g-MAH) were investigated. The morphological observations showed that the addition of POE-g-MAH enhanced the OBC particle dispersion in the PA6 matrix, suggesting a better interfacial compatibility between the pure PA6 and OBC. The results of the Fourier transform infrared (FTIR) spectroscopy analysis and the Molau test confirmed the compatibilization reactions between POE-g-MAH and PA6. The rheological test revealed that the melt viscosity, storage modulus (G'), and loss modulus (G") of the compatibilized PA6/OBC blends at low frequency were increased with the increasing POE-g-MAH content. The thermal analysis indicated that the addition of OBC had little effect on the crystallization behavior of PA6, while the incorporation of POE-g-MAH at high content (7 wt%) in the PA6/OBC blend restricted the crystallization of PA6. In addition, the compatibilized blends exhibited a significant enhancement in impact strength compared to the uncompatibilized PA6/OBC blend, in which the highest value of impact strength obtained at a POE-g-MAH content of 7 wt% was about 194% higher than that of pure PA6 under our experimental conditions.