Structure and properties for biomass-based polyester blends of PLA and PBS

Structure and properties are studied for binary blends composed of poly(lactic acid) (PLA) and poly(butylene succinate) (PBS). The rheological measurements in the molten state reveal that the entanglement molecular weight of PLA is lower than that of PBS. Further, the interfacial tension of the immiscible blend system is evaluated employing a rheological emulsion model and found to be 3.5 [mN/m]. Moreover, thermal analysis directly detects that addition of PBS enhances the crystallization of PLA even though PBS is in a molten state. Further, the cold-crystallization for quenched blends occurs at lower temperature than that for a quenched PLA. This would be attributed to the nucleating ability of PBS, leading to generation of PLA crystallites during the quench operation.     

锌离子对聚乳酸结晶和热性能的影响

本文发现了Zn(II)离子掺杂可以加快聚乳酸的结晶过程. 测试了三种Zn(II)盐(ZnCl₂、ZnSt和ZnOAc),并与其它离子Mg(II)和Ca(II)进行对照. FT-IR以及变温拉曼光谱分析发现,经Zn(II)离子掺杂后,聚乳酸的结晶度和结晶速率均增加,差示扫描量热技术以及X射线衍射分析也进一步证实. 差示扫描量热技术测定PLA/ZnSt-0.4 wt%材料的结晶率达到22.46%,PLA/ZnOAc-0.4 wt%材料的结晶率达到24.83%.     

Crystallization behavior and electroactive properties of PVDF,P(VDF-TrFE) and their blend films

PVDF, poly(vinylidene fluoride), as a semi-crystalline polymer, has interesting electroactive properties but usual melt and solution processing techniques result in its thermodynamically favored non-polar α-phase. By comparison, poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE), PT for short, directly crystallizes in the polar β-phase under the same conditions as PVDF. In this study, blend thin films comprising PVDF and P(VDF-TrFE) were prepared by solvent casting method. The difference in the crystallization behavior is comprehensively investigated between the polymers: PVDF, P(VDF-TrFE), and the resulting blend films. It is found that replacement of the fluoride atom in TrFE monomer induces a strong steric hindrance that may alter the crystallization process to become more favorable for nucleation of the PVDF β-phase. To figure out the effect of TrFE content on the crystallization behavior and electroactive properties, films with different blend ratios of PVDF and P(VDF-TrFE) were prepared. We found that the PVDF films exhibit higher crystallization activation energy (ΔE) as PT content increases. The atomic force microscopy (AFM) in the piezoresponse force microscopy (PFM) mode illustrated that P5T5 films with equal contents of PVDF and P(VDF-TrFE) induced the highest d₃₃ values.     

Crystallization kinetics and the fine morphological evolution of poly(ethylene oxide)/ionic liquid mixtures

The overall crystallization kinetics and spherulite morphologies of miscible poly(ethylene oxide)(PEO)/1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_6]) mixtures were studied by differential scanning calorimetry(DSC),polarized optical microscopy(POM) and rheological measurements. The finer crystal structures were further detected by wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS). Crystallization of PEO is largely suppressed by [BMIM][PF_6] addition especially at higher ionic liquid(IL) concentrations above 20 wt%. Both the overall crystallization rate and the spherulite growth decrease with the increase of IL content and crystallization temperature; however, the crystallization mechanism keeps unchanged as evidenced by the similar Avrami exponent n and WAXD results. The addition of [BMIM][PF_6] could induce more nuclei to some extent, but the induction time of crystallization is evidently prolonged,and a linear to non-linear transition of the spherulite growth(R ∝ t to R ∝ t~(1/2)) can be observed. At higher IL concentration,the spherulite texture changes apparently from particular serrated to branch surface due to the diffusion-controlled growth and the dilution effect, which also as a main factor contributes to the increasing trend of the long period of crystals.     

Influence of clay surface modification with urethane groups on the crystallization behavior of in situ polymerized poly(butylene succinate) nanocomposites

The crystallization behavior and fine structure of poly(butylene succinate) (PBS) nanocomposites with intercalation (30B20) and exfoliation (30BM20) morphologies, respectively, were investigated via isothermal crystallization testing and synchrotron small-angle X-ray scattering (SAXS). The dynamic viscosity of 30BM20 was markedly increased due to favorable interactions between the PBS matrix and the urethane group on the clay surface. However, 30BM20 showed similar crystallization rates to that of homo PBS because the surface urethane modification for 30BM20 precluded PBS matrix from the metallic group into clay to difficult in contact with each other, resulting in a reduced nucleation activity for the metallic group. SAXS profiles revealed that the long period and amorphous region size for 30B20 drastically decreased during isothermal crystallization. Meanwhile, 30BM20 was similar to those of homo PBS. This result also supports the above explanation for isothermal crystallization behavior. Considering all results in total, the introduction of a urethane modification considerably enhanced the physical properties of PBS but caused delayed crystallization rates.     

Crystallinity and dimensional stability of biaxial oriented poly(lactic acid) films

Transparent biaxial oriented poly(lactic acid) (BOPLA) films with improved dimensional stability were successfully prepared by controlling the crystallization of poly(lactic acid) (PLA). The crystalline morphology of PLA films can be manipulated by changing certain processing parameters, such as stretch ratio, heat setting temperatures, and heat setting time. Optical and mechanical properties as well as dimensional stability of the resulting polymer films are governed by their crystallinity and crystalline morphology. Crystallization behavior and kinetics of PLA, therefore, were investigated using wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS), and differential scanning calorimetry (DSC) techniques. Mechanical properties and the dimensional stability of the biaxial oriented PLA films were obtained and correlated with their processing conditions. Poly(lactic acid) films prepared by melt extrusion methods have great potential for food packaging, shrink labeling and protective film applications. However, shrinkage at elevated processing temperature should be minimized to avoid puckering of the polymer film. Shrinkage of less than 2% was achieved for a BOPLA film stretched 300% in both directions at 75 °C and then annealed at 160 °C for 30 s. Fabrication, properties, and potential applications of a series of biodegradable films will be described.     

Novel poly(butylene succinate-co-lactic acid) copolyesters: Synthesis, crystallization, and enzymatic degradation

A series of aliphatic biodegradable poly(butylene succinate-co-dl-lactide) (PBSLA) copolyesters were synthesized with the aim of improving the degradation rate of poly(butylene succinate) (PBS) by incorporation of dl-oligo(lactic acid) (OLA) into the PBS molecular chains. The composition and sequential structure of the aliphatic copolyesters were investigated by proton nuclear magnetic resonance (¹H NMR) spectroscopy. The crystallization behaviors, the crystal structure and morphology of the copolyesters were investigated by using differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarizing optical microscopy (POM), respectively. The results indicate that the crystallization of the copolyesters was restricted by the incorporation of lactide (LA) units, which further tuned the mechanical properties of the copolyesters. The copolyesters could form complete spherulites and exhibit the same crystal structure as that of PBS. Enzymatic study indicated that the copolyesters with higher content of LA units degraded faster, and the degradation began in the amorphous regions and then in the crystalline regions. The morphology and the resulting degradation products of the copolyesters were investigated by scanning electron microscopy (SEM) and ¹H NMR analysis during the degradation process.     

Impact of plasticizers and tackifiers on the crystallization of isotactic poly(1-butene)

Crystallization of a semi-crystalline polyolefin in the presence of low molecular weight modifiers was quantified by differential scanning calorimetry and optical microscopy. The polyolefin was a commercial grade of isotactic poly(1-butene) (iPB). Two modifiers were used: an oligomeric plasticizer, designated HOAO, which decreased the glass transition temperature (T_g) of the system, and an oligomeric tackifier, designated HOCP, which increased T_g. Binary iPB/modifier blends containing 10% or 20% by weight of HOAO or HOCP were examined to determine how their addition affects T_g, while ternary iPB/HOAO/HOCP blends containing 10% or 20% by weight of total modifier were examined to determine the effects of dilution by using a ratio of HOAO to HOCP that matched the T_g of iPB. The addition of modifier decreased the nucleation rate, spherulitic crystal growth rate, and final crystallinity of each blend. However, only the nucleation rate showed a dependence on the type of modifier, with nucleation retarded more by HOCP than by HOAO. A Hoffman-Weeks analysis of the melting point as a function of crystallization temperature confirmed that the driving force for nucleation was reduced, and that the effect was larger for HOCP. An Avrami analysis of the bulk crystallization kinetics was consistent with these observations, as the Avrami exponents were in the range of 3-4.     

Crystallization, mechanical and thermal properties of sorbitol derivatives nucleated polypropylene/calcium carbonate composites

<正>The effect ofαphase nucleating agent(NA) 1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol(DMDBS) on crystallization and physical properties of polypropylene/calcium carbonate(PP/CaCO_3) composites has been comparatively investigated.Compared with binary PP/CaCO_3 composites,in which CaCO_3 exhibits weak heterogeneous nucleation, inconspicuous reinforcement and toughening effects for PP,the introduction of a few amounts of DMDBS induces a great increase of the degree of crystallinity.Largely improved tensile properties,fracture toughness at relatively higher temperature and heat deformation temperature(HDT) are observed for DMDBS nucleated PP/CaCO_3 composites.     

Synthesis and characterization of tin containing molybdophosphate and tungstophosphate glasses

Two series of tin containing molybdophosphate and tungstophosphate glasses and glass-ceramics were achieved by means of a domestic microwave oven under air. During melting, a redox reaction takes place between Sn²⁺ and Mo⁶⁺ generating the crystallization of a Na(Sn^IV,Mo^IV)(PO₄)₃ solid solution with a NZP (NaZr₂P₃O₁₂) type structure. Such reactivity was not underlined in the case of the W-series. All the samples were characterized from a thermal and mechanical point of view as a function of the RO₃ (R = Mo, W) for SnO substitution. Two types of behaviors were identified. For the Mo-series, all the characteristics, except density, present an extremum value for the chemical composition with a 1:1 SnO-MoO₃ molar ratio. This is strongly correlated to the amount of NZP crystals present in the glass ceramic, the different behavior observed for the density being due to the low compactness of the NZP phase. For the W-series, all these different characteristics varies monotonously according to a progressive strengthening of the network by replacement of a low field strength ion (Sn²⁺) by a higher field strength ion (W⁶⁺). In addition, the solid state reactivity of a 1:1 SnO-RO₃ mixture was examined confirming the absence of any redox process between SnO and WO₃ during the glass synthesis.