Morphology and properties of super-toughened bio-based poly(lactic acid)/poly(ethylene-co-vinyl acetate) blends by peroxide-induced dynamic vulcanization and interfacial compatibilization

Super-toughened poly(lactic acid) (PLA)/poly(ethylene-co-vinyl acetate) (EVA) blends were prepared via 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD) induced dynamic vulcanization and in situ interfacial compatibilization. The effects of AD on the morphology and properties of PLA/EVA blends were studied using a Brabender torque rheometer, gel content test, scanning electron microscopy (SEM), differential scanning calorimetry (DSC) thermogravimetric analysis (TGA) and mechanical properties test. The torque and gel content demonstrated that EVA and PLA was successfully vulcanized in the presence of free radicals obtained by the decomposition of the 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (AD). Additionally, the gel content results indicated that, compared with PLA, EVA is more aggressive with free radicals. The SEM revealed that a relatively uniform phase morphology and good interfacial compatibilization were achieved in the dynamically vulcanized PLA/EVA/AD blends. The interfacial reaction and compatibilization between the component polymers resulted in the formation of super-toughened PLA/EVA blended materials.     

CL-20/TNT共晶炸药的分子动力学研究

运用分子动力学(MD)方法,选择凝聚态分子势能优化力场(COMPASS),对六硝基六氮杂异伍兹烷(ε-CL-20)、2,4,6-三硝基甲苯(TNT)晶体及其等摩尔比的CL-20/TNT混合炸药和共晶炸药进行不同温度下恒定粒子数等压等温(NPT)系综模拟研究.结果表明,CL-20/TNT共晶的内聚能密度(CED)和结合能随温度的升高逐渐减小;共晶的CED比混合炸药的大,结合能是混合炸药的2倍多,预示其稳定性明显增强.对相关函数和局部放大结构显示共晶中组分分子间作用主要来自TNT中H和CL-20中O以及CL-20中H和TNT中O之间形成的氢键.通过波动法求得的弹性力学性能结果表明,CL-20/TNT共晶的拉伸模量(E)、体积模量(K)和剪切模量(G)介于ε-CL-20和TNT晶体之间,且随温度的升高而下降,符合一般预期;但共晶炸药的柯西压(C12-C44,Cij弹性系数)、K/G和泊松比(ν)均比其组分炸药ε-CL-20和TNT高得多,预示该共晶具有异常高的延展性和弹性伸长,主要是二组分呈层状交替排列且之间存在较强相互作用所致.     

Influence of the e-beam irradiation and photo-oxidation aging on the structure and properties of LDPE-OMMT nanocomposite films

In this paper two systems, polyethylene (LDPE) and polyethylene/commercial organo-modified montmorillonite (LDPE/OMMT) nanocomposite, were subjected to e-beam irradiation at different doses and both the molecular modifications and mechanical properties have been investigated through solubility, FT-IR, calorimetric and tensile tests. Moreover, in some of the irradiated systems photo-oxidation aging was performed and its effects were studied. The results show an enhancement with irradiation of the positive effect of the nano-filler loading, related to the increase of the mechanical properties, due to the increase of the nano-filler polymer interaction.Nevertheless calorimetric and FT-IR data indicate that the well known reduction of LDPE/OMMT nanocomposite resistance to photo-oxidation ageing, with respect to LDPE, is amplified by ionizing radiation.     

Magnetomechanical training of single crystalline Ni-Mn-Ga alloy

A 5M Ni-Mn-Ga single crystal was investigated, supplied by Adaptamat Ltd, Finland. Especially low temperature magnetic actuation as well as cyclic tensile-compression tests revealed promising properties, which provide useful insights for training concepts in polycrystalline materials. Successive compressions lead to a significant reduction of the twinning stress by a factor of two.     

Micro- and nano-mechanical characterization of polyamide 11 and its composites containing cellulose nanofibers

Nanocomposites from polyamide 11 and dried cellulose nanofibers (CNs), 16–30 nm in thickness and 50–400 nm in length, were prepared via direct melt mixing and their micro- and nano-mechanical properties were studied. (PF) QNM (Quantitative Nanomechanical Mapping) method was used to map nanomechanical properties at the surface of polyamide 11 and nanocomposites. This new AFM method emphasized both the increased modulus in nanocomposites as compared to the matrix and the microstructure on different levels in polyamide 11 and its nanocomposites. PF QNM showed that their crystalline structure consists of bundles of lamellar stacks, 200–350 nm in width and 20–40 nm wide lamellar stacks. Moreover, PF QNM study emphasized higher structural order in nanocomposites with 3 and 5 wt.% CNs and lower in the nanocomposite with 8 wt.% CNs as compared to the reference. These observations were verified and are consistent with both crystallinity values determined by DSC and micro-mechanical test results. The oriented bundles of lamellar stacks, observed by PF QNM, could be considered as the main blocks determining high mechanical properties for the studied nanomaterials.     

Tailoring the properties of electrospun PHBV mats: Co-solution blending and selective removal of PEO

Microstructure, surface topography, thermal and mechanical features of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) electrospun non-woven mats were modified, modulated and tailored through blending with different polyethylene oxide (PEO) amounts (20, 30 and 50% wt/wt). The optimal parameters of the soaking protocol for the selective removal of the sacrificial polymer were accurately identified by means of scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy, simultaneous thermogravimetric and differential analyses (TG-DTA) and differential scanning calorimetry (DSC). The complete PEO removal after soaking in H₂O for 7 days with daily refreshment was confirmed. The resulting samples were only comprised of PHBV fibers characterized by a remarkable decrease of the average size with respect to the respective blends. Their surface topography was corrugated and rough and presented nodules, pits, nanopores, shallow and elongated nanostructured indents/grooves along the fiber axis. A remarkable reduction (>75%) of the tensile modulus (E) of electrospun PHBV mats (15–20 MPa) was obtained, maintaining comparable elongation at break (ε_max) values (20–30%).     

Micromechanics of polymers

Polymers possess a very large inherent capacity for property modifications. The bridge between structure or morphology and mechanical properties is created by the micromechanical processes of deformation and fracture, the “micromechanics.” Developments mainly in electron microscopy (EM) (scanning, transmission, and high-voltage electron microscopy) and scanning force microscopy (SFM) opened up a wide range of experiments previously impossible, including the in situ study of micromechanical processes. These new techniques are reviewed and used to study micromechanical properties of amorphous and semi-crystalline polymers and several toughened polymers. On the basis of the detailed knowledge of micromechanical mechanisms, a new method of polymer modification becomes a realistic possibility, a method of micromechanical construction of new polymeric systems.     

Mixed mode fracture of a piezoelectric–piezomagnetic bi-layer structure with two un-coaxial cracks parallel to the interface and each in a layer

The purpose of the present work is to study the mixed mode fracture of a piezoelectric–piezomagnetic composite with two un-coaxial cracks parallel to the interface and each in a layer. Methods of generalized dislocation simulation, Green’s function, Cauchy singular integral equation and Lobatto–Chebyshev collocation are combined together to get the numerical results of mechanical strain energy release rate (MSERR). Three kinds of effects are revealed by parametric studies, i.e., the free-surface effect, the shielding effect and the interference effect, and they are used to interpret the characteristics of COD and MSERR curves. In addition, the effects of shear loading, magnetic loading and electric loading on MSERR are also disclosed, respectively, by varying the corresponding loading factor.     

REACTIONS IN SOLID STATE WITHIN POLYURETHANES. KINETICS AND POSTCURE REACTION MECHANISM IN CASTING POLYURETHANE ELASTOMERS

The solid state postcure reaction mechanism of polyurethane elastomers (PU) synthesized using a relatively small excess (up to 10%) of isocyanate was studied. The postcure process succeeds especially with the assistance of atmospheric humidity and, its process velocity depends on PU sample thickness. The polymer network is consolidated mainly by the formation of a new urea group. The formation of allophanate, uretidinedione, and isocyanurate groups and possible reticulations by the intermediary amine groups formed, play only a secondary role in the studied conditions. Kinetic equations regarding the postcure evolution were followed by means of the changes in mechanical properties. The evolution of the process was correlated to different kinetic measurements regarding the elementary processes involved like the consumption of NCO groups, absorption of water from the atmospheric humidity, and desorption of CO₂ resulted during the formation of urea group. The CO₂ desorption appears to be the slowest dynamic process.     

Dielectric studies of a bioactive tetramic acid and its complexes with Cu(II) and Co(II)

The 3-acyl tetramic acids constitute a growing class of natural products displaying a range of biological activities. The g , g ' tricarbonyl moiety present in the 3-acyl tetramic acid provides a suitable site for bidentate complexation to a metal, which increases the biological activity. For the dielectric study of N-acetyl-3-butanoyl tetramic acid and a series of its complexes with Cu(II) and Co(II) in symmetric and asymmetric forms, we used the Thermally Stimulated Depolarization Currents (TSDC) technique. The drastic decrease of the intensity of the TSDC peaks of the symmetric and asymmetric complexes, compared to the above mentioned ligand, suggested that the polarizability of the side groups is considerably reduced. This result enhances the proposed complexation mode of the ligand through oxygen next to carbons 3 and 4 of the 5-member ring.