Local process-dependent structural and mechanical properties of extrusion blow molded high-density polyethylene hollow parts

Although applied for several decades, production of hollow plastic parts by extrusion blow molding (EBM) is still over-dimensioned. To overcome this issue, a thorough investigation of the process-structure-property relationship is required. In this study, the local process-structure-property relationship for high-density polyethylene EBM containers is analyzed with differential scanning calorimetry and dynamic mechanic analysis microindentation. Local process-dependent crystallinity and complex modulus data at various processing conditions are supplemented with wide-angle X-ray diffraction and transmission electron microscopy (TEM). The crystallinities and the complex moduli clearly show lower values close to the mold side than at the inner side and the middle of the cross-section, which reflects the temperature gradient during processing. Additionally, the orientation of the polymer chain (c-axis) reveals a low level of biaxiality with a slight tendency towards transverse direction. The biaxiality increases for low mold temperature and high draw ratio. Finally, biaxiality is confirmed with TEM, which reveals no preferred lamellar orientation.     

Balancing the Crystallinity and Film Formation of Metal–Organic Framework Membranes through In Situ Modulation for Efficient Gas Separation

Polycrystalline metal–organic framework (MOF) layers hold great promise as molecular sieve membranes for efficient gas separation. Nevertheless, the high crystallinity tends to cause inter-crystalline defects/cracks in the nearby crystals, which makes crystalline porous materials face a great challenge in the fabrication of defect-free membranes. Herein, for the first time, we demonstrate the balance between crystallinity and film formation of MOF membrane through a facile in situ modulation strategy. Monocarboxylic acid was introduced as a modulator to regulate the crystallinity via competitive complexation and thus concomitantly control the film-forming state during membrane growth. Through adjusting the ratio of modulator acid/linker acid, an appropriate balance between this structural “trade-off” was achieved. The resulting MOF membrane with moderate crystallinity and coherent morphology exhibits molecular sieving for H₂/CO₂ separation with selectivity up to 82.5.     

Crystalline and spectroscopic characterization of poly(2-aminoethyl methacrylate hydrochloride) chains grafted onto poly[(R)-3-hydroxybutyric acid]

The present study is aimed to investigate the degree of crystallinity of poly(3-hydroxybutyrate) P(3HB) grafted with poly(2-aminoethyl methacrylate hydrochloride) (PAEMA) chains using WAXS, micro Raman, and FTIR spectroscopy. The samples were obtained by radiation induced graft polymerization of the monomer in the substrate using different solvents for comparison. The results of crystallinity are consistent with those obtained of lower crystallinity in grafting copolymer relative to the substrate P(3HB). The low crystallinity is directly related to the increase of the degree of grafting, meaning that although the P(3HB) amorphous region is grafted, the crystalline zone is also affected in some extent by the grafting process and the environment of the new molecule. Three different methods were surveyed to determine the variation of crystallinity degree with the grafting degree. It is shown that all methods provide linear relationships between these variables, but WAXS method was found more acceptable than the others (FTIR and Raman). A detailed characterization of the vibrational bands characteristic of amorphous and helical crystalline structure of the grafting copolymers are also highlighted.     

Efficient P3HT:PC61BM solar cells employing 1,2,4-trichlorobenzene as the processing additives

The efficiency of the poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl C_(61)-butyric acid methyl ester(PC_(61)BM) based organic solar cells was enhanced by using 1,2,4-trichlorobenzene(TCB) as a processing additive to control the blend morphology. The addition of TCB improved the arrangement of P3HT which resulted in good phase separated blend films. Correspondingly, the optimized solar cells showed a power conversion efficiency(PCE) of 4.17% with a fill factor(FF) of 0.69, which were higher than those of common thermal annealing devices(PCE 3.84%, FF 0.67). The efficiency was further improved to 4.74% by thermal annealing at 150 °C for 10 min with a higher FF of 0.74.     

Influence of processing methods on starch properties

Native potato starch was prepared using different processing methods. The samples were characterized by wide-angle X-ray scattering (WAXS), optical microscopy, differential scanning calorimetry (DSC), and microhardness. Compression molding of the starch granules led to sintered relatively brittle materials. Here, the amylopectin crystals of the native powder remained grossly preserved. Preparation of dry films from aqueous gels resulted in disintegration of the structure of the native starch granules and in the formation of a new semicrystalline structure comprised of crystallized amylose molecules. Injection molding of native starch was found to be a processing method that gives rise to amorphous materials with superior mechanical properties.     

Effect of moisture content on the heat-sealing property of starch films from different botanical sources

In this study, we investigated the differences in the crystallinity of starch films (mung bean, water chestnut, sweet potato, and cassava starches) with different moisture contents stored in different humidity conditions (11%, 22%, 33%, 43%, 54%, 75%, and 84%) and evaluated their thermal adhesion and sealing properties. X-ray diffraction analysis revealed an association between the degree of crystallinity and the moisture content in starch films: crystallinity decreased with an increase in the moisture content. Field Emission Scanning Electron Microscopy (FE-SEM) analysis showed that films with low moisture content failed to completely adhere, but films with a high moisture content and lower crystallinity showed good adherence, with two films perfectly adhered at the same temperature because water molecules acted as a mobility enhancer. The peeling test demonstrated the failure modes of the heat-bound films. The cassava starch film, which had a low amylose content and crystallinity, showed better adhesion compared to other starch films.     

Achieving highly crystalline rate and crystallinity in Poly(l-lactide) via in-situ melting reaction with diisocyanate and benzohydrazine to form nucleating agents

The drawback of the application for poly(_l-lactide) (PLLA) is the low crystalline rate and crystallinity obtaining via normal processing methods. Modifying crystallization of PLLA has been found to be an efficient way to improve its mechanical and heat resistance properties. In this wok, 4, 4′-diphenylmethane diisocyanate (M) and benzohydrazine (P) were employed into PLLA melt to in-situ form nucleating agents. The in-situ melting reaction was confirmed by a nuclear magnetic resonance spectroscopy. The crystallization behavior and crystalline morphology were investigated by a differential scanning calorimetry, a polarized optical microscopy and a field emission scanning electron microscope. The crystalline rate of PLLA was abruptly enhanced by adding (M+P) and melting reaction with PLLA. The crystallization half-time of PLLA dramatically decreased from 42.0 to 1.1 min at 130 °C by the in-situ formation of nucleating agents. The crystallinity of PLLA increased from 10.3 to 42.1 by adding 0.25% (M+P) and melting reaction for 8 min. Furthermore, the size of PLLA crystals was dramatically reduced because of the nucleating effect. Accompanied with improvement on crystallinity, the Vicat softening temperature of PLLA shifted from 57.4 °C to 93.7 °C by the in-situ reaction with 6.00% (M+P), and indicating heat resistance enhancement.     

Alkali treatment of lignocellulosic fibers extracted from sugarcane bagasse: Composition,structure, properties

Lignocellulosic fibers extracted from sugarcane bagasse were treated with NaOH solutions of different concentration (0-40 wt%) to study the effect of alkali treatment on the composition, structure and properties of the fibers. Composition was determined by the van Soest method, structure was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM), while mechanical properties by tensile testing. Hemicellulose and lignin content decrease, while cellulose content goes through a maximum as a function of alkali concentration. Crystallinity changes only slightly and microfibril angle (MFA) remains constant thus structural effects and especially MFA are not the primary reasons for changing properties. The Young's modulus of the fibers shows a slight maximum at around 2-4 wt% NaOH content, while tensile strength goes through a much more pronounced one at around 5-8 wt%. Direct correlation between structure and mechanical properties was not found indicating that composition is more important in the determination of properties than structure. Regression analysis proved that the combination of several compositional variables determines mechanical properties in a non-linear manner. The improvement in fiber properties was explained with the dissolution of weak amorphous fractions and the relative increase of cellulose content.     

Mechanical properties of amphiphilic urethane acrylate ionomer hydrogels having heterophasic gel structure

Amphiphilic urethane acryale hydrogels containing ionic groups (dimethylolpropionic acid) were prepared by varying the molecular weight of the soft segment (polyether type) and the type of diisocyanate, and their mechanical properties were examined. They showed heterophasic gel structure composed of ionic hard domains induced by aggregation of the ionic groups and polyether soft domains comprising the urethane acrylate network. This heterophasic structure could be confirmed by dynamic mechanical analysis (DMA) and by wide-angle X-ray scattering analysis (WAXS); the crystallinity detected by WAXS and the transition peak of the ionic hard domains detected by DMA strongly suggested that there were ionic aggregates. These ionic aggregates acted as reinforcing fillers in the network, which eventually enhanced the tensile strength of the hydrogels. Above all, the tensile properties of the hydrogels were of interest in that the trends of the stress-strain curves were consistent with the rubbery ones. It is believed that the higher purity of the polyether soft domains resulted from the heterophasic gel structure imparting further elastomeric properties on the network. Received: 31 July 1998 Accepted in revised form: 15 October 1998