Uta Reuter

Effect of sol–gel derived in situ silica on the morphology and mechanical behavior of natural rubber and acrylonitrile butadiene rubber blends

Silica particles were generated and grown in situ by sol–gel method into rubber blends comprised of natural rubber (NR) and acrylonitrile butadiene rubber (NBR) at various blend ratios. Silica formed into rubber matrix was amorphous in nature. Amount of in situ silica increased with increase in natural rubber proportion in the blends during the sol–gel process. Morphology studies showed that the generated in situ silica were nanoparticles of different shapes and sizes mostly grown into the NR phase of the blends. In situ silica filled NR/NBR blend composites showed improvement in the mechanical and dynamic mechanical behaviors in comparison to those of the unfilled and externally filled NR/NBR blend composites. For the NR/NBR blend at 40/60 composition, in particular, the improvement was appreciable where size and dispersion of the silica particles into the rubber matrix were found to be more uniform. Dynamic mechanical analysis revealed a strong rubber–in situ silica interaction as indicated by a positive shift of the glass transition temperature of both the rubber phases in the blends.

Structure–property relationships in super-toughened polypropylene-based ternary blends of core–shell morphology

Structure–property relationships in PP/EPDM-g-MA/PA6 (70/15/15) ternary blends were studied in detail. PP-based reactive ternary blends with greatly improved impact strength were obtained via manipulation of phase morphology by applying different processing methods. SEM and TEM techniques were employed to study the phase morphology, which was shown to have a significant effect on the different properties, especially a tremendous improvement in the impact toughness. Reactive ternary blends showed core–shell morphology (core: PA6, shell: EPDM-g-MA in PP matrix) with quite different dispersed structures, in the form of mainly individual core–shells, clusters of core–shell particles, or percolation of clusters. Phase compatibility and thermal properties of the blends were studied by DMA and DSC analysis. A super-toughened PP-based reactive ternary blend with an impact strength much higher than the PP/EPDM (70/30) binary blend and about 15 times higher than that of pure PP was achieved. This was ascribed to a unique “percolated” structure of core–shell particles in the matrix, indicating the importance of the dispersion state of modifier particles in enhancing the impact strength. Fracture behavior and toughening micro-mechanisms were rationalized by post-mortem fractography of the impact-fractured surfaces. Synergistic effects of the interconnected structure and suitable interfacial adhesion together with cavitation and irreversible plastic growth of micro-voids caused massive shear yielding of the matrix material in the super-toughened blends.

Properties of Segmented Block Copolymers in PEEK/PSU Blends

As a method of compatibilization of immiscible polyether ether ketone (PEEK)/polysulfone (PSU) blends, the addition of segmented PEEK/PSU block copolymers based on amorphous bisphenol A-containing PEEK was studied. This approach was evaluated for blends consisting of PEEK and PSU homopolymers with different molecular weights and different amounts of compatibilizers (segmented PEEK/PSU block copolymers and reactive end-functionalized PEEK and PSU oligomers). The compatibilizers were added under varying melt-processing conditions and effectively allowed the homopolymers to interact with the segmented block copolymers in the blend. The influence of the compatibilizers on the phase behavior was examined in both binary and ternary blends. Interactions in the amorphous phase, which effectively induce an enhancement of the toughness properties of the final product, could be detected.

Analysis of dynamic oscillatory rheological properties of PP/EVA/organo-modified LDH ternary hybrids based on generalized Newtonian fluid and generalized linear viscoelastic approaches

A comprehensive investigation was performed on single-step melt processed polypropylene (PP)/(ethylene vinyl acetate copolymer (EVA)/organo-modified layered double hydroxide (LDH) counterpart ternary hybrids to explore the effect of LDH loading on small-amplitude oscillatory shear (SAOS) rheological properties and to correlate the properties with microstructure. The rheological results were analyzed in detail from qualitative and quantitative perspectives. Using qualitative interoperation of storage modulus and complex viscosity alteration against LDH loading, and also quantitative analysis by viscosity models based on both the generalized Newtonian fluid (GNF) and generalized linear viscoelastic (GLVE) approaches, detailed predictions were carried out on the microstructure of samples and also partitioning of the organo-modified LDH particles and their intercalation and exfoliation extent within hybrids. By comparing the elasticity and relaxation spectrum of PP-rich/LDH with those of EVA-rich/LDH hybrids, it was predicted that organo-modified LDH platelets, in the case of PP-rich samples, have been located at the interface or within the EVA dispersed particles, while in the case of EVA-rich samples, they mainly localized within the matrix. In addition, the crossover frequency and slope of G′ and G″ curve at terminal region were correlated with the extent of intercalated and exfoliated structures of filler. The validity of these predictions on microstructure of the developed hybrids was confirmed visually using transmission electron microscope (TEM) micrographs.

Polypropylene/Layered Double Hydroxide Nanocomposites: Influence of LDH Intralayer Metal Constituents on the Properties of Polypropylene

Sonication-assisted delamination of layered double hydroxides (LDHs) resulted in smaller-sized LDH nanoparticles (∼50–200 nm). Such delaminated Co–Al LDH, Zn–Al LDH, and Co–Zn–Al LDH solutions were used for the preparation of highly dispersed isotactic polypropylene (iPP) nanocomposites. Transmission electron microscopy and wide-angle X-ray diffraction results revealed that the LDH nanoparticles were well dispersed within the iPP matrix. The intention of this study is to understand the influence of the intralayer metal composition of LDH on the various properties of iPP/LDH nanocomposites. The sonicated LDH nanoparticles showed a significant increase in the crystallization rate of iPP; however, not much difference in the crystallization rate of iPP was observed in the presence of different types of LDH. The dynamic mechanical analysis results indicated that the storage modulus of iPP was increased significantly with the addition of LDH. The incorporation of different types of LDH showed no influence on the storage modulus of iPP. But considerable differences were observed in the flame retardancy and thermal stability of iPP with the type of LDH used for the preparation of nanocomposites. The thermal stability (50% weight loss temperature (T0.5)) of the iPP nanocomposite containing three-metal LDH (Co–Zn–Al LDH) is superior to that of the nanocomposites made of two-metal LDH (Co–Al LDH and Zn–Al LDH). Preliminary studies on the flame-retardant properties of iPP/LDH nanocomposites using microscale combustion calorimetry showed that the peak heat release rate was reduced by 39% in the iPP/Co–Zn–Al LDH nanocomposite containing 6 wt % LDH, which is higher than that of the two-metal LDH containing nanocomposites, iPP/Co–Al LDH (24%) and iPP/Zn–Al LDH (31%). These results demonstrated that the nanocomposites prepared using three-metal LDH showed better thermal and flame-retardant properties compared to the nanocomposites prepared using two-metal LDH. This difference might be due to the better char formation capability of three-metal LDH compared to that of two-metal LDH.

Temperature-Dependent Reinforcement of Hydrophilic Rubber Using Ice Crystals

This is the first study on the impact of ice crystals on glass transition and mechanical behavior of soft cross-linked elastomers. A hydrophilic elastomer such as epichlorohydrin–ethylene oxide–allyl glycidyl ether can absorb about ∼40 wt % of water. The water-swollen cross-linked network exhibits elastic properties with more than 1500% stretchability at room temperature. Coincidently, the phase transition of water into solid ice crystals inside of the composites allows the reinforcement of the soft elastomer mechanically at lower temperatures. Young’s modulus of the composites measured at −20 °C remarkably increased from 1.45 to 3.14 MPa, whereas at +20 °C, the effect was opposite and the Young’s modulus decreased from 0.6 to 0.03 MPa after 20 days of water treatment. It was found that a part of the absorbed water, ∼74% of the total absorbed water, is freezable and occupies nearly 26 vol % of the composites. Simultaneously, these solid ice crystals are found to be acting as a reinforcing filler at lower temperatures. The size of these ice crystals is distributed in a relatively narrow range of 400–600 nm. The storage modulus (E′) of the ice crystal-filled composites increased from 3 to 13 MPa at −20 °C. The glass transition temperature (−37 °C) of the soft cross-linked elastomer was not altered by the absorption of water. However, a special transition (melting of ice) occurred at temperatures close to 0 °C as observed in the dynamic mechanical analysis of the water-swollen elastomers. The direct polymer/filler (ice crystals) interaction was demonstrated by strain sweep experiments and investigated using Fourier transform infrared spectroscopy. This type of cross-linked rubber could be integrated into a smart rubber application such as in adaptable mechanics, where the stiffness of the rubber can be altered as a function of temperature without affecting the mechanical stretchability either below or above 0 °C (above the glass temperature region) of the rubber.

Evaluation of mechanical and dynamic mechanical properties of multiwalled carbon nanotube-based ethylene–propylene copolymer composites mixed by masterbatch dilution

A two-step masterbatch mixing technique was studied for preparation of carbon nanotube-filled ethylene–propylene diene elastomer compounds, and compared to conventional one-step mixing process. In the two-step process, a masterbatch compound with carbon nanotube content of 50 parts per hundred was prepared by melt-mixing ethylene–propylene diene elastomer. This material was then compounded with pristine ethylene–propylene diene elastomer and composites with different carbon nanotube concentrations were compared. The aim of this study is to compare the efficiency of two different mixing processes on the dispersion of carbon nanotubes and to facilitate the handling of carbon nanotubes, as the masterbatch can be prepared in a controlled way and used for further dilution without the problems related to carbon nanotube processing. The compound properties were studied with emphasis on mechanical characterization and dynamic mechanical thermal analysis. Masterbatch mixing resulted in the similar mechanical properties of the composites compared to the direct mixing method. At the relatively low loadings of carbon nanotubes, the considerable improvements of the mechanical properties were observed. The aspect ratio of the carbon nanotubes determined by transmission electron microscope was found to be similar to the one calculated from the Guth equation. It showed a considerable reduction in aspect ratio independent of the used mixing method.

Modification of Polysulfones by Carboxylic Acids

The modification of aromatic polysulfones (PSU) in the melt in continuous mixing aggregates (on the small-scale: twin-screw microcompounder; on the large-scale: twin-screw extruder) by low-molecular weight dicarboxylic acids is presented. Owing to the drastic conditions experienced by the melt in the extruder operating at 320 °C, chain scission of the polysulfones as well as the formation of reactive groups attached to the PSU chains was expected, using either trimellitic acid anhydride or terephthalic acid as dicarboxylic acids. However, no functional groups indicating a reaction between the PSU and the carboxylic acids were detected in the melt-processed PSU compounds. Nevertheless, the resulting thermal and mechanical properties of the PSU compounds were influenced remarkably by the carboxylic acids due to their different mixing behavior with the PSU melt. The tensile stiffness and strength of the compounds were significantly increased in comparison with the PSU reference. PSU compounds containing the trimellitic acid anhydride (at concentrations exceeding 5.7 wt.%) showed a particularly high strength at break, while all compounds had a lower toughness in comparison with the neat PSU.

Phase separation and surface properties of poly(propyl methacrylate-b-methyl methacrylate) diblock copolymers

The phase separation and surface characteristics of poly(propyl methacrylate-b-methyl methacrylate) (PPrMA-b-PMMA) diblock copolymers were studied and compared to strongly phase-separated poly(pentyl methacrylate-b-methyl methacrylate) (PPMA-b-PMMA) block copolymers (BCPs). PPrMA-b-PMMA with varied compositions and molar masses was synthesized by living anionic polymerization. The phase separation was studied by DSC, SAXS, TEM and AFM. The experimental data were compared to the calculated phase diagram. PPrMA-b-PMMA BCPs were weakly phase-separated, and indications for the existence of a relative broad interface between the blocks were observed. Nevertheless, two ordered morphologies—hexagonally packed cylinders and lamellae—depending on the molar composition were distinguished. The phase separation in thin films was studied by AFM in comparison with PPMA-b-PMMA. The wetting behavior of the thin films was examined by contact angle measurements. The water contact angles on PPrMA-b-PMMA were clearly influenced by both blocks. XPS confirmed the presence of both blocks in the top surface layer, which was different to PPMA-b-PMMA diblock copolymers where the top layer consisted only of PPMA blocks. Thus, only the weakly phase-separated PPrMA-b-PMMA BCP system allowed the generation of phase-separated films with tunable wetting characteristics.

In Situ Polymorphic Alteration of Filler Structures for Biomimetic Mechanically Adaptive Elastomer Nanocomposites

A mechanically adaptable elastomer composite is prepared with reversible soft-stiff properties that can be easily controlled. By the exploitation of different morphological structures of calcium sulfate, which acts as the active filler in a soft elastomer matrix, the magnitude of filler reinforcement can be reversibly altered, which will be reflected in changes of the final stiffness of the material. The higher stiffness, in other words, the higher modulus of the composites, is realized by the in situ development of fine nanostructured calcium sulfate dihydrate crystals, which are formed during exposure to water and, further, these highly reinforcing crystals can be transformed to a nonreinforcing hemihydrate mesocrystalline structure by simply heating the system in a controlled way. The Youngs modulus of the developed material can be reversibly altered from ∼6 to ∼17 MPa, and the dynamic stiffness (storage modulus at room temperature and 10 Hz frequency) alters its value in the order of 1000%. As the transformation is related to the presence of water molecules in the crystallites, a hydrophilic elastomer matrix was selected, which is a blend of two hydrophilic polymers, namely, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer and a terpolymer of ethylene oxide-propylene oxide-allyl glycidyl ether. For the first time, this method also provides a route to regulate the morphology and structure of calcium sulfate nanocrystals in a confined ambient of cross-linked polymer chains.