A Novel N‐Succinylchitosan‐graft‐Polyacrylamide/Attapulgite Composite Hydrogel Prepared through Inverse Suspension Polymerization

A novel N‐succinylchitosan‐graft‐polyacrylamide/attapulgite composite hydrogel was prepared by using N‐succinylchitosan, acrylamide and attapulgite through inverse suspension polymerization. The result from FTIR spectra showed that ? OH of attapulgite, ? OH and ? NHCO of N‐succinylchitosan participated in graft polymerization with acrylamide. The introduced attapulgite could enhance thermal stability of the hydrogel. Scanning electron microscopy observation indicates that the composite hydrogel has a microporous surface. The volume ratio of heptane to water, weight ratio of acrylamide to N‐succinylchitosan and attapulgite content have great influence on swelling ability of the composite hydrogel. The composite hydrogel shows higher swelling rate and pH‐sensitivity compared to that of without attapulgite.

     

Near Infrared Reflection Spectroscopy: A Versatile Tool for Rapid Characterization of Olefin Copolymers and High‐Throughput Experiments

Near infrared (NIR) spectroscopy was developed as a rapid analytical method for the determination of the composition of olefin copolymers obtained in high‐throughput screening. NIR spectra of ethene/propene and ethene/1‐hexene copolymers, also characterized by means of ¹³C NMR spectroscopy, were recorded and used to design multivariate calibration models. Different methods for the preprocessing of the spectra, including the linearization by non‐linear transformations, were compared. Optimal methods and error estimates were established using crossvalidation. This technique is of particular interest for the rapid on‐line analysis of high‐throughput experiments in the field of polymer and catalyst design employing methods from combinatorial chemistry.

Predicted versus true value of the propene incorporation and standard deviation for ethene/propene copolymers.     

Methionine‐Containing Poly(amino acid) Hybrid Fibers via Self‐Assembly at Aqueous Interface

Summary: Using sulfonium groups to create a novel fiber material, methionine‐containing hybrid fibers were prepared from S‐methylated poly(L ‐methionine) and poly(L ‐lysine, L ‐methionine) solutions with gellan solution by polyion complex (PIC) formation via self‐assembly at the aqueous interface. The breaking strain of the PIC fibers were increased by incorporation of methionine residues into the poly(L ‐lysine). These findings may provide a new approach for preparing a wool‐like fiber in aqueous media using the synthetic water‐soluble methionine‐containing poly(amino acid)s.

SEM image of Met‐containing PIC fiber: (a) poly[Met¹⁹Met(SMe)⁸¹]‐gellan fiber (magnification, ×500).     

Segmented Block Copolymers with Monodisperse Hard Segments: The Influence of H‐Bonding on Various Properties

The properties of segmented‐copolymer‐based H‐bonding and non‐H‐bonding crystallisable segments and poly(tetramethylene oxide) segments were studied. The crystallisable segments were monodisperse in length and the non‐hydrogen‐bonding segments were made of tetraamidepiperazineterephthalamide (TPTPT). The polymers were characterised by DSC, FT‐IR, SAXS and DMTA. The mechanical properties were studied by tensile, compression set and tensile set measurements. The TPTPT segmented copolymers displayed low glass transition temperatures (T_g, ?70 °C), good low‐temperature properties, moderate moduli (G′ ≈ 10–33 MPa) and high melting temperatures (185–220 °C). However, as compared to H‐bonded segments, both the modulus and the yield stress were relatively low.

     

Rigid‐Rod Polymers: Synthesis,Processing, Simulation,Structure, and Properties

Synthesis, structure, and properties of rigid‐rod polymers with special emphasis on poly(p‐phenylene benzobisoxazole) (PBO) and poly(p‐phenylene benzobisthiazole) (PBZT) have been reviewed. Recent studies on chemical modifications and molecular simulations have also been given. After nearly 20 years of research and development, PBO fiber was commercialized in the late 1990s. However, due to processing difficulties, the concept of the so called molecular composites has not been successful. Development of the high compressive strength M5 and dihydroxy‐PBI fibers clearly suggest that there is potential for further developing properties of this class of materials. Opto‐electronic properties have also been reviewed.

Synthesis of PBZT.     

Fabrication of Aligned Poly(L‐lactide) Fibers by Electrospinning and Drawing

A new target collector was designed for taking up aligned nanofibers by electrospinning. The collector consists of a rotor around which several fins were attached for winding electrospun filaments continuously in large amounts. The alignment of the nanofibers wound on the collector was affected by the electrospinning conditions, such as the needle‐to‐collector distance and the applied voltage, but not by the rotation speed of the collector. At a voltage of 0.5 kV · cm^?1, about 60% of the fibers were found to be aligned within an angle of ± 5° relative to the rotational direction of the collector. The fiber alignment was improved to 90% by drawing the fiber bundle 2–3 times at 110 °C. The drawing was also effective for crystal orientation of the fibers as revealed by WAXD. The drawn fibers show improved mechanical properties.

     

A Novel Route to Multiphase Polymer Systems Containing Nano‐Droplets: Radical Polymerization of Vinylic Monomers in Gelled Water‐in‐Oil Miniemulsions

Summary: A new strategy for the synthesis of composite polymers with larger volume fraction of aqueous inclusions less than 1 µm in diameter is presented. A water‐in‐oil miniemulsion of aqueous droplets in a continuous, cross‐linkable monomer phase is prepared. The addition of an organo‐gelator allows the immobilization of the droplets in a solid gel, thus avoiding the usual demixing upon polymerization of the continuous phase. This pregelled system is then converted into a composite polymer by photoinitiated free radical polymerization. Such coatings may be used for an improved climate control of buildings or as a deposit for the controlled release of actives from polar nano‐droplets.

SEM image of a cross‐linked composite polymer showing controlled droplet inclusions with a maximal diameter of 500 nm.     

Analysis of Crosslinked Styrene‐Butadiene Rubbers by Liquid Chromatography and FT‐IR Spectroscopy, 1

Crosslinked styrene‐butadiene and butadiene rubbers can efficiently be analyzed by liquid chromatography and FT‐IR spectroscopy. In a first step the vulcanizate is pyrolyzed under mild conditions. The resulting high molar mass fragments are extracted from the bulk material and analyzed by size exclusion chromatography. The molar masses of the extractables are in the range of 3 000 to 25 000 g/mol. The chemical composition as a function of molar mass is visualized by coupled SEC‐FT‐IR spectroscopy. By quantitative analysis of the FT‐IR spectra the concentrations of the different structural units, including styrene, 1,4‐trans‐butadiene, 1,2‐vinylbutadiene, and 1,4‐cis‐butadiene, are determined. It is shown that the chemical composition of the original non‐crosslinked rubbers and the chemical composition of the extractables are rather identical. Therefore, this technique can be used to obtain structural information on rubber formulations even in the case when the material is already vulcanized.

SEC chromatograms of SBR 1712 and the extractables after pyrolysis, stationary phase: SDV linear, mobile phase: THF, detector: ELSD.     

Bio‐Based Rubbers by Concurrent Cationic and Ring‐Opening Metathesis Polymerization of a Modified Linseed Oil

Bio‐based rubbers prepared by tandem cationic polymerization and ROMP using a norbornenyl‐modified linseed oil, Dilulin?, and a norbornene diester, NBDC, have been prepared and characterized. Increasing the concentration of the NBDC in the mixture results in a decrease in the glass transition temperature. The new bio‐based rubbers exhibit tensile test behavior ranging from relatively brittle (18% elongation) to moderately flexible (52% elongation) and with decreasing values of tensile stress with increasing NBDC content. Thermogravimetric analysis reveals that the bio‐based rubbers have maximum decomposition temperatures of over 450 °C with their thermal stability decreasing with increasing loadings of NBDC.

     

Poly(acrylonitrile‐butadiene‐styrene)/Poly(ether ether ketone) Blends: an Attempt Towards a Polymer Reinforced Polymer Composite

Summary: Blends of poly(acrylonitrile‐butadiene‐styrene) (ABS) and poly(ether ether ketone) (PEEK), in which PEEK has been used as a reinforcing medium for the ABS matrix in ratios up to 20 wt.‐% of the blend, were prepared by melt mixing using a laboratory mixer. All the blend compositions were processed at the ABS processing temperature so that the PEEK was dispersed in the ABS matrix without actually melting. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) studies revealed that the glass transition temperature (T_g) of the ABS phase in the blend did not show any appreciable change with composition. The dynamic storage modulus measured by DMA was found to be higher for the blend as compared to pure ABS due to reinforcement of the matrix by PEEK. The tensile strength and modulus behavior of these blends were found to follow the curves predicted using models proposed for composite systems having perfect adhesion, which shows the presence of some physical interaction between the blend components. The good tensile properties of the blend have been correlated with the observed morphology. The disperse phase in the blend has been found to be present in extremely small (sub‐micron) dimensions, which not only provides more surface area for possible interactions between the blend components but also result in efficient stress transfer between the matrix and the dispersed phase during the tensile tests. The thermal stability of the blends was investigated using thermogravimetric analysis (TGA). TGA further revealed that the constituents degraded at their respective decomposition temperatures.

SEM micrograph of tensile fractured surface of an ABS/PEEK 90/10 blend.     

Processing,Structure, and Properties of PAN/MWNT Composite Fibers

Conventional dry‐jet wet fiber spinning techniques were used to fabricate continuous PAN/MWNT composite fibers with up to 20 wt.‐% nanotube loading. PAN at the MWNT interface exhibited lower solubility under thermodynamically favorable conditions than in bulk PAN, indicating good interfacial interaction. Due to the PAN/MWNT interaction at the interface, thermal shrinkage decreases with increasing MWNT loading (5 to 20 wt.‐%). For high MWNT loadings, PAN/MWNT composite fiber at 15 wt.‐% MWNT loading showed an axial electrical conductivity of 1.24 S · m^?1. For all loadings, PAN/MWNT composite fibers exhibited higher tensile moduli than theoretically predicted by rule‐of‐mixture calculations, suggesting good reinforcement of the PAN by MWNT.

     

Structure and Properties of Cellulose Films Reinforced by Chitin Whiskers

Cytocompatible nanocomposite films are prepared by blending α‐chitin whiskers and cellulose solution in NaOH/urea. Structure and properties of the chitin/cellulose composite films are characterized by FT‐IR, XRD, ¹³C NMR, SEM, UV‐Vis, TGA, and tensile tests. The results reveal that the chitin whiskers are dispersed homogeneously, leading to good miscibility and properties of the chitin/cellulose composite films. By varying the chitin whisker content, the tensile strength and elastic modulus of the films can be controlled. HeLa and T293 cells are seeded onto the surfaces of the nanocomposite films, showing that the composite films were nontoxic to both cell types and that the addition of chitin whiskers promotes cell adhesion and proliferation.

     

Preparation and Characterization of Organic/Inorganic Polymer Composites Based on Mg‐Silicates

Summary: An organic‐inorganic hybrid material consisting of a 3‐(methacryloxy)propyl functionalized SiO₂/MgO framework was synthesized. This hybrid was successfully reacted with styrene, butyl acrylate and butyl methacrylate via a free radical emulsion polymerization to form polymer composites. The polymer composites were investigated by means of FT‐IR spectroscopy, TGA, DSC and rheometry. It is shown that the polymer is linked covalently to the organic/inorganic hybrid. Although the polymer content is rather low, the composites exhibit a polymer‐like character and enhanced mechanical properties compared to the corresponding homopolymers.

     

Preparation of Poly(ethylene‐octene) Elastomer/Clay/Wood Flour Nanocomposites by a Melting Method

Summary: The new nanocomposites consisting of metallocene poly(ethylene‐octene) (POE), silicate clay and wood flour (WF) were prepared by means of a melt blending method. In addition, maleic anhydride grafted poly(ethylene‐octene) (POE‐g‐MAH) was studied as an alternative to POE. The samples were characterized by XRD, FT‐IR spectroscopy, DSC, TGA, SEM, and mechanical testing. Based on the consideration of thermal and mechanical properties, it was found that the clay content of 11 wt.‐% was optimal for the preparation of POE‐g‐MAH/clay nanocomposites. The POE‐g‐MAH/clay/WF hybrid could obviously improve the mechanical properties of POE‐g‐MAH/WF hybrid since the former had the smaller WF phase size (being always less than 1.5 µm), the Si? O? C bond and the nanoscale dispersion of silicate layers in the polymer matrix. The biodegradation studies showed that the mass of hybrids reduced by about the content of WF. The new POE‐g‐MAH/clay/WF nanocomposites produced from our laboratory can provide a plateau tensile strength at break when the WF content was up to 50 wt.‐%.

     

Fracture Behaviour of Styrene/Butadiene Block Copolymers having Different Molecular Architecture

The crack toughness behaviour of styrene/butadiene block copolymers of triblock and star architectures was investigated using instrumented Charpy impact testing. In order to evaluate adequately the toughness behaviour of the investigated materials, different concepts of elastic‐plastic mechanics (J‐integral and crack‐tip opening displacement, CTOD concepts) were used. Although the lamellar block copolymers showed a remarkably enhanced ductility in the tensile test than the neat block copolymer having hexagonal PB cylinders in PS matrix, no pronounced difference in crack toughness was found. This behaviour implies that the tensile strain cannot be regarded as the only parameter defining the toughness value. A brittle/tough transition was observed in a lamellar star block copolymer on blending with a linear thermoplastic elastomeric SBS triblock copolymer.

SEM micrograph showing the details of the stable crack propagation region in a binary block copolymer blend.     

Metallized Organoclays as New Intermediates for Aqueous Nanohybrid Dispersions,Nanohybrid Catalysts and Antimicrobial Polymer Hybrid Nanocomposites

Summary: The chemical metallization of aqueous bentonite dispersions afforded stable aqueous hybrid nanoparticle dispersions containing simultaneously dispersed sodium bentonite nanoplatelets together with bentonite supported silver, palladium, or copper nanoparticles with average metal nanoparticle diameters varying between 14 and 40 nm. Such aqueous bentonite/metal hybrid nanoparticle dispersions were blended with cationic PMMA latex to produce PMMA hybrid nanocomposites containing exfoliated polymer‐grafted organoclay together with bentonite supported metal nanoparticles. This dispersion blend formation was investigated with respect to the role of nanostructure formation and mechanical properties. Palladium/bentonite hybrid dispersions were used as catalysts for hydrogenation reactions and the electroless plating of copper. In contrast to the conventional organoclay nanocomposites, the PMMA hybrid nanocomposites, containing simultaneously dispersed organoclay nanoplatelets together with organoclay supported silver nanoparticles, exhibited high antimicrobial activity against the ubiquitous bacterium Staphylococcus aureus, even at low silver content.

Preparation of a polymer hybrid nanocomposite.     

Photoinduced Polymerization in the Wall of Hollow Capsules

Summary: Novel light‐sensitive hollow capsules were fabricated from the small molecule 3‐sulfopropylacrylate potassium (SPA) and poly(allylamine hydrochloride) (PAH). With UV irradiation, SPA could be photopolymerized in the wall of hollow capsules. After photopolymerization the capsule size and surfaces showed pronounced differences. The capsules became much more rigid as indicated by an increase in the modulus of more than a factor of 5.

CLSM image of SPA/PAH hollow capsule emission at 554 nm, from rhodamine B after photopolymerization.     

Viscoelasticity in Polymer Films on Rigid Substrates

The viscoelasticity of two thermally crosslinked polymer coatings was examined in terms of relaxation of the applied stress after a sudden strain. Two different transient methods were utilized: flat‐ended cylindrical indentation testing of a polymer film on a rigid substrate and tensile testing of a corresponding free‐standing polymer film. The correlation between tensile and indentation tests was studied. The mechanical response of a viscoelastic layer deposited on a rigid substrate was investigated as a function of indentation depth. There was good agreement between the results of the tensile and indentation tests for thick film layers at moderate indentation depths. The findings indicate that the substrate influences the coating performance by reducing the viscous contribution to the stress response and amplifying the magnitude of the equilibrium modulus for large indentation depths. The indentation method utilized here was shown to be a potentially suitable tool for the determination of Poisson's ratio of polymer films.

     

Flexible Use of Single‐Screw Extruders through Multiple‐Process Optimization

Using general‐purpose screws to process different types of material offers considerable cost advantages over special‐purpose screws. Designing screws of this type is generally a difficult task, since modifications to different aspects of the geometry can run counter to each other in some cases. Optimization software is thus of particular benefit here. For this reason, a program was developed for the optimization of general‐purpose screws. A central feature of this program is an appraisal system for the computer‐aided evaluation of single‐screw simulations. The performance of the software was verified on the basis of actual extrusion experiments.

Temperature measuring cross for measuring thermal homogeneity.     

Morphology,Electrical, and Rheological Properties of Silane‐Modified Silver Nanowire/Polymer Composites

Electrically conducting films containing AgNws, hydrophilic and hydrophobic resins were prepared. FT‐IR reveals that the interface between the AgNws and epoxy could be successfully modified by APTES. XPS shows that the AgNws were attracted by hydrogen bonds of ? NH₂ and ? NH? groups after APTES modification. SEM analysis shows that the AgNws were well dispersed in the resin. The AgNws were also blended with hydrophilic and acrylic resins, and the resulting blends were compared with AgNws/epoxy blends. Results show that AgNw/PVA‐resin films possess the lowest surface electrical resistance. The AgNw/PVA‐resin and silane‐modified AgNw/epoxy resin conductive films possess a similar electrical percolation threshold.