Viscoelastic Behavior and Force Nature of Thermo‐Reversible Epoxy Dry Adhesives

The gecko adhesion phenomenon has stimulated efforts to produce synthetic patterned dry adhesives. Besides introducing surface patterns on dry adhesives, it is also highly desirable to understand their intrinsic material properties. This communication reports the viscoelastic behavior of non‐patterned epoxy elastomers exhibiting intrinsic adhesion that is much higher than that of elastomers typically used for structure patterning. The diverse molecular origin of the adhesion is revealed through the study of adhesion against various substrates.

     

Silica‐Protected Micron and Sub‐Micron Capsules and Particles for Self‐Healing at the Microscale

A generalized silica coating scheme is used to functionalize and protect sub‐micron and micron size dicyclopentadiene monomer‐filled capsules and polymer‐protected Grubbs' catalyst particles. These capsules and particles are used for self‐healing of microscale damage in an epoxy‐based polymer. The silica layer both protects the capsules and particles, and limits their aggregation when added to an epoxy matrix, enabling the capsules and particles to be dispersed at high concentrations with little loss of reactivity.

     

Synthesis and Dispersion Characteristics of Multi‐Walled Carbon Nanotube Composites with Poly(methyl methacrylate) Prepared by In‐Situ Bulk Polymerization

Multi‐walled carbon nanotubes (MWNT) purified by acidic solution were processed with PMMA via an in‐situ polymerization. Experimental evidences indicate the role of radical initiator (AIBN) and MWNT, showing increases of polymerization rate and MWNT diameter. Induced radicals on the MWNT by AIBN were found to trigger the grafting of PMMA. Moreover, the solvent cast film showed a better nanoscopic dispersion of MWNT and possibilities of CNT composites in engineering applications.

Fractured surface of multi‐walled carbon nanotube composite with PMMA prepared by in‐situ bulk polymerization.     

Thermal Degradation Processes in Poly(acyl sulfides) Investigated by Pyrolysis–Gas Chromatography/Mass Spectrometry

A series of poly(acyl sulfides) were synthesized by polycondensation of acid dichlorides with sodium sulfide using tetrabutylammoniumhydrogen sulfate as a phase transfer catalyst. The thermal stability of these polymers was determined by thermogravimetric analysis. A unique phenomenon of exothermic degradation behavior was observed by differential thermal analyses, which is attributed to the energetics of the acylsulfide linkage during the thermal degradation. The mechanism of formation of degradation products was investigated by the pyrolysis–gas chromatography/mass spectrometry (Py‐GC/MS) technique.

The acylsulfide linkage containing polymers synthesized exhibit unique degradation behavior.     

A Template‐Free Method toward Urchin‐Like Polyaniline Microspheres

Urchin‐like PANI microspheres with an average diameter of 5–10 µm have been successfully prepared. Their surfaces consist of highly oriented nanofibers of ≈30 nm diameter and 1 µm length. The solvent composition plays an important role in the formation process of urchin‐like PANI microspheres. The structure of the products has been characterized by FT‐IR, UV‐vis, and XRD. To investigate the self‐assembly of urchin‐like PANI microspheres, the effect of polymerization time on the morphology of the products has been studied. The morphological evolution process indicates that the urchin‐like microspheres originate from the self‐assembly of nanoplates, which then grow into urchin‐like microstructures with nanofibers on the surface.

     

Polyaniline Microspheres Consisting of Highly Crystallized Nanorods

The preparation of self‐assembled polyaniline (PANi) microspheres via facile interfacial oxidation polymerization of aniline in the presence of DL ‐tartaric acid dopant is reported. Compared with PANis reported in the literature, the PANi prepared in this study exhibits a nanorod‐bundle morphology with exceptionally high crystallinity. These nanorods or nanorod bundles can self‐assemble into microspheres with unique alignment. The chemistry, morphology, and crystal structure of DL ‐tartaric acid doped microspheres were studied using SEM, TEM, SAED, XRD, and FTIR.

     

Photochemical Generation of Ferrocene‐Based Redox‐Polymer Networks

A photochemical approach toward the generation of enzyme‐containing redox polymer networks, which are the key material in enzymatic sensors and biofuel cells, is described. The approach is based on the incorporation of photo‐reactive benzophenone groups into the redox polymers. The obtained polymers are then deposited on the surface of glassy carbon electrodes and cross‐linked by illumination with UV light at 365 nm. If this step is done in the presence of the enzyme glucose oxidase, functional electrodes are obtained that yield electrical power upon addition of glucose. This work specifically addresses the question of electrode stability in buffer and demonstrates how slight variations in the chemistry of the redox polymer have a dramatic effect on the electrochemical performance of the electrodes. Different ferrocene‐containing redox polymer networks are synthesized and their properties in physiological buffer are studied.

     

A Composite Polymer Film with both Superhydrophobicity and Superoleophilicity

Summary: A composite film composed of porous polyurethane (PU) and polystyrene (PS) microspheres with both superhydrophobicity and superoleophilicity has been prepared. In this film, the dual‐scale structure enhances both the hydrophobicity and oleophilicity of the surface material. The composite film with such an ‘intelligent’ wettability property can be utilized to separate oil and water systems efficiently.

The composite film can be used to separate diesel oil and water.     

Antioxidant Activity of Graft Chitosan Derivatives

Graft chitosan derivatives (CMCTS‐g‐MAAS and CMCTS‐g‐AAS) were prepared by the graft copolymerization of methacrylic acid sodium (MAAS) and acrylic acid sodium (AAS) onto the etherification product of chitosan‐carboxymethyl chitosan (CMCTS). Their antioxidant activity was estimated as superoxide anion scavengers by chemiluminescence techniques. The derivatives with low grafting percentages have a relatively low 50% inhibition concentration (IC₅₀), which could be related to the fact that they have different contents of hydroxyl and amino groups in the polymer chains.

Superoxide radical scavenging activity of CMCTS‐g‐MAAS.     

Electrical Conductivity of an Individual Polyaniline Nanotube Synthesized by a Self‐Assembly Method

Camphor sulfonic acid (CSA) doped polyaniline (PANI) nanotubes (175 nm in outer diameter and 120 nm in inner diameter) were synthesized successfully by a self‐assembly method. It is found that the room‐temperature conductivity of an individual PANI nanotube is 30.5 S · cm⁻¹; in particular, the intrinsic resistance of an individual nanotube (30 kΩ) is much smaller than the contact resistance of crossed nanotubes (500 kΩ).

A SEM image of two crossed PANI‐CSA nanotubes and the attached Pt electrodes.     

Multiphase‐Separated Polyurethanes Studied by Micro‐Raman Spectroscopy

Micro‐Raman spectroscopy has been used to investigate the chemical micro‐heterogeneity of multiphase‐separated poly(ether urethanes) (PETU). Analysis of PETU cross‐sections by means of micro‐Raman spectroscopy revealed the nearly complete absence of soft segments in AI aggregates (called globules). These aggregates are in the order of a few micrometers in size. The composition of the matrix and the AII aggregates (spherulites) was comparable.

Example of an AFM image (sample 706, scan size 25 μm, converted to monochromatic image).     

Raspberry‐Like Aggregates Containing Secondary Nanospheres of Polystyrene‐block‐poly(4‐vinylpyridine) Micelles

Summary: Raspberry‐like aggregates containing secondary nanospheres were studied. The formation of raspberry‐like aggregates was due to complexation between core‐shell microspheres and core‐corona micelles. The core‐shell microspheres were synthesized with soap‐free polymerization of styrene and methyl acrylic acid, which included carboxyl groups in the periphery. The micelles were self‐assembled by polystyrene‐block‐poly(4‐vinylpyridine), which contained pyridine groups in the corona. The driven force to form raspberry‐like aggregates was due to the affinity between the carboxyl and pyridine groups. The morphology of the raspberry‐like aggregates could be tuned by changing the ratio of the microspheres to micelles. IR measurements suggested that the raspberry‐like aggregates were like zwitterions.

TEM image of the raspberry‐like aggregates formed at a molar ratio of MAA to 4VP at 1:4.     

Kinetic Modeling of Semi‐Interpenetrating Polymer Network (SIPN) Process ‐ A Comprehensive Study on the Case of Polyethylene/Polystyrene Semi‐I IPN

A comprehensive kinetic model is developed for a semi‐interpenetrating polymer network (SIPN) process, which involves simultaneous crosslinking, grafting, and degradation. Computational expense has been reduced considerably through a new component decomposition strategy, where a continuous variable approximation and a fixed pivot technique are applied for modeling each component. The inter‐polymer formulation is then reconstructed by a statistical approach. Based on the kinetic parameters obtained from the literature and a series of experiments, the model provides consistent agreement for gel fraction, joint molecular weight distribution (MWD) and polymer composition predicted in the studied cases, showing promising capability for the SIPN industrial application as well as for other polymer composite systems.

     

Drug Delivery Systems Based on Porous Chitosan/Polyacrylic acid Microspheres

Porous microspheres have been prepared by suspension free radical polymerization of acrylic acid (AA) in the presence of chitosan (CHI). The microspheres were characterized by FTIR and environmental SEM. The PAA content of the microspheres was estimated to be in the range 45–50 wt.‐%. The swelling degree of these particles is almost constant in the range 2 < pH < 5, but it increases considerably as the pH is raised from 5 to 10. The release profiles of microspheres loaded with meclofenamic acid (MF) were determined at pH 2, 7.4, and 10. The in vitro release of MF at different pHs was modulated by the solubility of the drug. These microcapsules are biodegradable and presented good biocompatibility and biodegradability during in vivo experiments.

ESEM microphotograph of the porous PAA/CHI microspheres.     

Polyelectrolyte Multilayer Microspheres as Carriers for Bienzyme System: Preparation and Characterization

Summary: Polyelectrolyte multilayer microspheres were prepared by alternating adsorption of dextran sulfate and protamine on melamine formaldehyde cores followed by the partial decomposition of the core. Peroxidase and glucose oxidase were immobilized in the prepared microspheres. Retention of enzymatic activity of the peroxidase/glucose oxidase system incorporated into the microspheres was demonstrated. Applicability of the bienzyme system immobilized in the microspheres for kinetic glucose assay was shown.

SEM image of the polyelectrolyte multilayer microsphere.     

On‐Chip Alginate Microencapsulation of Functional Cells

We report the use of a PTFE‐based microfluidic device for the encapsulation of living, therapeutically‐active cells within monodisperse alginate microspheres. We present a novel microfluidic platform and a flexible experimental method for the production of alginate microspheres. Cell lines HEK293, U‐2 OS and PC12 were separately encapsulated using this method, with minimal loss of cell viability.

     

Copolymerization of Ethylene and 10‐Undecen‐1‐ol using a Montmorillonite‐Intercalated Metallocene Catalyst: Synthesis of Polyethylene/Montmorillonite Nanocomposites with Enhanced Structural Stability

Summary: Ethylene and 10‐undecen‐1‐ol have been successfully copolymerized by an organically modified montmorillonite (OMMT)‐intercalated metallocene catalyst, Et[Ind]₂ZrCl₂, activated by methylaluminoxane (MAO). The obtained hydroxy‐functionalized polyethylene (PE‐OH)/OMMT nanocomposites exhibit enhanced structural stability as compared with the neat PE‐based ones, with no significant collapse of the nanocomposite structure being detected by WAXD examination after high‐temperature processing. The simultaneous polyolefin functionalization provides an effective and convenient solution to stabilize the PE/MMT nanocomposite structure formed by in‐situ polymerization.

     

Nonaggregated Zinc Phthalocyanine in Mesoporous Nanocrystalline TiO2 Thin Films

Summary: A simple sonochemical approach has been successfully developed to deposit poorly dissolved phthalocyanine dyes onto the surface of a highly‐ordered mesoporous nanostructured TiO₂ thin film. The aggregation‐free phthalocyanines are effectively encapsulated and stabilized in the nanopore arrays of the zeolite‐like mesoporous nanocrystalline TiO₂ thin film. Highly dispersed dye∥TiO₂ heterojunction arrays with a large contact area can be obtained by using this interesting approach.

The incorporation of phthalocyanine dyes into the surface of a highly‐ordered mesoporous nanostructured TiO₂ thin film, a potential photocatalyst.