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.     

The Solid State Postcondensation of PET, 3

Summary: It was demonstrated that it is possible to produce prepolymers with a number‐average degree of polymerisation on the order of 5–40 directly in a liquid‐liquid dispersion in less than three hours. It was also shown that prepolymers made via this route and rapidly crystallised by the addition of a dispersant at ambient temperature are more porous than prepolymers made in an industrial liquid melt process.

SEM micrograph of prepolymers pLL‐PTA with \overline {DP} _{\rm n} = 28, d_p ∈ 63–125 μm.     

Colloidal Crystalline Arrays of β‐Polymorphic Poly(vinylidene fluoride)

Stable layers of nearly monodisperse spheres of β‐polymorphic poly(vinylidene fluoride) with iridescent properties are prepared. The colloidal crystalline arrays (CCAs) were characterized by optical microscopy, differential scanning calorimetry (DSC), and FT‐IR spectroscopy. FT‐IR spectroscopic and wide‐angle X‐ray scattering (WAXS) studies revealed a β‐polymorphic PVF₂ structure, the DSC study showed that the level of crystallinity in the CCA was much higher than that in the melt‐crystallized sample, and UV‐visible spectroscopy showed extinction peaks at 323 and 510 nm in the CCAs. The β‐polymorphic PVF₂ structure, along with the optical extinction properties of these CCAs, raises the prospect of their application in optical filters and/or piezoelectric sensors.

Optical micrograph of PVF₂ CCA films cast on glass substrates.     

Synthesis of Block Copolymers containing Chain‐Controlled Aramid and Fluoroethylene Segments

Summary: Novel block copolymers containing aromatic polyamide (aramid) and fluoroethylene segments were synthesized by a two‐step solution polycondensation. This synthetic method could control the chain‐length of aramid segments and these copolymers could have high structural regularity. The number‐average molecular weight ( ) of one of these polymers is over 2.0 × 10⁴. Incorporating fluoroethylene segments improves the solubility of the resulting polymer compared with conventional aramids.

The synthesis of the fluoroethylene‐aramid block copolymers.     

Design of a Microfluidic System to Investigate the Mechanical Properties of Layer‐by‐Layer Fabricated Capsules

A microfluidic system was designed, fabricated and implemented to study the behavior of polyelectrolyte capsules flowing in microscale channels. The device contains microchannels that lead into constrictions intended to capture polyelectrolyte microcapsules which were fabricated with the well‐known layer‐by‐layer (LbL) assembly technique. The behavior of hollow capsules at the constrictions was visualized and the properties of the capsules were investigated before and after introduction into the device.

Time series of video frames showing capsules being compressed into a constriction.     

Isobornyl Methacrylate as a Reactive Solvent of Polyethylene

Summary: Solutions containing 15 wt.‐% of a low‐molar‐mass polyethylene (PE) in isobornyl methacrylate (IBoMA), containing 0, 5 or 10 wt.‐% of 1,4 butanediol dimethacrylate (BDDMA) as crosslinker, were polymerized using either benzoyl peroxide (BPO), at 80 °C, or dicumyl peroxide (DCPO), with a thermal cycle attaining 150 °C, as initiators. Phase separation of an amorphous PE‐rich phase took place when carrying out the reaction at temperatures higher than the PE melting temperature. Partial crystallization of PE was observed when cooling to room temperature. Depending on the initial amount of BDDMA, the fraction of PE that was phase separated varied between 57 and 66% of the initial amount, with crystalline fractions in the range of 15 to 42%. The use of IBoMA as a reactive solvent of PE has two main advantages over other reactive solvents reported in the literature: a) it has a very low vapor pressure, and b) its free‐radical polymerization gives a polymer with a relatively high glass transition temperature.

Part of the cloud‐point curve for IBoMa, PIBoMA and PE solutions at 80 °C.     

PTFE Micropowder Functionalized with Carboxylic Acid Groups

PTFE powder irradiated in air at room temperature was studied by infrared spectroscopy, potentiometric titration with sodium hydroxide, and polyelectrolyte titration with poly(diallyl dimethylammonium chloride). Through the radiation‐induced degradation ? COF groups are formed in the material, which can be hydrolyzed to ? COOH groups. About 10–20% of the ? COOH groups are located at the surface of the PTFE particle. The ? COOH groups start to decompose under oxidizing conditions at temperatures above 200 °C. The decarboxylation results in the formation of ? CF?CF₂ groups, which are oxidized to ? COF groups in the presence of air.

     

Crystalline and Conductive Poly(3‐hexylthiophene) Fibers

Intrinsically conducting polymer fibers are prepared from P3HT by melt spinning. High crystallinity is achieved by drawing the fibers after the spinning process, applying a draw ratio of 1:2. DSC and XRD measurements confirm the continuous increase of crystalline phases with drawing. For comparison, poly(ethylene terephthalate) fibers are coated with P3HT and drawn as well. Again, the drawing of the coated fiber results in a significant increase in crystallinity of the P3HT coating. The high amount of crystalline phases is associated with a dramatic increase in conductivity (350 S · cm^?1) after doping with FeCl₃ in nitromethane.

     

Modeling of Ethylene‐Norbornene Copolymer Microstructure in Solution Polymerization with Homogeneous Metallocene Catalysts

Summary: The microstructure of ethylene‐norbornene copolymer produced in solution polymerization is analyzed through kinetic modeling and experiments using homogeneous rac‐Et(1‐indenyl)₂ZrCl₂/methylaluminoxane catalyst in toluene at 70 °C. The sequence distribution function and average chain length equations are derived for terminal model and penultimate model. The model simulations show that both models provide similar predictions of average copolymer composition, especially at low norbornene concentration in the copolymer. However, at higher norbornene concentrations the penultimate model yields much better predictions of norbornene sequence length distribution than the terminal model. The terminal model has been inadequate in describing the copolymerization rate, whereas the penultimate model yields excellent predictions of rate behavior. The model calculations also indicate that at norbornene concentration in the copolymer larger than about 10 mol‐%, the maximum ethylene block length is smaller than 70, prohibiting the formation of crystalline copolymer.

Ethylene sequence distribution curves at different mol‐% of norbornene in copolymer.     

Preparation and Characterization of Conducting Systems based on EPDM/PE/PS‐co‐DVB/HSb

Summary: Blends of different compositions were prepared from: a thermoplastic elastomer (EPDM), a low density polyethylene (PE), a polystyrene crosslinked with a small amount of divinylbenzene (PS‐co‐DVB) and an inorganic proton conductor: antimonic acid (HSb). The blends obtained were sulfonated heterogeneously with chlorosulfonic acid and were then structurally and electrically characterized by means of the following techniques: differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), crystallization kinetics under non‐isothermal conditions and complex impedance spectroscopy.

Dynamic mechanical analysis for EPDM and EP‐3 blends series.     

An Application of Silica‐Based Monolithic Membrane Emulsification Technique for Easy and Efficient Preparation of Uniformly Sized Polymer Particles

Summary: Uniformly sized polymer particles were prepared by an emulsification and polymerization technique utilizing a silica monolithic membrane, namely the “silica monolithic membrane emulsification technique”. In this paper, we utilized silica monolithic membrane as a device for the preparation of uniformly sized polymer particles. A mixture of monomers, diluents and oil‐soluble initiator was emulsified into a continuous medium through the silica monolithic membrane and polymerized. The particles obtained had a higher size uniformity than that of particles prepared by previously reported membrane emulsification techniques, such as the Shirasu Porous Glass (SPG) emulsification technique. Through the silica monolithic membrane emulsification technique, we could prepare particles having availability as a possible packing material for solid‐phase extraction (SPE) and high performance liquid chromatography (HPLC).

SEM photograph of silica particles prepared through capillary plate membrane.     

Nylon 6‐Polyesteramide Block Copolymers (NBC) and NBC/Phenolic Resin Composites, 1

Summary: A series of NBC/phenolic resin composites, containing 0, 1, 3, 5 or 7 wt.‐% of a powdered phenolic resin of different particle diameter, was prepared by the reaction injection molding (RIM) process. It was determined by SEM analysis that there exists a strong interaction between particles and matrix and that such interaction occurs through hydrogen‐type bonds as determined by FTIR analysis. According to the results it is thought that the glass transition temperature of the NBC/phenolic resin composites depends on two competing factors: the rigidity promoted by the hard solid filler and the flexibility imparted by the nylon 6 amorphous phase, whose proportion becomes more important with increasing amounts of phenolic resin particles. The elastic and flexural moduli of the NBC were improved by the addition of phenolic resin confirming the reinforcing effect of this filler. On the contrary, the impact strength diminishes with increasing amounts of phenolic resin, although this property is strongly dependent on the particle diameter.

SEM micrograph of the nylon 6‐polyesteramide block copolymer (80/20).     

Compatibilization of Polyamide‐6/Polyarylate Blends by Means of an Ionomer

Summary: Polyamide‐6 (PA6)/polyarylate of bisphenol A (PAr) blends rich in PA6 and modified with an additional 15% poly[ethylene‐co‐(methacrylic acid)] partially neutralized with zinc (PEMA‐Zn) as a compatibilizer were obtained by melt mixing. Their phase structure, morphology, and mechanical performance were compared with those of the corresponding binary blends. The ternary blends were composed of a PA6 amorphous matrix and a dispersed PAr‐rich phase in which reacted PA6 and PEMA‐Zn were present. Additionally, minor amounts of a crystalline PA6 phase, and a PEMA‐Zn phase were also present. The chemical reactions observed led to a clear decrease in the dispersed particle size when PEMA‐Zn was added, indicating compatibilization. Consequently, the mechanical behavior of the blends with PEMA‐Zn improved, leading, mainly in the case of the blend with 10% PAr, to significant increases in both ductility and impact strength with respect to those of the binary blends. These increases were more remarkable than the slight decrease in stiffness as a consequence of the rubbery nature of the compatibilizer.

Cryogenically fractured surface of the PA6/PAr‐PEMA‐Zn 70/30‐15 ternary blend.     

A Novel Impact Modifier for Nylon 6

A new carboxylated styrene‐butadiene rubber (CSBR) in ultrafine powder form was used to modify the properties of nylon 6. The nylon 6/CSBR blends possessed higher toughness than nylon 6/maleic anhydride‐grafted polyethylene‐octene elastomer (POE‐g‐MAH) system. TEM micrographs revealed the fine dispersion of CSBR particles with a diameter of 150 nm. The effective toughening of nylon 6 with CSBR was attributed to the good interface, fine dispersion, and shear yielding.

TEM photograph of undeformed Nylon 6/CSBR (80/20) blend (×40 000).     

Thermal and Thermomechanical Behaviour of Polycaprolactone and Starch/Polycaprolactone Blends for Biomedical Applications

Summary: Polycaprolactone (PCL) and starch/PCL blends (SPCL) are shown to have the potential to be used in a range of biomedical applications and can be processed with conventional melting‐based procedures. In this paper, the thermal and thermomechanical analyses of PCL and SPCL were performed, using DSC, optical microscopy and DMA. Starch effectively increased the non‐isothermal crystallisation rate of PCL. Non‐isothermal crystallisation kinetics was analyzed using Ozawa model, and a method, which combines the theories of Avrami and Ozawa. Starch effectively reinforced PCL and enhanced its damping properties, which indicated that SPCL could be more suitable than PCL in some biomedical applications, as it might help in the dissipation of the mechanical energy generated by the patient movements.

Dynamic mechanical behaviour of PCL and SPCL at 1 Hz.     

The Reinforcement of Elastomeric Networks by Fillers

Summary: The mechanisms involved in rubber reinforcement are discussed. A better molecular understanding of these mechanisms can be obtained by combining characterization of the mechanical behavior with an analysis of the chain segmental orientation accompanying deformation. While the strain dependence of the stress is the most common quantity used to assess the effect of filler addition, experimental determination of segmental orientation can be used to quantify the interfacial interactions between the elastomeric matrix and the mineral inclusions.

SEM micrograph of natural rubber containing 10 wt.‐% of organomodified clay.     

Influence of Screw Speed on Electrical and Rheological Percolation of Melt‐Mixed High‐Impact Polystyrene/MWCNT Nanocomposites

The influence of screw speed on the electrical and rheological percolation of HIPS/MWCNT composites prepared via melt mixing was investigated. Microscopic examination of these composites using POM, FESEM and HRTEM revealed optimum MWCNT dispersion was achieved at intermediate screw speeds. On addition of MWCNTs to HIPS, the electrical conductivity of HIPS increased by up to 12 orders of magnitude. At screw speeds up to 100 rpm an electrical percolation of 1–3 wt.‐% was achieved. This increased to 3–5 wt.‐% when the screw speed was increased to 150 rpm. The onset of a rheological percolation was detected for an MWCNT loading of 5 wt.‐%, irrespective of screw speed employed. An up‐shift in the Raman G‐band of 24 cm^?1 was observed, implying strong interfacial interaction between HIPS and MWCNTs.

     

Crystallization and Morphology of Poly(ethylene 2,6‐naphthalene dicarboxylate) Containing Additives

The influence of nucleating agents (AClyn^®, Surlyn^® and sodium benzoate (SB)) alone and together with nucleating promoter (Ceraflour^® 993 and Ceraflour^® 991 and poly(1,4‐butylene sebacate)) on the crystallization and morphology of poly(ethylene 2,6‐naphthalene dicarboxylate) (PEN) was investigated by means of differential scanning calorimeter, polarized optical microscopy and small angle light scattering. It was revealed that AClyn, Surlyn and SB effectively accelerate nucleation and crystallization of PEN with increasing the ratio of nucleating agent up to 1 wt.‐%. A combination of nucleating agent and nucleating promoter leads to further increase in crystallization rate at low temperature, but only a slight change at high temperature. Hedrites were obtained in pure PEN and the addition of SB and Ceraflour 993 produces small crystals with poor perfection upon crystallization in high temperature region. When crystallization temperature was below 210 °C, spherulites were observed in pure PEN and also in the samples of PEN/Ceraflour 993 and PEN/SB but with smaller size.

Crystal morphology of PEN crystallized at 240 °C for 40 min.     

Structure and Mechanical Properties of Polyurethane/Silica Hybrid Coatings

Summary: Polyurethane/silica hybrid coatings were prepared via in situ (IS) or blending (BL) method using different acidic silica sols. The effects of preparation methods, silica types, and content on the structure and mechanical properties of the hybrid coatings were investigated. It was found that there existed two types of silica phases in the hybrid coatings: silica‐rich agglomerate and primary silica‐rich phase, whose size and compactness depended upon the silica types and the preparation methods. Introducing silica could result in obvious changes in surface free energy, atomic composition, and mechanical properties of the hybrid coatings.

Typical SEM image of the fractured surface of hybrids obtained by the in situ method.