Structure Formation of Integral Asymmetric Composite Membranes of Polystyrene‐block‐Poly(2‐vinylpyridine) on a Nonwoven

The formation of an integral asymmetric membrane composed of a cylinder‐forming polystyrene‐block‐poly(2‐vinylpyridine) on a nonwoven by using solvent casting followed by solvent/nonsolvent exchange (phase inversion) is reported for the first time. The influence of parameters such as solvent composition, evaporation time of the solution‐cast block copolymer film before phase inversion, and immersion bath temperature is demonstrated. The optimized membranes are characterized in terms of stimuli‐responsive water flux properties. The morphologies of the membranes as well as of the bulk of the block copolymer are imaged by scanning force microscopy, scanning electron microscopy, and transmission electron microscopy.

     

Control of Bubble Size and Location in Nano‐/Microscale Cellular Poly(propylene)/Rubber Blend Foams

Plastic foam with nano‐/micro‐scale cellular structures was prepared from a poly(propylene) (PP)/propylene‐ethylene copolymer (PER) blend by controlling bubble nucleation sites and bubble growth in disperse PER domains. Batch foaming experiments using a CO₂ pressure quench method were conducted at room temperature. The bubble size and location were highly controlled in disperse PER domains by exploiting the differences in CO₂ solubility and viscoelasticity between the PER domains and the PP matrix. The average cell diameter of PP/PER blend foams can be controlled within 0.5–2 µm by the PP/PER ratio, depressurization rate, and foaming temperature.

     

Coaxial Electrospinning with Triton X‐100 Solutions as Sheath Fluids for Preparing PAN Nanofibers

Coaxial electrospinning using surfactants as sheath fluid for preparing high‐quality polymer nanofibers is studied. PAN nanofibers are fabricated using this process with Triton X‐100 solutions in DMF. FESEM demonstrates that the Triton X‐100 solution has a significant influence on the quality of the nanofibers. The nanofiber diameters can be controlled by adjusting the concentration of Triton X‐100 in the sheath fluids with a scaling law D = 640 C^?0.32. The mechanism of the influence of Triton X‐100 solutions on the formation of PAN fibers is discussed and it is demonstrated that coaxial electrospinning with surfactant solution is a facile method for achieving high‐quality polymer nanofibers.

     

Polyurethane Foams of Improved Thermal Stability

In reactions of polyetherols prepared from hydroxymethyl derivatives of uric acid and typical oxiranes with isocyanates and water one obtains a new group of polyurethane foams containing purine rings in their structure. These polyurethanes withstand prolonged heating at temperatures as high as 200 °C. Preliminary results on the effect of the type of polyetherol and the composition used in preparation of the polyurethane foams on their properties are presented. The results of studies on thermal stability and mechanical properties of the foams before and after thermal treatment are also reported.

     

Lignocellulosic Flour from Cladodes of Opuntia ficus‐indica Reinforced Poly(propylene) Composites

Summary: A lignocellulosic flour was obtained by grinding dried cladodes of Opuntia ficus‐indica. It was used as low cost natural filler in PP and the effect of the treatment of the filler with MAPP was also investigated. The morphology and thermal properties of these composites were evaluated by SEM and DSC, respectively. MAPP coating resulted in a better adhesion between the filler and the matrix and higher homogeneity of the material. A decrease of the degree of crystallinity of the PP matrix in presence of the untreated filler was observed. Dynamic mechanical analysis and tensile properties were also studied. High‐strain tensile properties display enhanced mechanical properties for MAPP treated‐based composites only. When conditioned in highly moist atmosphere (98% RH), both the water uptake and water diffusion coefficient decrease when the filler was treated. These effects were ascribed to the promoting interfacial adhesion induced by the coating treatment. In liquid water, this increased adhesion between the filler and the matrix results in a higher weight loss of the material. It is due to the removal of the grafted polymer from the material during the dissolution of part of the filler.

SEMs of freshly fractured surface for a PP film filled with 10 wt.‐% of MAPP treated OFI cladode (top) and calcium oxalate crystallite within the PP matrix for a 3 wt.‐% filled composite (bottom).     

1,8‐Naphthalimides as Blue Emitting Fluorophores for Polymer Materials

The copolymerization of 1,8‐naphthalimide derivatives (as fluorophore) with acrylonitrile has been investigated. The photophysical characteristics of monomeric and polymeric fluorophores in N,N‐dimethylformamide solution have been determined and discussed. During copolymerization, no changes in the chromophoric systems of the fluorophore occur. The influence of the studied monomeric 1,8‐naphthalimide fluorophores upon the structurally bleached polyacrylonitrile has been determined. Infrared absorption characteristics of the polymerizable 4‐alkoxy‐ and 4‐allyloxy‐N‐substituted‐1,8‐naphthalimides have been measured and discussed. The effect of the substituents upon the vibration frequencies of the carbonyl and allylic groups has been established.

Blue fluorescent polyacrylonitrile copolymers with 1,8‐naphthalimides side‐group.     

Direct Melt Extrusion Processing of Nylon 6/Clay Nanocomposites Based on Pristine Montmorillonite

Summary: An original direct melt extrusion processing of nylon 6/clay nanocomposites was reported based on pristine (Na⁺‐based) montmorillonite as well as a simple approach using a typical two‐screw extruder. By the application of intercalation agents as the thermodynamic assistants, this method is as an appropriate procedure for industrialized manufacture together with much lowered production cost. Interestingly enough, the synergistic effects of montmorillonite with other inorganic particulates was observed for the first time here.

X‐ray diffraction patterns of pristine MMT and nylon 6/MMT composites with grouped intercalation agents.     

New Polylactide/Layered Silicate Nanocomposites, 6

The measurement of rheological properties of any polymeric material under molten state is crucial to gain fundamental understanding of the processability of that material. In the case of polymer/layered silicate nanocomposites, the measurements of rheological properties are not only important to understand the knowledge of the processability of these materials, but is also helpful to find out the strength of polymer‐layered silicate interactions and the structure‐property relationship in nanocomposites. This is because rheological behaviors are strongly influenced by their nanoscale structure and interfacial characteristics. In order to get this knowledge in the case of polylactide/montmorillonite nanocomposites, we have studied melt rheological properties of these materials in detail. On the basis of rheological data, we have conducted foam processing of pure polylactide and one representative nanocomposite by a newly developed pressure cell technique using carbon dioxide as a physical‐blowing agent.

The time variation of the elongational viscosity of one of the intercalated polylactide/montmorillonite nanocomposites.     

Morphological Characterization of PMMA/PAN Composite Particles in Nano to Submicro Size

Summary: It is necessary to use a selective staining agent to enhance image contrast for transmission electron microscopy (TEM) morphological characterization of polymer composite particles. However, the typical selective staining agents osmium tetraoxide and ruthenium tetraoxide are neither suitable for poly(methyl methacrylate) (PMMA)/polyacrylonitrile (PAN) composite particles. In this study, it was found that phosphotungstic acid (PTA) solution with 6.4 pH value is unsuitable for PMMA, but it can stain PAN. Therefore, it can be a selective staining agent in the TEM for PMMA/PAN composite particles. By controlling different thermodynamic and kinetic polymerization parameters, PMMA/PAN and PMMA/P(AN‐MMA) composite particles with nano to submicro sizes having different morphological structures were synthesized. TEM micrographs of all these composite particles with their predicted morphology have been compared, and the experimental results are completely consistent with the predictions.

TEM micrograph of PMMA/PAN composite particles.     

Use of Nitrogen as a Blowing Agent for the Production of Fine‐Celled High‐Density Polyethylene Foams

Summary: While many experiments have been performed to examine the effects of administering CO₂ as a blowing agent in the foaming process, very few studies have investigated the use of N₂ for this purpose. In this study, foaming experiments were conducted in extrusion using HDPE as a polymeric material and N₂ as a blowing agent. Talc was used as a nucleating agent, and three different pressure‐drop rates were applied to study the effects of pressure‐drop rates on HDPE foams. The experimental results revealed that the void fraction of high‐density foams blown with N₂ was not affected by the die temperature, contrasting the situation in low‐density foams. Surprisingly, it was the cell density which determined the void fraction of high‐density foams. It was also found that the use of talc significantly increased the cell density and the void fraction of the foams and minimized the role played by the pressure‐drop rate in cell nucleation.

Effect of N₂ content on the cell density of HDPE foams.     

Nanocellular Foams of PS/PMMA Polymer Blends

A nanocellular PS/PMMA polymer blend foam was prepared, where bubble nucleation was localized in the PMMA domains. The blend, which contains dispersed nanoscale PMMA islands, was prepared by polymerizing MMA monomers in a PS matrix to form highly dispersed PMMA domains in the PS matrix by diffusion mixing. The resulting blend was foamed with CO₂ at room temperature. A higher depressurization rate at lower foaming temperature made the bubble diameter smaller and the bubble density larger, and a higher PS composition in the blend resulted in a larger bubble density. A void with 40–50 nm in average diameter and a pore density of 8.5 × 10¹⁴ cm^?3 was obtained as for the finest nanocellular foams.

     

The Effect of Mixing on the Mechanical Properties of Hyaluronan‐Based Injectable Hydrogels

A method for determining the correlation between the mixing of two reactive polymers and the structural and mechanical properties of the formed hydrogels is presented. Rheological measurements show that insufficient mixing gives rise to soft and not fully crosslinked hydrogels while excessive mixing beyond gel point results in weaker hydrogels due to potential breakage of their 3D network. Furthermore, the hydrogels swell significantly more in cell culture medium than in phosphate‐buffered saline, attributed to interactions with additional molecules such as proteins. Thus, moderate mixing gives rise to the most homogenous and mechanically stable hydrogels and the choice of medium e.g., for release experiments, should be consistent in order to avoid unnecessary variations in the data caused by different swelling profiles.

     

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.

     

Blown Soybean Oil Ceramer Coatings for Corrosion Protection

A series of ceramer coatings were formulated using blown soybean oil as the organic phase, and sol‐gel precursors [titanium(IV ) isopropoxide, titanium(IV ) diisopropoxide bisacetoacetonate, and zirconium propoxide] as the inorganic phase. The corrosion resistance of the ceramer coatings was evaluated using failure‐at‐scribe and electrochemical impedance spectroscopy (EIS) on aluminium after exposure in a Prohesion Chamber. Scanning electron microscopy (SEM) and energy dispersive X‐ray analysis (EDXA) were also used to evaluate the coatings after exposure. The ceramer coatings demonstrated higher pull‐off adhesion, impedance modulus (after exposure), and lower failure‐at‐scribe than the blown soybean oil film. It was surmised that the addition of sol‐gel precursor enhanced the corrosion protective properties of the ceramer coatings via a self‐assembling layer of metal‐oxo clusters at the film substrate (aluminium) interface.

Impedance modulus of TIP‐based ceramer coatings as a function of exposure time.     

Improved Design of Shearing Sections with New Calculation Models Based on 3D Finite‐Element Simulations

New models for the Maddock and spiral shearing sections have been developed, employing three‐dimensional finite element analysis (3D FEA). These models describe the pressure‐throughput and power consumption behavior of the shearing sections for both the extrusion and the injection molding process and have been implemented in the REX 6.0 and PSI 4.0 simulation software. As a consequence it is now possible to describe the process behavior of these shearing sections within just a few seconds with the accuracy of FEA calculations.

Actual Maddock shearing section (left) and actual spiral shearing section (right).     

Enhanced Properties of Dissimilar Rubber Blends Using Microencapsulated Sulfur Through Acetylene Plasma Polymerization

Surface modification of sulfur by vacuum plasma polymerization with acetylene was applied in order to modify its surface properties without losing reactivity for vulcanization. A nm‐thin layer of crosslinked polyacetylene was deposited on the surface of the sulfur powder. Its surface energy was decreased as monitored by wetting in liquids of various polarities. A delay in the onset of weight loss by sublimation in thermal gravimetric analysis was shown by the plasma‐modified sulfur. Scanning electron microscopy showed a core/shell structure of the coated sulfur. In 50:50 blends of styrene‐butadiene rubber and ethylene‐propylene‐diene rubber, the encapsulated sulfur samples resulted in pronounced improvements in the mechanical properties relative to the use of unmodified sulfur.

     

Novel Foams Based on Freeze‐Dried Renewable Vital Wheat Gluten

A new way of producing rigid or semi‐rigid foams from vital wheat gluten using a freeze‐drying process is reported. Water/gluten‐based mixtures were frozen and freeze‐dried. Different foam structures were obtained by varying the mixing process and wheat gluten concentration, or by adding glycerol or bacterial cellulose nanofibers. MIP revealed that the foams had mainly an open porosity peaking at 93%. The average pore diameter ranged between 20 and 73 µm; the sample with the highest wheat gluten concentration and no plasticizer had the smallest pores. Immersion tests with limonene revealed that the foams rapidly soaked up the liquid. An especially interesting feature of the low‐wheat‐concentration foams was the “in situ” created soft‐top‐rigid‐bottom foams.

     

Low‐Density Nanocellular Foams Produced by High‐Pressure Carbon Dioxide

A new type of nanocellular polymeric material based on PMMA and a MAM triblock copolymer is presented. The production avoids the use of physical additives and leads to completely homogeneous nanostructured polymers with a large number of CO₂ nucleation sites. The foamed materials show average cell sizes <200 nm and relative foam densities of 0.4, presenting a homogeneous cell structure. A physical effect not measured before in nanocellular materials is demonstrated, which leads to an increase of the glass transition temperature due to the confining effect of PMMA chains in the cell walls of the nanocellular foam. The effects of changing saturation pressure and MAM content in the cellular structure are described, together with three‐point bending Young's modulus measured using DMA.

     

Porous Cellulose Acetate Butyrate Foams with a Tunable Bimodality in Foam Morphology Produced with Supercritical Carbon Dioxide

Porous cellulose acetate butyrate foams with a bimodal cell size distribution were produced using supercritical carbon dioxide as a blowing agent. It is demonstrated that the cell size distribution is tunable, due to the semi‐crystalline nature of the polymer. The resulting morphology will either be homogeneous or bimodal, depending on the depressurization rate. Mercury intrusion porosimetry shows that the produced cellulose acetate butyrate foams possess an open cellular structure.

     

Interpenetrating Polymer Networks of Hydrocarbon and Fluorocarbon Polymers: Epoxy/Fluorinated Acrylic Macromonomers

A fluorinated acrylic resin was synthesized for use as a co‐monomer with a commercially available epoxy resin for UV‐cured interpenetrating polymer network preparation. Hybrid IPN networks were achieved with morphology ranging from a co‐continuous IPN to complete phase separation simply by changing monomer ratios. Highly hydrophobic coatings with good adhesion properties on glass substrates were obtained.