Novel Poly(N‐isopropylacrylamide)‐graft‐poly(vinylidene fluoride) Copolymers for Temperature‐Sensitive Microfiltration Membranes

In the present work, we report on the synthesis and characterization of poly(vinylidene fluoride) (PVDF) with N‐isopropylacrylamide (NIPAAM) polymer side chains from molecular graft copolymerization in solution. The copolymer can be readily cast into temperature‐sensitive microfiltration (MF) membranes by the phase inversion technique. The copolymer approach to membrane fabrication allows a much better control of the physicochemical nature of the membrane pores through the variation in graft concentration, membrane casting temperature and concentration of the membrane casting solution.

     

Manufacturing Carbon Nanotube/PVDF Nanocomposite Powders

A procedure for the production of carbon nanotube (CNT) reinforced poly(vinylidine difluoride) (PVDF) powders has been developed. These powders are versatile precursors for a range of nanocomposite materials. The morphology of the CNT/PVDF powder can be related to the interaction between filler and matrix, which depends on the degree of modification of the polymer with grafted maleic anhydride (MAH‐graft‐PVDF). The mechanical performance of the nanocomposite containing 2.5 wt.‐% CNT and 1.25 ppm of MAH increased in tensile modulus, tensile strength, and strain to failure by 34, 30, and 22%, respectively, as compared to PVDF.

     

Polyolefin/Lignosulfonate Blends, 9

Summary: In the present study, the compatibility, properties and degradability of polyolefin/lignin blends have been studied. Blends of three maleic anhydride grafted copolymers of ethylene‐propylene rubbers containing various content of functional groups with epoxy‐modified lignosulfonate have been investigated by microscopy, X‐ray diffraction, surface and mechanical indices determination, electron spin resonance, IR spectroscopy, differential scanning calorimetry and thermogravimetry. To assess the environmental degradation characteristics, the behavior of the blends during soil burial test has been investigated. The influence of the buried polymer blends on the physiological vegetative processes of the Vicia X Hybrida hort plant has been monitored.

Optical microscopy images of blend EP‐g‐MA 0.3/5 LER, undegraded (left) and degraded (right).     

Morphology Dependent Double Yielding in Injection Molded Polycarbonate/Polyethylene Blend

Summary: Polycarbonate (PC)/polyethylene (PE) blend was injection molded at different molding temperatures. The morphological observation by scanning electronic microscope (SEM) indicated that the sample molded at 190 °C contained only uniformly dispersed spherical PC particles. The samples molded at 230 and 275 °C had a typical skin‐core structure, and there were many injection‐induced PC fibers in the subskin. While the sample molded at 190 °C had the usual stress‐strain behavior, the samples obtained at 230 and 275 °C showed apparently double yielding behavior. It was suggested that the double yielding points were morphology‐dependent. The first one was the result of the yielding of PE at low strain, and the second one was caused by the yielding of the PC fibers. Moreover, it is the frictional force in the interfaces between PC and PE that transferred the stress to the PC fibers, hence giving rise to the reinforcement of PE by PC.

Stress‐strain curves of PC/PE blends injection molded at various temperatures showing first (I) and second (II) yielding points.     

Electrospun Polycaprolactone/Silk Fibroin/Small Intestine Submucosa Composites for Biomedical Applications

Natural biomaterials were used to improve the biocompatibility of synthetic biopolymers. PCL was electrospun with natural biopolymers, silk fibroin, and small intestine submucosa. Due to increased electrical conductivity, the diameter of the composite fibers highly depended on the amount of SIS in the polymer solution. PCL/SF/SIS electrospun composites exhibited various synergistic effects, including enhanced mechanical properties and incredibly improved hydrophilicity compared to those of pure PCL and PCL/SF fibers. An initial cell attachment test demonstrated that the interactions between PC‐12 nerve cells and the PCL/SF/SIS composites were more favorable than those between PC‐12 cells and a PCL/SF composite.

     

Friction and Wear Mechanisms of Sintered and Thermoplastic Polyimides under Adhesive Sliding

Polyimides function under high‐temperature sliding. The available literature explains transitions in friction and wear mainly by mechanical effects, such as influences of normal load, sliding velocity and humidity on polymer transfer to steel counterfaces. Theoretical models are evaluated for sintered and thermoplastic polyimides. Tribologists have been interested in tribochemical and tribophysical reactions in the sliding interface for about 25 years. Reactions such as hydrolysis, imidisation and/or degradation occur as a function of sliding temperature and are reviewed in this paper. An overview of polyimide synthesis and degradation is presented, while new insights in sliding mechanisms are obtained from a detailed study of Raman spectroscopy on worn polymer surfaces.

     

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.

     

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.     

Diffraction Gratings in Hybrid Sol‐Gel Films: On the Understanding of the Relief Generation Process

Hybrid organic‐inorganic materials based on the sol‐gel synthesis of an organically modified silicon alkoxide have demonstrated their great potential for optical applications. They offer a high versatility in terms of chemical, physical properties and macroscopic shape molding of the final component. Recently, a photolithographic process allowed the generation of relief optical elements without requiring a wet treatment to reveal the latent image. It enabled a low cost, simple and quick method for the fabrication of integrated optical components. The aim of the present paper is to give new insights into the mechanisms of surface self‐corrugation leading to gratings generation in hybrid sol‐gel films. A study of the relief formation was led by giving particular attention to the kinetic aspects of the polymerization of the organic component. The control of the C?C double bonds conversion of methacrylate functionalized alkoxides in case of photopolymerization is therefore an essential issue to tailor material properties. The study also focuses on the influence of physico‐chemical parameters that govern the relief generation and underlines the particular role of temperature. Kinetics of surface corrugation point out the importance of strain relaxation, mass‐transfer by flowing and organic network formation during the photolithographic process. Some illustrations of the generated diffraction gratings are given.

Interferogram of the diffraction grating obtained after 120 s exposure through a chromium mask.     

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).     

Development of a 3D‐Finite Element Module for the Prediction of the Fibre Orientation in Injection Moulded Parts

This article presents a 3D‐finite element simulation package for the prediction of the fibre orientation in injection moulding. The fibre orientation is calculated by using a mathematical model based on orientation tensors, which not only takes into account the 3D‐flow field, but also the shape of the fibres and the fibre‐fibre interaction. The tensor model has been verified in many scientific investigations and has proven to yield satisfying results. Therefore we decided to use this model for implementation into a 3D‐finite element simulation package, which is currently being developed at the Institute of Plastics Processing (IKV) at RWTH Aachen University, Germany. The implementation of this model using both the finite element method and the finite volume method is described and the different parameters used in this model are analysed and discussed separately, as are the parameters used for the injection moulding process. The results obtained are compared to similar results from literature.

Model of the flow channel (10 mm × 10 mm × 100 mm) used for the simulations.     

N-n-Alkylpyridinium Derivatives of Mica-Type Layer Silicates

This paper deals with the cation exchange of N-n-alkylpyridinium ions against inorganic ions in mica type layer silicates. The arrangements of these ions in the interlayer space is derived from basal spacing measurements.     

Palladium(II)‐Catalyzed Sequential Aminopalladation and Oxidative Coupling with Acetylenes/Enones: Synthesis of Newly Substituted Quinolines from 2‐Aminophenyl Propargyl Alcohols

Palladium catalyzed conversion of 1‐(2‐aminophenyl)‐propargyl alcohols to 3‐alkynyl quinolines is realized via a cascade that involves aminopalladation, oxidative coupling with alkynes and dehydration. The method is shown to have a broad substrate scope with respect to propargyl alcohols as well as alkynes. Vinyl ketones as coupling partners in the same reaction afforded 3‐alkenyl quinolines with equal ease.

     

Morphology and Properties of Polyethylene/Clay Nanocomposite Drawn Fibers

The influence of an elongational flow on the morphology of PE/clay nanocomposite drawn fibers was studied. An increase of the elastic modulus and the tensile strength as well as a decrease of the elongation at break are observed with increasing draw ratio. The applied elongational gradient orients the polymer chains and the clay particles along the spinning direction. When the applied flow results in the formation and the orientation of exfoliated nanoparticles, a pronounced increase of the mechanical properties is observed. The dispersed clay particles can be broken and oriented by the extensional flow, which might indicate a flow‐induced intercalated/exfoliated morphology transition.

     

Effect of Nucleating Agents on Crystallization and Melting Behavior and Mechanical Properties of Nucleated Syndiotactic Poly(propylene)

Summary: The effects of various nucleating agents [e.g. 1,3:2,4‐dibenzylidene sorbitol (DBS), 1,3:2,4‐di‐p‐methyldibenzilidene sorbitol (MDBS), 1,3:2,4‐di‐m,p‐methylbenzylidene sorbitol (DMDBS), kaolin, talcum, marl, titanium dioxide (TiO₂) and silica (SiO₂)] on non‐isothermal melt crystallization and the subsequent melting behavior and mechanical properties of nucleated syndiotactic poly(propylene) (sPP) in comparison with those of the neat sample were investigated. Analysis of the non‐isothermal melt‐crystallization exotherms revealed that the ability of these fillers to nucleate sPP could be ranked from the best to the worst as follows: DBS > talcum > MDBS > kaolin > SiO₂ > DMDBS > marl > TiO₂. The subsequent melting endotherms for most of the sPP compounds exhibited double melting peaks, while that for the marl‐filled sPP exhibited triple melting peaks. Wide‐angle X‐ray diffraction analysis showed that addition of these fillers did not affect the crystal modification of the sPP matrix. Mechanical property measurements revealed that both the tensile strength and the percentage of elongation at yield for the sPP compounds investigated were not much different from those of the neat sPP. After natural weathering for 1 month, the tensile strength at yield for the sPP compounds investigated increased, at the expense of the percentage of elongation at yield, but, after natural weathering for 3 months, both the tensile strength and the percentage of elongation at yield were found to decrease.

Effects of various organic and inorganic nucleating agents on non‐isothermal melt‐crystallization of syndiotactic poly(propylene) (recorded at a cooling rate of 10 °C · min^?1).     

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.

     

Grafting of Hindered Amine Stabilizer in Poly(propylene) Films under γ‐Irradiation

Summary: In this paper, the grafting of a hindered amine stabilizer (HAS) is studied in isotactic poly(propylene) (PP) films under γ‐irradiation. The HAS used has a definite structure that combines a hindered amine functionality and a UV‐absorbing unit (benzylidene malonate ester group) detectable at 308 nm in the UV spectrum of PP film and 314 nm in chloroform. The stabilizer is added to the polymer at various concentration ratios: 0.1, 0.2, and 0.3 wt.‐%. The percentage of HAS grafting in the PP film at various additive concentrations is determined as a function of γ‐radiation dose in the range of 0–100 kGy by direct spectroscopic measurements through the absorption band of the stabilizer in the UV spectra of the PP film. The percentage of free HAS extracted with chloroform from the PP film versus the radiation dose is determined by UV spectroscopy for all the additive concentrations used. This study reveals that only 80% of the HAS is grafted on the 100 kGy irradiated PP matrix independent of the additive concentration used. However, the percentage of HAS grafted on PP films displays an exponential dependence on γ‐radiation dose. These results are consistent with the data obtained on the free HAS content. γ‐Irradiation grafting of HAS in the PP is accompanied by the oxidative degradation of the polymer substrate that is evaluated by increasing the carbonyl index and reducing significantly the oxidation induction time of the PP films.

The percentage of hindered amine stabilizer grafted to the PP film as a function of γ‐radiation dose.     

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.     

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.     

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.