Turgut Nugay

Real-Time Monitoring of Chemical and Topological Rearrangements in Solidifying Amphiphilic Polymer Co-Networks: Understanding Surface Demixing

Amphiphilic polymer co-networks provide a unique route to integrating contrasting attributes of otherwise immiscible components within a bicontinuous percolating morphology and are anticipated to be valuable for applications such as biocatalysis, sensing of metabolites, and dual dialysis membranes. These co-networks are in essence chemically forced blends and have been shown to selectively phase-separate at surfaces during film formation. Here, we demonstrate that surface demixing at the air-film interface in solidifying polymer co-networks is not a unidirectional process; instead, a combination of kinetic and thermodynamic interactions leads to dynamic molecular rearrangement during solidification. Time-resolved gravimetry, low contact angles, and negative out-of-plane birefringence provided strong experimental evidence of the transitory trapping of thermodynamically unfavorable hydrophilic moieties at the air-film interface due to fast asymmetric solvent depletion. We also find that slow-drying hydrophobic elements progressively substitute hydrophilic domains at the surface as the surface energy is minimized. These findings are broadly applicable to common-solvent bicontinuous systems and open the door for process-controlled performance improvements in diverse applications. Similar observations could potentially be coupled with controlled polymerization rates to maximize the intermingling of bicontinuous phases at surfaces, thus generating true three-dimensional, bicontinuous, and undisturbed percolation pathways throughout the material.

Inter polymer complexes of poly(methyl methacrylate)-block-poly(4-vinylpyridine) with polyacrylic acid and polyacrylic acid-block-poly(methyl methacrylate)

Abstract Inter polymer complex formations between poly(methyl methacrylate)-block-poly(4-vinylpyridine) diblock copolymer and polyacrylic acid as well as poly(acrylic acid)-block-poly(methyl methacrylate) diblock copolymers have been studied. The structures of the complex were identified with 1H-NMR, FTIR and differential scanning calorimetry techniques. The thermal stability of the complexes was investigated by thermogravimetric analysis. Optical clarity of the block copolymer complexes were determined.

Transport-Limited Adsorption of Plasma Proteins on Bimodal Amphiphilic Polymer Co-Networks: Real-Time Studies by Spectroscopic Ellipsometry

Traditional hydrogels are commonly limited by poor mechanical properties and low oxygen permeability. Bimodal amphiphilic co-networks (β-APCNs) are a new class of materials that can overcome these limitations by combining hydrophilic and hydrophobic polymer chains within a network of co-continuous morphology. Applications that can benefit from these improved properties include therapeutic contact lenses, enzymatic catalysis supports, and immunoisolation membranes. The continuous hydrophobic phase could potentially increase the adsorption of plasma proteins in blood-contacting medical applications and compromise in vivo material performance, so it is critical to understand the surface characteristics of β-APCNs and adsorption of plasma proteins on β-APCNs. From real-time spectroscopic visible (Vis) ellipsometry measurements, plasma protein adsorption on β-APCNs is shown to be transport-limited. The adsorption of proteins on the β-APCNs is a multistep process with adsorption to the hydrophilic surface initially, followed by diffusion into the material to the internal hydrophilic/hydrophobic interfaces. Increasing the cross-linking of the PDMS phase reduced the protein intake by limiting the transport of large proteins. Moreover, the internalization of the proteins is confirmed by the difference between the surface-adsorbed protein layer determined from XPS and bulk thickness change from Vis ellipsometry, which can differ up to 20-fold. Desorption kinetics depend on the adsorption history with rapid desorption for slow adsorption rates (i.e., slow-diffusing proteins within the network), whereas proteins with fast adsorption kinetics do not readily desorb. This behavior can be directly related to the ability of the protein to spread or reorient, which affects the binding energy required to bind to the internal hydrophobic interfaces.

Tuning of heavy metal removal efficiency from water via micro algae/hydrogel composites

Abstract A series of micro algea-based hydrogel composites were prepared from polyacrylamide and Spirulina (PAAm-sp). Free radical polymerization of acrylamide (AAm) in the presence of N,N-methylene bis-acrylamide (BAAm), as a crosslinker, and Spirulina microalgae in different loadings was conducted. Chromium metal adsorption capacity was determined with UV-VIS spectroscopy whereas mechanical performance of the resultant hydrogel composites was followed with uniaxial compression experiments. It has been found that efficiency can be tuned by Spiriluna composition in hydrogel. PAAm hydrogel composite having 0.5 % Spirulina had the maximum compression strength, good swelling in water as well as improved thermal stability due to the special and beneficial ‘fishnet morphology” observed via scanning electron microscopy (SEM). The observed high performance of this composition is proved to be due to this morphology where all potential binding sites are under receptive position for metal adsorption. Spirulina by itself in water can remove only about 2 % of its weight of Cr+3 ion, however in the hydrogel structure this removal increases up to 200 % which makes this biotechnological approach superior in the metal removal from the water.

Preparation of super HIPS via nanocomposite assemblies in the presence of toughener- intercalant

Abstract Highly toughened super high-impact polystyrene (HIPS)/organophilic montmorillonite (Org-MMT) nanocomposite was prepared by solution blending method. Organophilic modification of MMT layered silicate was achieved by using a special toughener-intercalant, quaternary ammonium salt of α-tertiary amine functionalized polybutadiene and shown by X-ray diffraction analysis. The resulting HIPS/Org-MMT nanocomposite was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA), and static and dynamic mechanical analyses. The morphological study of HIPS/Org-MMT nanocomposite showed that nanolayers were exfoliated in nanocomposite and moreover caused much more well dispersed and reduced PS occluded rubber domains. This mechanism was found to be responsible for dramatic increase in toughness of nanocomposites. Additionally, improved thermal and dynamic mechanical properties of the resultant nanocomposite promises to open a new way for highly toughened super HIPSs via nanocomposite assemblies even with a very low degree of clay loading.

UV induced reversible chain extension of 1-(2-anthryl)-1-phenylethylene functionalized polyisobutylene

Abstract The synthesis of novel 1-(2-anthryl)-1-phenylethylene (APE) di-telechelic polyisobutylenes is described. Utilization of a difunctional cationic initiator and the in situ addition of the non-homopolymerizable APE lead to the formation of di-anthryl telechelic polyisobutylenes. Products were characterized by 1H NMR spectroscopy and Size Exclusion Chromatography. The polymers were UV irradiated at 365 and 254 nm and the reversible photocycloaddition of anthryl moieties was investigated. The chain extension of di-anthryl telechelic PIBs through photocoupling at 365 nm produced higher molecular weight products from low molecular weight precursors. The effect of precursor polymer concentration on the degree of chain extension was investigated, and intermolecular interactions leading to the formation of tetramers was observed. The photocoupled products were UV irradiated at 254 nm to induce the reversal of photocycloaddition of anthryl groups and to follow the consequent photoscission of polymers.

Synthesis and properties of poly(4-vinylpyridine)/ montmorillonite nanocomposites

Abstract 4-Vinylpyridine monomer was mixed with organically modified montmorillonite (MMT) and polymerized in the presence of 2,2’-azoisobutyronitrile as radical initiator. Organophilic montmorillonite was obtained by using a block copolymer of poly(methyl methacrylate) and quaternized poly(4-vinylpyridine) (P4VP) in different compositions. X-ray diffraction (XRD) and thermogravimetric analysis confirmed that the block copolymer is inserted between MMT layers while the interlayer distance is expanded. The P4VP nanocomposites obtained from the block copolymer with the longer P4VP block exhibited no XRD peak, suggesting an exfoliated structure. These composites showed increased storage modulus and thermal stability at a very low loading of 1 - 2 wt.-%, compared to neat P4VP. Scanning electron microscopy and atomic force microscopy analyses were also conducted for selected nanocomposites.

Tuning of nanotube/elastomer ratio for high damping/tough and creep resistant polypropylene/SEBS-g-MA/HNT blend nanocomposites

Polypropylene (PP)/maleic anhydride grafted polystyrene-b-poly (ethylene/butylene)-b-polystyrene (SEBS-g-MA)/organophilic halloysite nanotube clay ternary nanocomposites were produced by using HNT/SEBS-g-MA masterbatches at different nanotube loadings (1 wt%, 3 wt%, and 5 wt%). The masterbatches with different ratios of HNT/SEBS-g-MA (1/1, 1/2, and 1/3) were prepared via a revolution/rotation type mixing-assisted masterbatch process. All nanocomposites showed higher storage moduli and damping at low temperatures as compared to neat polypropylene. The nanocomposites having HNT/SEBS-g-MA ratio of 1/3 were found to act as effective dampers with their relatively higher damping values. In terms of short-term creep performance, 1 wt% and 3 wt% organophilic halloysite nanotube loaded systems with low amount of SEBS-g-MA (<9 wt%) enhanced dimensional stability of polypropylene with their lower creep strain and permanent deformation values. More specifically, among the nanocomposites, 3 wt% organophilic halloysite nanotube loaded nanocomposite with HNT/SEBS-g-MA ratio of 1/3 and co-continuous like morphology not only exhibited an effective damping over a wide range of temperature (from −70℃ to 50℃) but also showed relatively higher storage moduli at low temperature region together with lower permanent creep deformation as compared to neat polypropylene. As a result, the HNT/SEBS-g-MA masterbatch in 1/3 ratio was found to be the most suitable in polypropylene blend nanocomposites. It may be advantageous for polypropylene nanocomposite based applications where high damping/toughness at low temperature conditions and high dimensional stability under load are desired.

Weld line behaviour of exfoliated and toughened polypropylene layered silica nanocomposites

Abstract Exfoliated and toughened polypropylene nanocomposites prepared by an introduction of a rubber in the form of compatibilizer toughener: ethylene propylene diene based rubber grafted with maleic anhydride (EPDM-g-MAH) were studied in terms of weld line properties and morphology. Effects of addition of rubber and nanolayer on weld line strength under tensile loading condition of polypropylene matrix were investigated. Data showed that in the absence of either EPDM or nanolayers, a sharp decrease in weld line strength cannot be avoided whereas in the presence of each in optimum ratio, the drastic increase in both toughness and weld line strength values can be easily reached. The beneficial effect is believed to come from the selective placing of nanolayers around the rubber droplets and making them smaller in size which contributes to diffused weld line regions with high mechanical strength.