Search results for: zwitterionic polymer brushes

Authors: Esther Van Andel, Stefanie C. Lange, Maarten M. J. Smulders, Han Zuilhof

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False outcomes of diagnostic tests are a major concern in medical health care. To improve the reliability of surface-based diagnostic tests, it is of crucial importance to diminish background signals that arise from the non-specific binding of biomolecules, a process called fouling. The aim is to create surfaces that repel all biomolecules except the molecule of interest. This can be achieved by incorporating antifouling protein repellent coatings in between the sensor surface and it’s recognition elements (e.g. antibodies, sugars, aptamers). Zwitterionic polymer brushes are considered excellent antifouling materials, however, to be able to bind the molecule of interest, the polymer brushes have to be functionalized and so far this was only achieved at the expense of either antifouling or binding capacity. To overcome this limitation, we combined both features into one single monomer: a zwitterionic sulfobetaine, ensuring antifouling capabilities, equipped with a clickable azide moiety which allows for further functionalization. By copolymerizing this monomer together with a standard sulfobetaine, the number of azides (and with that the number of recognition elements) can be tuned depending on the application. First, the clickable azido-monomer was synthesized and characterized, followed by copolymerizing this monomer to yield functionalizable antifouling brushes. The brushes were fully characterized using surface characterization techniques like XPS, contact angle measurements, G-ATR-FTIR and XRR. As a proof of principle, the brushes were subsequently functionalized with biotin via strain-promoted alkyne azide click reactions, which yielded a fully zwitterionic biotin-containing 3D-functionalized coating. The sensing capacity was evaluated by reflectometry using avidin and fibrinogen containing protein solutions. The surfaces showed excellent antifouling properties as illustrated by the complete absence of non-specific fibrinogen binding, while at the same time clear responses were seen for the specific binding of avidin. A great increase in signal-to-noise ratio was observed, even when the amount of functional groups was lowered to 1%, compared to traditional modification of sulfobetaine brushes that rely on a 2D-approach in which only the top-layer can be functionalized. This study was performed on stoichiometric silicon nitride surfaces for future microring resonator based assays, however, this methodology can be transferred to other biosensor platforms which are currently being investigated. The approach presented herein enables a highly efficient strategy for selective binding with retained antifouling properties for improved signal-to-noise ratios in binding assays. The number of recognition units can be adjusted to a specific need, e.g. depending on the size of the analyte to be bound, widening the scope of these functionalizable surface coatings.

Keywords: antifouling, signal-to-noise ratio, surface functionalization, zwitterionic polymer brushes

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Authors: Xiaoxiao Zhao

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We report macroscopic evidence of the liquidlike nature of surface-tethered poly(dimethylsiloxane) (PDMS) brushes by studying their adhesion to ice. Whereas ice permanently detaches from solid surfaces when subjected to sufficient shear, commonly referred to as the material’s ice adhesion strength, adhered ice instead slides over PDMS brushes indefinitely. When additionally methylated, we observe a Couette-like flow of the PDMS brushes between the ice and silicon surface. PDMS brush ice adhesion displays shear-rate-dependent shear stress and rheological behavior reminiscent of liquids and is affected by ice velocity, temperature, and brush thickness, following scaling laws akin to liquid PDMS films. This liquidlike nature allows it to detach solely by self-weight, yielding an ice adhesion strength of 0.3 kPa, 1000 times less than low surface energy, perfluorinated monolayer. The methylated PDMS brushes also display omniphobicity, repelling all liquids essentially with vanishingly small contact angle hysteresis. Methylation results in significantly higher contact angles than previously reported, nonmethylated brushes, especially for polar liquids of both high and low surface tension.

Keywords: omniphobic, surface science, polymer brush, icephobic surface

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Authors: Bilge Bozdogan, Selda T. Sendogdular, Levent Sendogdular

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We report a technique to control chain conformation during the plasticization process to achieve homogeneous and stable thin films, which allows to reduce post-process annealing times along with enhanced properties like controlled irreversible adsorbed layer (Guiselin brushes) formation. In this study, spin coating temperature was considered as a parameter; hence, all equipment, including the spin coater, substrate, vials, and the solution, was kept inside the same heated fume hood where solution was spin-coated after the temperature was stabilized at a desired value. AFM and SEM results revealed severe difference for solid and air interface between ambient and temperature-controlled samples, which suggest that enthalpic contribution dynamically helps to control film stability in a way where chain entanglements and conformational restrictions are avoided before film growing and allowing to control grafting density through spin coating temperature. The adsorbed layer was also characterized with SEM and Raman-spectroscopy technique right after seeding the adsorbed layer with gold nanoparticles. Stabilized gold nanoparticles and their surface distribution manifest the existence of a controllable polymer brush structure. Acknowledgments: This study was funded by Erciyes University Scientific Research Projects (BAP) Funding(Project ID:10058)

Keywords: chain stability, Guiselin brushes, polymer thin film, spin coating temperature

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Authors: P. Saha, R. Ganguly, N. K .Singha, A. Pich

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Microgel, a smart class of material, has drawn attention in the past few years due to its response to external stimuli like temperature, pH, and ionic strength of the solution. Among them, one type of polymer becomes soluble, and the other becomes insoluble in water upon heating displaying upper critical solution temperature (UCST) (e.g., polysulfobetaine, PSB) and lower critical solution temperature (LCST) (e.g., poly(N-vinylcaprolactam, PVCL)) respectively. Polyzwitterions, electrically neutral polymers are biocompatible, biodegradable, and non-cytotoxic in nature, and presence of zwitterionic pendant group in the main backbone makes them stable against temperature and pH variations and strong hydration capability in salt solution promotes them to be used as interfacial bio-adhesion resistance material. Majority of zwitterionic microgels have been synthesized in mini- emulsion technique using free radical polymerization approach. Here, a new route to synthesize dual thermo-responsive PVCL microgels decorated with appreciable amount of zwitterionic PSB chains was developed by a purely water-based surfactant-free reversible addition–fragmentation chain transfer (RAFT) precipitation polymerization. PSB macro-RAFTs having different molecular weights were synthesized and utilized for surface-grafting with PVCL microgels varying the macro-RAFT concentration using N,N′-methylenebis(acrylamide) (BIS) as cross-linker. Increasing the PSB concentration in the PVCL microgels resulted in a linear increase in UCST but decrease in hydrodynamic radius due to strong intrachain coulombic attraction forces acting between the opposite charges present in the zwitterionic groups. Anti- fouling effect was observed on addition of BSA protein solution on the microgel-coated membrane surfaces as studied by fluorescence spectrophotoscopy.

Keywords: microgels, polyzwitterions, upper critical solution temperature-lower critical solution temperature, UCST-LCST, ionic crosslinking

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Authors: A. Chouaih, N. Benhalima, N. Boukabcha, R. Rahmani, F. Hamzaoui

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Zwitterionic compounds have received the interest of chemists and physicists due to their applications as nonlinear optical materials. Recently, zwitterionic compounds exhibiting high nonlinear optical activity have been investigated. In this context, the molecular electron charge density distribution of the title compound is described accurately using the multipolar model of Hansen and Coppens. The net atomic charge and the molecular dipole moment have been determined in order to understand the nature of inter- and intramolecular charge transfer. The study reveals the nature of intermolecular interactions including charge transfer and hydrogen bonds in the title compound. In this crystal, the molecules form dimers via intermolecular hydrogen bonds. The dimers are further linked by C–H...O hydrogen bonds into chains along the c crystallographic axis. This study has also allowed us to determine various nonlinear optical properties such as molecular electrostatic potential, polarizability, and hyperpolarizability of the title compound.

Keywords: organic compounds, polarizability, hyperpolarizability, dipole moment

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Authors: Bo Keun Lee, Doo Yeon Kwon, Ji Hoon Park, Gun Hee Lee, Ji Hye Baek, Heung Jae Chun, Young Joo Koh, Moon Suk Kim

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Thermo-responsive materials are viscoelastic materials that undergo a sol-to-gel phase transition at a specific temperature and many materials have been developed. MPEG-b-PCL (MPC) as a thermo-responsive material contained hydrophilic and hydrophobic segments and it formed an ordered crystalline structure of hydrophobic PCL segments in aqueous solutions. The ordered crystalline structure packed tightly or aggregated and finally induced an aggregated gel through intra- and inter-molecular interactions as a function of temperature. Thus, we introduced anionic and cationic groups into the end positions of the PCL chain to alter the hydrophobicity of the PCL segment. Introducing anionic and cationic groups into the PCL end position altered their solubility by changing the crystallinity and hydrophobicity of the PCL block domains. These results indicated that the properties of the end group in the hydrophobic PCL blockand the balance between hydrophobicity and hydrophilicity affect thermo-responsivebehavior of the copolymers in aqueous solutions. Thus, we concluded that determinant of the temperature-dependent thermo-responsive behavior of MPC depend on the ionic end group in the PCL block. So, we introduced zwitterionic end groups to investigate the thermo-responsive behavior of MPC. Methoxypoly(ethylene oxide) and ε-caprolactone (CL) were randomly copolymerized that introduced varying hydrophobic PCL lengths and an MPC featuring a zwitterionic sulfobetaine (MPC-ZW) at the chain end of the PCL segment. The MPC and MPC-ZW copolymers were obtained formed sol-state at room temperature when prepared as 20-wt% aqueous solutions. The solubility of MPC decreased when the PCL block was increased from molecular weight. The solubilization time of MPC-2.4k was around 20 min and MPC-2.8k, MPC-3.0k increased to 30 min and 1 h, respectively. MPC-3.6k was not solubilized. In case of MPC-ZW 3.6k, However, the zwitterion-modified MPC copolymers were solubilized in 3–5 min. This result indicates that the zwitterionic end group of the MPC-ZW diblock copolymer increased the aqueous solubility of the diblock copolymer even when the length of the hydrophobic PCL segment was increased. MPC and MPC-ZW diblock copolymers that featuring zwitterionic end groups were synthesized successfully. The sol-to-gel phase-transition was formed that specific temperature depend on the length of the PCL hydrophobic segments introduced and on the zwitterion groups attached to the MPC chain end. This result indicated that the zwitterionic end groups reduced the hydrophobicity in the PCL block and changed the solubilization. The MPC-ZW diblock copolymer can be utilized as a potential injectable drug and cell carrier.

Keywords: thermo-responsive material, zwitterionic, hydrophobic, crystallization, phase transition

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Authors: M. A. Deyab

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The effect of zwitterionic surfactant (ZS) on erosion-corrosion of API X52 steel in oil sands slurry was studied using Tafel polarization and anodic polarization measurements. The surface morphology of API X52 steel was examined with scanning electron microscopy (SEM) and atomic force microscopy (AFM). ZS inhibited the erosion-corrosion of API X52 steel in oil sands' slurry, and the inhibition efficiency increased with increasing ZS concentration but decreased with increasing temperature. Polarization curves indicate that ZS act as a mixed type of inhibitor. Inhibition efficiencies of ZS in the dynamic condition are not as effective as that obtained in the static condition.

Keywords: corrosion, surfactant, oil sands slurry, erosion-corrosion

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Authors: Konstans Ruseva, Kristina Ivanova, Katerina Todorova, Margarita Gabrashanska, Tzanko Tzanov, Elena Vassileva

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Zwitterionic polymers (ZP) are well-known with their ultralow biofouling. They are successfully competing with poly(ethylene glycols) (PEG), which are considered as the “golden standard” in this respect. These unique properties are attributed to their strong hydration capacity, defined by the dipole-dipole interactions, arising between the ZP pendant groups as well as to the dipoles interaction with water molecules. Beside, ZP are highly resistant to bacterial adhesion thus ensuring an excellent anti-biofilm formation ability. Moreover, ZP are able to respond upon external stimuli such as temperature, pH, salt concentration changes which in combination with their anti-biofouling effect render this type of polymers as materials with a high potential in biomedical applications. The present work is focused on the development of zwitterionic hydrogels for efficient treatment of highly exudating and hard-to-heal chronic wounds. To this purpose, two types of ZP networks with different crosslinking degree were synthesized - polysulfobetaine (PSB) and polycarboxybetaine (PCB) ones. They were characterized in terms of their physico-mechanical properties, e.g. microhardness, swelling ability, smart behaviour. Furthermore, the potential of ZP networks to resist biofilm formation towards Staphylococcus aureus and Escherichia coli was studied. Their ability to reduce the high levels of myeloperoxidase and metalloproteinase, two enzymes that are part of the chronic wounds enviroenment, was revealed. Moreover, the in vitro cytotoxic assessment of PSB and PCB networks along with their in vivo performance in rats was also studied to reveal their high biocompatibility.

Keywords: absorption properties, biocompatibility, enzymatic inhibition activity, wound healing, zwitterionic polymers

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Authors: S. M. Chabane sari S. Zargou, A.R. Senoudi, F. Benmouna

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Immobilization of nano particles (NPs) is the subject of numerous studies pertaining to the design of polymer nano composites, supported catalysts, bioactive colloidal crystals, inverse opals for novel optical materials, latex templated-hollow inorganic capsules, immunodiagnostic assays; “Pickering” emulsion polymerization for making latex particles and film-forming composites or Janus particles; chemo- and biosensors, tunable plasmonic nano structures, hybrid porous monoliths for separation science and technology, biocidal polymer/metal nano particle composite coatings, and so on. Particularly, in the recent years, the literature has witnessed an impressive progress of investigations on polymer coatings, grafts and particles as supports for anchoring nano particles. This is actually due to several factors: polymer chains are flexible and may contain a variety of functional groups that are able to efficiently immobilize nano particles and their precursors by dispersive or van der Waals, electrostatic, hydrogen or covalent bonds. We review methods to prepare polymer-immobilized nano particles through a plethora of strategies in view of developing systems for separation, sensing, extraction and catalysis. The emphasis is on methods to provide (i) polymer brushes and grafts; (ii) monoliths and porous polymer systems; (iii) natural polymers and (iv) conjugated polymers as platforms for anchoring nano particles. The latter range from soft bio macromolecular species (proteins, DNA) to metallic, C60, semiconductor and oxide nano particles; they can be attached through electrostatic interactions or covalent bonding. It is very clear that physicochemical properties of polymers (e.g. sensing and separation) are enhanced by anchored nano particles, while polymers provide excellent platforms for dispersing nano particles for e.g. high catalytic performances. We thus anticipate that the synergetic role of polymeric supports and anchored particles will increasingly be exploited in view of designing unique hybrid systems with unprecedented properties.

Keywords: gold, layer, polymer, macromolecular

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Authors: Rama Seshu Doguparti

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This paper presents the experimental investigation on the bond behavior of geo polymer concrete. The bond behavior of geo polymer concrete cubes of grade M35 reinforced with 16 mm TMT rod is analyzed. The results indicate that the bond performance of reinforced geo polymer concrete is good and thus proves its application for construction.

Keywords: geo-polymer, concrete, bond strength, behaviour

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Authors: R. Sharma, A. Sil, S. Ray

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Nanocomposites gel polymer electrolytes are gaining more and more attention among the researchers worldwide due to their possible applications in various electrochemical devices particularly in solid-state Li-ion batteries. In this work we have investigated the effect of nanofibers on the electrical properties of PVDF-HFP based gel electrolytes. The nanocomposites polymer electrolytes have been synthesized by solution casting technique with 10wt% of ZrO2. By analysis of impedance spectroscopy it has been demonstrated that the incorporation of ZrO2 into PVDF-HFP–(PC+DEC)–LiClO4 gel polymer electrolyte system significantly enhances the ionic conductivity of the electrolyte. The enhancement of ionic conductivity seems to be correlated with the fact that the dispersion of ZrO2 to PVDF-HFP prevents polymer chain reorganization due to the high aspect ratio of ZrO2, resulting in reduction in polymer crystallinity, which gives rise to an increase in ionic conductivity. The decrease of crystallinity of PVDF-HFP due the addition of ZrO2 has been confirmed by XRD. The interaction of ZrO2 with various constituents of polymer electrolytes has been studied by FTIR spectroscopy. TEM results show that the fillers (ZrO2) has distributed uniformly in the polymer electrolytes. Moreover, ZrO2 added gel polymer electrolytes offer better thermal stability as compared to that of ZrO2 free electrolytes as confirmed by TGA analysis.

Keywords: polymer electrolytes, ZrO2, ionic conductivity, FTIR

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Authors: Hiroyuki Aoki

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The physical properties of polymer materials are dependent on the conformation and molecular motion of a polymer chain. Therefore, the structure and dynamic behavior of the single polymer chain have been the most important concerns in the field of polymer physics. However, it has been impossible to directly observe the conformation of the single polymer chain in a bulk medium. In the current work, the novel techniques to study the conformation and dynamics of a single polymer chain are proposed. Since a fluorescence method is extremely sensitive, the fluorescence microscopy enables the direct detection of a single molecule. However, the structure of the polymer chain as large as 100 nm cannot be resolved by conventional fluorescence methods because of the diffraction limit of light. In order to observe the single chains, we developed the labeling method of polymer materials with a photo-switchable dye and the super-resolution microscopy. The real-space conformational analysis of single polymer chains with the spatial resolution of 15-20 nm was achieved. The super-resolution microscopy enables us to obtain the three-dimensional coordinates; therefore, we succeeded the conformational analysis in three dimensions. The direct observation by the nanometric optical microscopy would reveal the detailed information on the molecular processes in the various polymer systems.

Keywords: polymer materials, single molecule, super-resolution techniques, conformation

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Authors: Udayakumar Vee, Franck Quero

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Zwitterionic polymers generally have been viewed as a new class of antimicrobial and non-fouling materials. They offer a broad versatility for chemical modification and hence great freedom for accurate molecular design, which bear an equimolar number of homogenously distributed anionic and cationic groups along their polymer chains. This study explores the effectiveness of the auxetic zwitterion carboxylate/sulfonate hydrogel in the diabetic-induced mouse model. A series of silver metal-doped auxetic zwitterion carboxylate/sulfonate/vinylaniline copolymer hydrogels is designed via a 3D printer. Zwitterion monomers have been characterized by FT-IR and NMR techniques. The effect of changing the monomers and different loading ratios of Ag over zwitterion on the final hydrogel materials' antimicrobial properties and biocompatibility will be investigated in detail. The synthesized auxetic hydrogel has been characterized using a wide range of techniques to help establish the relationship between molecular level and macroscopic properties of these materials, including mechanical and antibacterial and biocompatibility and wound healing ability. This work's comparative studies and results provide new insights and guide us in choosing a better auxetic structured material for a broad spectrum of wound healing applications in the animal model. We expect this approach to provide a versatile and robust platform for biomaterial design that could lead to promising treatments for wound healing applications.

Keywords: auxetic, zwitterion, carboxylate, sulfonate, polymer, wound healing

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Authors: Sukruthai Sapniwat, Falan Srisuriyachai

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Polymer Flooding is one of the most well-known methods in Enhanced Oil Recovery (EOR) technology which can be implemented after either primary or secondary recovery, resulting in favorable conditions for the displacement mechanism in order to lower the residual oil in the reservoir. Polymer substances can lower the mobility ratio of the whole process by increasing the viscosity of injected water. Therefore, polymer flooding can increase volumetric sweep efficiency, which leads to a better recovery factor. Moreover, polymer adsorption onto rock surface can help decrease reservoir permeability contrast with high heterogeneity. Due to the reduction of the absolute permeability, effective permeability to water, representing flow ability of the injected fluid, is also reduced. Once polymer is adsorbed onto rock surface, polymer molecule can be desorbed when different fluids are injected. This study is performed to evaluate the effects of the adsorption and desorption process of polymer solutions to yield benefits on the oil recovery mechanism. A reservoir model is constructed by reservoir simulation program called STAR® commercialized by the Computer Modeling Group (CMG). Various polymer concentrations, starting times of polymer flooding process and polymer injection rates were evaluated with selected values of polymer desorption degrees including 0, 25, 50, 75 and 100%. The higher the value, the more adsorbed polymer molecules to return back to flowing fluid. According to the results, polymer desorption lowers polymer consumption, especially at low concentrations. Furthermore, starting time of polymer flooding and injection rate affect the oil production. The results show that waterflooding followed by earlier polymer flooding can increase the oil recovery factor while the higher injection rate also enhances the recovery. Polymer concentration is related to polymer consumption due to the two main benefits of polymer flooding control described above. Therefore, polymer slug size should be optimized based on polymer concentration. Polymer desorption causes polymer re-employment that is previously adsorbed onto rock surface, resulting in an increase of sweep efficiency in the further period of polymer flooding process. Even though waterflooding supports polymer injectivity, water cut at the producer can prematurely terminate the oil production. The injection rate decreases polymer adsorption due to decreased retention time of polymer flooding process.

Keywords: enhanced oil recovery technology, polymer adsorption and desorption, polymer flooding, reservoir simulation

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Authors: Anjan Sil, Rajni Sharma, Subrata Ray

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The effect of carbon nanofibers (CNFs) on the electrical properties of Poly(vinylidene fluoride-hexafluoropropylene) (P(VdF-HFP)) based gel polymer electrolytes has been investigated in the present work. The length and diameter ranges of CNFs used in the present work are 5-50 µm and 200-600 nm, respectively. The nanocomposite gel polymer electrolytes have been synthesized by solution casting technique with varying CNFs content in terms of weight percentage. Electrochemical impedance analysis demonstrates that the reinforcement of carbon nanofibers significantly enhances the ionic conductivity of the polymer electrolyte. The decrease of crystallinity of P(VdF-HFP) due the addition of CNFs has been confirmed by X-ray diffraction (XRD). The interaction of CNFs with various constituents of nanocomposite gel polymer electrolytes has been assessed by Fourier Transform Infrared (FTIR) spectroscopy. Moreover, CNFs added gel polymer electrolytes offer superior thermal stability as compared to that of CNFs free electrolytes as confirmed by Thermogravimetric analysis (TGA).

Keywords: polymer electrolytes, CNFs, ionic conductivity, TGA

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Authors: M. Sarikanat, E. Akar, I. Şen, Y. Seki, O. C. Yılmaz, B. O. Gürses, L. Cetin, O. Özdemir, K. Sever

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Chitosan is a natural, nontoxic, polyelectrolyte, cheap polymer. In this study, chitosan based electroactive polymer (CBEAP) was fabricated. Electroactive properties of this polymer were investigated at different voltages. It exhibited excellent tip displacement at low voltages (1, 3, 5, 7 V). Tip displacement was increased as the applied voltage increased. Best tip displacement was investigated as 28 mm at 5V. Characterization of CBEAP was investigated by scanning electron microscope, X-ray diffraction and tensile testing. CBEAP exhibited desired electroactive properties at low voltages. It is suitable for using in artificial muscle and various robotic applications.

Keywords: chitosan, electroactive polymer, electroactive properties

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Authors: Maha A. Younus, Dhefaf H. Badri, Maha A. Al Abayaji, Taha M. Salih

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Polymer metal complexes of poly vinyl alcohol and Cu (II), Ni (II), Mn (II) and Co (III) were prepared from the reaction of PVA with three different percentages of urea. The compound was characterized by fourier transform infrared spectrometry (FTIR) analysis and differential scanning calorimetric (DSC) Analysis. It has been established that the polymer and its metal complexes showed good activities against nine pathogenic bacteria (Escherichia coli, Klebsiellapneumonae, Staphylococcusaureus, Staphylococcus Albus, Salmonella Typhoid, Pseudomonas Aeruginosa, Shigella Dysentery, Proteus Morgani, Brucella Militensis). The polymer metal complexes show activity higher than that of the free polymer. The increasing activities were in the order (polymer < pol-Mn< pol-Co < pol-Ni ˂ pol-Cu). The ability of these compounds to show antimicrobial properties suggests that they can be further evaluated for medicinal and/or environmental applications.

Keywords: antimicrobial activity, PVA, polymer-metal complex, urea

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Authors: Panupong Lohrattanarungrot, Falan Srisuriyachai

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Polymer flooding is a well-known technique used for controlling mobility ratio in heterogeneous reservoirs, leading to improvement of sweep efficiency as well as wellbore profile. However, low injectivity of viscous polymer solution attenuates oil recovery rate and consecutively adds extra operating cost. An attempt of this study is to improve injectivity of polymer solution while maintaining recovery factor, enhancing effectiveness of polymer flooding method. This study is performed by using reservoir simulation program to modify conventional single polymer slug into sequential polymer flooding, emphasizing on increasing of injectivity and also reduction of polymer amount. Selection of operating conditions for single slug polymer including pre-injected water, polymer concentration and polymer slug size is firstly performed for a layered-heterogeneous reservoir with Lorenz coefficient (Lk) of 0.32. A selected single slug polymer flooding scheme is modified into sequential polymer flooding with reduction of polymer concentration in two different modes: Constant polymer mass and reduction of polymer mass. Effects of Residual Resistance Factor (RRF) is also evaluated. From simulation results, it is observed that first polymer slug with the highest concentration has the main function to buffer between displacing phase and reservoir oil. Moreover, part of polymer from this slug is also sacrificed for adsorption. Reduction of polymer concentration in the following slug prevents bypassing due to unfavorable mobility ratio. At the same time, following slugs with lower viscosity can be injected easily through formation, improving injectivity of the whole process. A sequential polymer flooding with reduction of polymer mass shows great benefit by reducing total production time and amount of polymer consumed up to 10% without any downside effect. The only advantage of using constant polymer mass is slightly increment of recovery factor (up to 1.4%) while total production time is almost the same. Increasing of residual resistance factor of polymer solution yields a benefit on mobility control by reducing effective permeability to water. Nevertheless, higher adsorption results in low injectivity, extending total production time. Modifying single polymer slug into sequence of reduced polymer concentration yields major benefits on reducing production time as well as polymer mass. With certain design of polymer flooding scheme, recovery factor can even be further increased. This study shows that application of sequential polymer flooding can be certainly applied to reservoir with high value of heterogeneity since it requires nothing complex for real implementation but just a proper design of polymer slug size and concentration.

Keywords: polymer flooding, sequential, heterogeneous reservoir, residual resistance factor

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Authors: Sy-Wei Lo, Chi-Heng Yu

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A new design of aerostatic thrust bearing is proposed for high static stiffness. The bearing body, which is mead of polymer covered with metallic membrane, is held by a circular ring. Such a support helps form a concave air gap to grasp the air pressure. The polymer body, which can be made rapidly by either injection or molding is able to provide extra damping under dynamic loading. The smooth membrane not only serves as the bearing surface but also protects the polymer body. The restrictor is a capillary inside a silicone tube. It can passively compensate the variation of load by expanding the capillary diameter for more air flux. In the present example, the stiffness soars from 15.85 N/µm of typical bearing to 349.85 N/µm at bearing elevation 9.5 µm; meanwhile the load capacity also enhances from 346.86 N to 704.18 N.

Keywords: aerostatic, bearing, polymer, static stiffness

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Authors: Moulay Driss Mellaoui, Abdallah Imjjad, Rachid Boutiddar, Haydar Mohammad-Salim, Nivedita Acharjee, Hassan Bourzi, Souad El Issami, Khalid Abbiche, Hanane Zejli

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We have investigated the underlying molecular processes involved in the [3+2] cycloaddition (32CA) reactions between N-methyl-C-(2-furyl) nitrone and three acetylene derivatives: 4b, 5b, and 6b. For this investigation, we utilized molecular electron density theory (MEDT) and density functional theory (DFT) methods at the B3LYP-D3/6 31G (d) computational level. These 32CA reactions, which exhibit a zwitterionic (zw-type) nature, proceed through a one-step mechanism with activation enthalpies ranging from 8.80 to 14.37 kcal mol−1 in acetonitrile and ethanol solvents. When the nitrone reacts with phenyl methyl propiolate (4b), two regioisomeric pathways lead to the formation of two products: P1,5-4b and P1,4-4b. On the other hand, when the nitrone reacts with dimethyl acetylene dicarboxylate (5b) and acetylene dicarboxylic acid (but-2-ynedioic acid) (6b), it results in the formation of a single product. Through topological analysis, we can categorize the nitrone as a zwitterionic three-atom component (TAC). Furthermore, the analysis of conceptual density functional theory (CDFT) indices classifies the 32CA reactions of the nitrone with 4b, 5b, and 6b as forward electron density flux (FEDF) reactions. The study of bond evolution theory (BET) reveals that the formation of new C-C and C-O covalent bonds does not initiate in the transition states, as the intermediate stages of these reactions display pseudoradical centers of the atoms already involved in bonding.

Keywords: 4-isoxazoline, DFT/B3LYP-D3, regioselectivity, cycloaddition reaction, MEDT, ELF

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Authors: Opeyemi Elujulo, Aderonke Okoya, Kehinde Awokoya

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Molecularly imprinted polymers (MIP) for the adsorption of pyridine (PYD) was obtained from PYD (the template), styrene (the functional monomer), divinyl benzene (the crosslinker), benzoyl peroxide (the initiator), and water (the porogen). When the template was removed by solvent extraction, imprinted binding sites were left in the polymer material that are capable of selectively rebinding the target molecule. The material was characterized by Fourier transform infrared spectroscopy and differential scanning calorimetry. Batch adsorption experiments were performed to study the adsorption of the material in terms of adsorption kinetics, isotherms, and thermodynamic parameters. The results showed that the imprinted polymer exhibited higher affinity for PYD compared to non-imprinted polymer (NIP).

Keywords: molecularly imprinted polymer, bulk polymerization, environmental pollutant, adsorption

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Authors: Khaled Benyounes, Abderrahmane Mellak

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The rheology of aqueous solutions of polyelectrolyte (polyanionic cellulose, PAC) at high molecular weight was investigated using a controlled stress rheometer. Several rheological measurements; viscosity measurements, creep compliance tests at a constant low shear stress and oscillation experiments have been performed. The concentrations ranged by weight from 0.01 to 2.5% of PAC. It was found that the aqueous solutions of PAC do not exhibit a yield stress, the flow curves of PAC over a wide range of shear rate (0 to 1000 s-1) could be described by the cross model and the Williamson models. The critical concentrations of polymer c* and c** have been estimated. The dynamic moduli, i.e., storage modulus (G’) and loss modulus (G’’) of the polymer have been determined at frequency sweep from 0.01 to 10 Hz. At polymer concentration above 1%, the modulus G’ is superior to G’’. The relationships between the dynamic modulus and concentration of polymer have been established. The creep-recovery experiments demonstrated that polymer solutions show important viscoelastic properties of system water-PAC when the concentration of the polymer increases.

Keywords: polyanionic cellulose, viscosity, creep, oscillation, cross model

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Authors: Hiroyuki Aoki

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The glass transition phenomenon has been extensively studied for a long time. The glass transition of polymer materials is assigned to the transition of the dynamics of the chain backbone segment. However, the detailed mechanism of the transition behavior of the segmental motion is still unclear. In the current work, the single molecule detection technique was employed to reveal the trajectory of the molecular motion of the single polymer chain. The center segment of poly(butyl methacrylate) chain was labeled by a perylenediimide dye molecule and observed by a highly sensitive fluorescence microscope in a defocus condition. The translational and rotational diffusion of the center segment in a single polymer chain was analyzed near the glass transition temperature. The direct observation of the individual polymer chains revealed the intermittent behavior of the segmental motion, indicating the spatial inhomogeneity.

Keywords: glass transition, molecular motion, polymer materials, single molecule

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Authors: M. Grandcolas, N. Rival, H. Bu, S. Jahren, R. Schmid, H. Johnsen

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The concept of an autonomic self-healing material, where initiation of repair is integrated to the material, is now being considered for engineering applications and is a hot topic in the literature. Among several concepts/techniques, two are most interesting: i) Capsules: Integration of microcapsules in or at the surface of coatings or fibre-like structures has recently gained much attention. Upon damage-induced cracking, the microcapsules are broken by the propagating crack fronts resulting in a release of an active chemical (healing agent) by capillary action, subsequently repairing and avoiding further crack growth. ii) Self-healing polymers: Interestingly, the introduction of dynamic covalent bonds into polymer networks has also recently been used as a powerful approach towards the design of various intrinsically self-healing polymer systems. The idea behind this is to reconnect the chemical crosslinks which are broken when a material fractures, restoring the integrity of the material and thereby prolonging its lifetime. We propose here to integrate both self-healing concepts (capsules, self-healing polymers) in electrospun fibres and coatings. Different capsule preparation approaches have been investigated in SINTEF. The most advanced method to produce capsules is based on emulsification to create a water-in-oil emulsion before polymerisation. The healing agent is a polyurethane-based dispersion that was encapsulated in shell materials consisting of urea-benzaldehyde resins. Results showed the successful preparation of microcapsules and release of the agent when capsules break. Since capsules are produced in water-in-oil systems we mainly investigated organic solvent based coatings while a major challenge resides in the incorporation of capsules into water-based coatings. We also focused on developing more robust microcapsules to prevent premature rupture of the capsules. The capsules have been characterized in terms of size, and encapsulation and release might be visualized by incorporating fluorescent dyes and examine the capsules by microscopy techniques. Alternatively, electrospinning is an innovative technique that has attracted enormous attention due to unique properties of the produced nano-to-micro fibers, ease of fabrication and functionalization, and versatility in controlling parameters. Especially roll-to-roll electrospinning is a unique method which has been used in industry to produce nanofibers continuously. Electrospun nanofibers can usually reach a diameter down to 100 nm, depending on the polymer used, which is of interest for the concept with self-healing polymer systems. In this work, we proved the feasibility of fabrication of POSS-based (POSS: polyhedral oligomeric silsesquioxanes, tradename FunzioNano™) nanofibers via electrospinning. Two different formulations based on aqueous or organic solvents have shown nanofibres with a diameter between 200 – 450nm with low defects. The addition of FunzioNano™ in the polymer blend also showed enhanced properties in term of wettability, promising for e.g. membrane technology. The self-healing polymer systems developed are here POSS-based materials synthesized to develop dynamic soft brushes.

Keywords: capsules, coatings, electrospinning, fibers

Procedia PDF Downloads 238

Authors: Olesia Mikhailova, Pavel Rovnaník

Abstract:

In the present work, metakaolin-based geopolymer including different polymer admixtures was studied. Different types of commercial polymer admixtures VINNAPAS^® and polyethylene glycol of different relative molecular weight were used as polymer admixtures. The main objective of this work is to investigate the influence of different types of admixtures on the properties of metakaolin-based geopolymer mortars considering their different dosage. Mechanical properties, such as flexural and compressive strength were experimentally determined. Also, study of the microstructure of selected specimens by using a scanning electron microscope was performed. The results showed that the specimen with addition of 1.5% of VINNAPAS^® 7016 F and 10% of polyethylene glycol 400 achieved maximum mechanical properties.

Keywords: geopolymer, mechanical properties, metakaolin, microstructure, polymer admixtures, porosity

Procedia PDF Downloads 201

Authors: Jian Zheng

Abstract:

Three-dimensional (3D) network structure has been recognized as an effective approach to enhance the mechanical and thermal conductive properties of polymeric composites. However, it has not been applied in energetic materials. In this work, a fluoropolymer based composite with vertically oriented and interconnected 3D graphite network was fabricated for polymer bonded explosives (PBXs). Here, the graphite and graphene oxide platelets were mixed, and self-assembled via rapid freezing and using crystallized ice as the template. The 3D structure was finally obtained by freezing-dry and infiltrating with the polymer. With the increasing of filler fraction and cooling rate, the thermal conductivity of the polymer composite was significantly improved to 2.15 W m⁻¹ K⁻¹ by 1094% than that of pure polymer. Moreover, the mechanical properties, such as tensile strength and elastic modulus, were enhanced by 82% and 310%, respectively, when the highly ordered structure was embedded in the polymer. We attribute the increased thermal and mechanical properties to this 3D network, which is beneficial to the effective heat conduction and force transfer. This study supports a desirable way to fabricate the strong and thermal conductive fluoropolymer composites used for the high-performance polymer bonded explosives (PBXs).

Keywords: mechanical properties, oriented network, graphite polymer composite, thermal conductivity

Procedia PDF Downloads 130

Authors: Santiranjan Shannigrahi, Mohit Sharma, Ivan Tan Chee Kiang, Yong Anna Marie

Abstract:

Polymer-ceramics composites are gaining importance due to their high specific strength, corrosion resistance, and high mechanical properties, as well as low cost. As a result, polymer composites are suitable for various industrial applications, like automobiles, aerospace, and biomedical areas. The present work comprises the development of polymer-ceramic composite films and is tested for the harsh environment including weatherability and UV barrier property. The polymer composite films are kept in weather chamber for a fixed period of time followed by tested for their physical, mechanical and chemical properties. The composite films are fabricated using compounding followed by hot pressing. UV-visible spectroscopy results reveal that the pure polymer polyethylene (PE) films are transparent in the visible range and do not absorb UV. However, polymer ceramic composite films start absorbing UV completely even at very low filler loading amount of 5 wt.%. The changes in tensile properties of the various composite films before and after UV illuminations for 40 hrs at 60 degC are analyzed. The tensile strength of neat PE film has been observed 8% reduction, whereas the remarkable increase in tensile strength has been observed (18% improvement for 10 wt. % filled composites films). The UV exposure leads to strengthen the crosslinking among PE polymer chains in the filled composite films, which contributes towards the incremented tensile strength properties.

Keywords: polymer ceramic composite, processing, harsh environment, mechanical properties

Procedia PDF Downloads 359

Authors: Chung-Chih Lin, Chien-Liang Wu

Abstract:

The detection of the polymer melt state during manufacture process is regarded as an efficient way to control the molded part quality in advance. Online monitoring rheological property of polymer melt during processing procedure provides an approach to understand the melt state immediately. Rheological property reflects the polymer melt state at different processing parameters and is very important in injection molding process especially. An approach that demonstrates how to calculate rheological property of polymer melt through in-process measurement, using injection molding as an example, is proposed in this study. The system consists of two sensors and a data acquisition module can process the measured data, which are used for the calculation of rheological properties of polymer melt. The rheological properties of polymer melt discussed in this study include shear rate and viscosity which are investigated with respect to injection speed and melt temperature. The results show that the effect of injection speed on the rheological properties is apparent, especially for high melt temperature and should be considered for precision molding process.

Keywords: injection molding, melt viscosity, shear rate, monitoring

Procedia PDF Downloads 354

Authors: Ling Dai

Abstract:

Surface-sensing devices such as atomic force microscope have been widely used to characterize the surface structure and properties of nanoscale polymer films. However, using molecular dynamics simulations, we show that there is intrinsic and unavoidable inelastic deformation at polymer surfaces induced by the sensing tip. For linear chain polymers like perfluoropolyether, such tip-induced deformation derives from the differences in the atomic interactions which are atomic specie-based Van der Waals interactions, and resulting in atomic shuffling and causing inelastic alternation in both molecular structures and mechanical properties at the regions of the polymer surface. For those aromatic chain polymers like epoxy, the intrinsic deformation is depicted as the intra-chain rotation of aromatic rings and kinking of linear atomic connections. The present work highlights the need to reinterpret the data obtained from surface-sensing tests by considering this intrinsic inelastic deformation occurring at polymer surfaces.

Keywords: polymer, surface, nano, molecular dynamics

Procedia PDF Downloads 330

Authors: Vahidullah Tac, Ercan Gurses

Abstract:

There have been numerous attempts at modelling carbon nanotube – polymer composites micromechanically in recent years, albeit to limited success. One of the major setbacks of the models used in the scientific community is the lack of regard to the different phases present in a nanocomposite. We employ a multi-phase micromechanical model that allows functionally grading certain phases to determine the mechanical properties of nanocomposites. The model has four distinct phases; the nanotube, the interface between the nanotube and polymer, the interphase, and the bulk matrix. Among the four phases, the interphase is functionally graded such that its moduli gradually decrease from some predetermined values to those of the bulk polymer. We find that the interface plays little role in stiffening/softening of the polymer per se , but instead, it is responsible for load transfer between the polymer and the carbon nanotube. Our results indicate that the carbon nanotube, as well as the interphase, have significant roles in stiffening the composite. The results are then compared to experimental findings and the interphase is tuned accordingly.

Keywords: carbon nanotube, composite, interphase, micromechanical modeling

Procedia PDF Downloads 132